JP5501716B2 - Cyanine compound, optical recording material and color correction material using the compound - Google Patents

Description

  The present invention relates to a novel cyanine compound, an optical recording material containing the cyanine compound, and a color correction material. The cyanine compound is an optical element or the like, in particular, an optical recording medium for recording by applying information as an information pattern by a laser or the like, and more specifically, a high density by a laser having a wavelength in the ultraviolet and visible regions and a low energy laser or the like. It is useful as an optical recording material used for an optical recording layer of an optical recording medium capable of optical recording and reproduction. The cyanine compound is particularly useful as a color correction material (light absorber) to be contained in an optical filter for an image display device.

  Optical recording media are generally widespread because they have excellent characteristics such as a large recording capacity and non-contact recording or reproduction. In a write-once optical disc such as WORM, CD-R, DVD ± R, etc., the laser is focused on a very small area of the recording layer and recorded by changing the properties of the optical recording layer. Playback is performed by the difference.

  At present, in the above optical disk, the wavelength of the semiconductor laser used for recording and reproduction is 750 to 830 nm for CD-R and 620 to 690 nm for DVD-R, but 380 to 420 nm for BD-R. It is used.

  In an optical recording medium for short wavelength recording light, various compounds are used for forming an optical recording layer. For example, the following Patent Document 1 reports a hemicyanine dye, the following Patent Document 2 reports a trimethine compound, the following Patent Document 3 reports a porphyrin compound, and the following Patent Document 4 describes: Have reported monomethine cyanine dyes having a specific structure. However, these compounds have a problem that the optical recording material used for forming the optical recording layer does not necessarily have an absorption wavelength characteristic suitable or does not have an excellent recording characteristic. . Moreover, although the following patent document 5 disclosed the monomethine cyanine dye which improved these problems, it was not necessarily satisfactory in various physical properties.

  On the other hand, the image display device displays a color image with a combination of light of the three primary colors of red, blue, and green, but the display quality such as 550 to 620 nm between green and red is used for the light for displaying the color image. In addition, light that causes a decrease in the infrared remote control 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 500 nm and 540 to 560 nm. It is also necessary to absorb light having a wavelength of 300 to 390 nm as an ultraviolet absorber. Therefore, an optical filter containing a color correction material (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 450 to 620 nm has been demanded in order to ensure 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 6 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, and the following Patent Document 8 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 9 below discloses an organic soluble cationic dye having a fluorinated alkylsulfonyl counter ion, but does not describe or suggest that the cationic dye can be used in an optical filter.

JP 2001-342365 A JP 2004-98542 A JP-A-2005-59601 International Publication WO01 / 044374 International Publication No. WO2007 / 114073

JP 2003-57437 A JP 2004-310072 A JP 2003-57436 A JP-A-8-253705

  Accordingly, an object of the present invention is to provide a novel compound having optical characteristics suitable for the formation of an optical recording layer of an optical recording medium particularly for short wavelength recording light, and an optical recording material and an optical recording medium using the compound. There is to do.

  Another object of the present invention is novel, particularly suitable for color correction materials (light absorbers) that have steep light absorption particularly in the wavelength region of 450 to 620 nm and that are used in optical filters for image display devices. And a color correction material, a film-forming composition, and an optical filter using the compound.

  As a result of repeated studies, the present inventors have found that a cyanine compound having a specific molecular structure has absorption wavelength characteristics suitable for forming an optical recording layer of an optical recording medium for short-wavelength recording light. It has a sharp light absorption in the wavelength region, and it is found that the image characteristics of the image display device can be remarkably improved as compared with an optical filter using a conventional light absorber, and by using this, the above-mentioned problem It was found that it can be solved.

  The present invention has been made based on the above findings, and has achieved the above object by providing a cyanine compound represented by the following general formula (I).

（式中、Ｒ¹は下記一般式（II）で表される基を表し、
Ｒ²は炭素原子数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、下記一般式（II）で表される基又は下記一般式（III）で表される基を表し、
Ｘは酸素原子、硫黄原子、セレン原子又はＣＲ³ Ｒ ⁴ を表し、
Ｒ³ 及びＲ ⁴ は、それぞれ独立に、炭素原子数１〜２０のアルキル基又は下記一般式（II）で表される基を表し、Ｒ ³ とＲ⁴は、それぞれ連結して３〜６員環の脂環基を形成してもよい。
Ｙ ¹ 及びＹ ² は、それぞれ独立に、炭素原子数１〜２０のアルキル基、下記一般式（II）で表される基又は下記一般式（III）で表される基を表し、
Ｚ¹及びＺ²は、それぞれ独立に、炭素原子数１〜１０のアルキル基、ニトロ基、シアノ基、ハロゲン原子、炭素原子数１〜８の炭化水素基を有するスルホニル基又は炭素原子数１〜８のアルキル基を有するジアルキルアミノ基を表し、該置換基の水素原子はハロゲン原子で置換されてもよく、該置換基のメチレン基は−Ｏ−で中断されてもよく、複数のＺ¹同士、Ｚ²同士は結合して環構造を形成していてもよく、
Ｅは水素原子、ハロゲン原子、シアノ基又は炭素原子数１〜１０のアルキル基を表し、
ａ及びｂは、それぞれ独立に、０〜４の整数を表し、
Ａｎ^q-はｑ価の陰イオンを表し、
ｑは１又は２を表し、
ｐは電荷を中性に保つ係数を表す。）

(In the formula, R ¹ represents a group represented by the following general formula (II),
R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a group represented by the following general formula (II), or the following general formula ( III) represents a group represented by
X represents an oxygen atom, a sulfur atom, a selenium atom or a CR ³ R ^4,
R ³ and R ⁴ each independently represent a group represented by the alkyl group or the following formula carbon atoms 1 to 20 (II), R ³ and R ^4, 3-6 membered coupled respectively A ring alicyclic group may be formed.
Y ¹ and Y ² each independently represent an alkyl group having 1 to 20 carbon atoms, a group represented by the following general formula (II) or a group represented by the following general formula (III),
Z ¹ and Z ² each independently represent an alkyl group having 1 to 10 carbon atoms, nitro group, cyano group, C androgenic atom, a sulfonyl group or the number of carbon atoms having a hydrocarbon group having 1 to 8 carbon atoms Represents a dialkylamino group having 1 to 8 alkyl groups, the hydrogen atom of the substituent may be substituted with a halogen atom, the methylene group of the substituent may be interrupted with -O- , ¹ and Z ² may be bonded to each other to form a ring structure,
E represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 10 carbon atoms,
a and b each independently represents an integer of 0 to 4;
An ^q− represents a q-valent anion,
q represents 1 or 2,
p represents a coefficient for keeping the charge neutral. )

（式中、Ｚ³は炭素原子数１〜１０のアルキル基、ニトロ基又はハロゲン原子を表し、複数のＺ³同士は結合して環構造を形成していてもよく、
Ｑ¹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、
ｃは０〜４の整数である。）

(Wherein, Z ³ represents an alkyl group having 1 to 10 carbon atoms, represents nitro group or a halogen atom, Z ³ each other several may form a ring structure,
Q ¹ is to display the alkylene group having 1 to 8 carbon atoms which may have a direct bond or a substituent,
c is an integer of 0-4. )

（式中、Ｒ^a〜Ｒⁱは、水素原子を表し、
Ｑ ² 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−ＣＯ−で置換されてもよく、
Ｍ¹はＦｅを表す。）

(Wherein, R ^a to R ⁱ represents a water MotoHara child,
Q ² represents a direct bond or an alkylene group having 1 to 8 carbon atoms which may have a substituent,
A methylene group in the alkylene group - CO - may be substituted with,
M ¹ represents Fe . )

  The present invention also provides an indolenium compound represented by the following general formula (IV), which is a useful intermediate for producing the above cyanine compound.

（式中、Ｒ¹、Ｒ²、Ｅ、Ｙ¹、Ｚ¹、ａ、ｐ及びＡｎ^q-は、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , E, Y ¹ , Z ¹ , a, p and An ^q− are the same as those in the general formula (I).)

  The present invention also provides an optical recording material comprising at least one of the cyanine compounds used for forming the optical recording layer of an optical recording medium having an optical recording layer formed on a substrate.

  The present invention also provides an optical recording medium having an optical recording layer formed from the optical recording material on a substrate.

  The present invention also provides a color correction material comprising at least one of the above cyanine compounds.

  Moreover, this invention provides the composition for film formation formed by containing the said color correction material.

  Moreover, this invention provides the optical filter using the said composition for film formation.

  The present invention can provide a cyanine compound suitable for forming an optical recording layer of an optical recording medium and an optical recording material containing the cyanine compound. Since the cyanine compound of the present invention has a low decomposition point, its heat storage property is low, thermal interference is suppressed, and its light resistance is high, which is suitable for forming an optical recording layer of an optical recording medium.

  In addition, according to the present invention, a cyanine compound particularly suitable for a color correction material (light absorber) used for an optical filter for an image display device, and a color correction material, a film-forming composition and an optical material using the compound. A filter can be provided. Since the cyanine compound of the present invention has steep light absorption particularly in the wavelength region of 450 to 620 nm, the image characteristics of the image display device are remarkably improved by using the compound for an optical filter for the image display device. Can be made.

Hereinafter, the present invention will be described in detail based on preferred embodiments.
First, the cyanine compound of the present invention represented by the general formula (I) will be described.

Examples of the alkyl group in the general formula ^{(I), R 2, R} 3, R 4, R 5, 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, methoxyethoxyethoxy Ethyl, 3-methoxybut Examples of the aryl group having 6 to 30 carbon atoms include phenyl, naphthyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, and 3-isopropyl. Phenyl, 4-isopropylphenyl, 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-phenoxyethyl, - phenylthioethyl and the like, and as the arylalkyl group having 7 to 30 carbon atoms, benzyl, phenethyl, 2-phenylpropan-2-yl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, and the like. In addition, examples of the 3- to 6-membered alicyclic group that may be formed by connecting R ³ and R ⁴ include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

In the general formula (I), the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 20 carbon atoms, and the arylalkyl group having 7 to 20 carbon atoms represented by Z ¹ and Z ² are as follows: Among the groups exemplified in the description of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the arylalkyl group having 7 to 30 carbon atoms, those satisfying a predetermined number of carbon atoms are exemplified. It is done.

In the general formula (I), examples of the hydrocarbon group having 1 to 8 carbon atoms of the sulfonyl group or sulfinyl group represented by Z ¹ and Z ² include, for example, 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 Alkyl groups such as vinyl, 1-methylethen-1-yl, propen-1-yl, propen-2-yl, propen-3-yl, buten-1-yl, buten-2-yl, 2-methylpropene- Al, such as 3-yl, 1,1-dimethylethen-2-yl, 1,1-dimethylpropen-3-yl Kenyl group; phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butyl Aryl groups such as phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl; benzyl, Examples include aralkyl groups such as 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenethyl, 2-phenylpropan-2-yl, styryl, and the like, and an alkylamino group or dialkylamino represented by Z ¹ and Z ² Examples of the alkyl group having 1 to 8 carbon atoms in the group include the above-exemplified alkyl groups. Can be mentioned.

In the general formula (I), examples of the halogen atom represented by E, Z ¹ and Z ² include fluorine, chlorine, bromine and iodine.

In the general formula (I), the hydrogen atom of the group represented by Z ¹ and Z ² may be substituted with a halogen atom, and the methylene group of the group represented by Z ¹ and Z ² is —O—. , -CO-, -OCO- or -COO- may be interrupted, the substitution position of the halogen atom and the interruption position of -O-, -CO-, -OCO- or -COO- are arbitrary,- Also included are those in which O-, -CO-, -OCO- or -COO- is directly bonded to the ring. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

In the general formula (I), examples of the ring structure formed by combining the substituents of Z ¹ and Z ² include cyclopentane ring, cyclohexane ring, cyclopentene ring, benzene ring, piperidine ring, morpholine ring, lactone Examples thereof include 5- to 7-membered rings such as rings and lactam rings, and condensed rings such as naphthalene rings and anthracene rings.

In the general formula (I), examples of the anion represented by An ^q- include, for example, a monovalent halogen anion such as a chlorine anion, a bromine anion, an iodine anion, and a fluorine anion; Inorganic anions such as chlorate anion, chlorate anion, thiocyanate anion, hexafluorophosphate anion, antimony hexafluoride anion, boron tetrafluoride anion; benzenesulfonate anion, toluene Sulfonic acid anion, trifluoromethanesulfonic acid anion, diphenylamine-4-sulfonic acid anion, 2-amino-4-methyl-5-chlorobenzenesulfonic acid anion, 2-amino-5-nitrobenzenesulfonic acid anion, special Organic sulfonate anions such as sulfonate anions described in Kaikai 2004-53799; octyl phosphate Ions, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion, 2,2′-methylenebis (4,6-di-t-butylphenyl) phosphonate anion, etc. Organic phosphate anions, bistrifluoromethylsulfonylimide anion, bisperfluorobutanesulfonylimide anion, perfluoro-4-ethylcyclohexanesulfonate anion, tetrakis (pentafluorophenyl) borate anion, etc. As a bivalent thing, a benzene disulfonic acid anion, a naphthalene disulfonic acid anion, 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. Metallocene compound anions such as luteocene can also be used as necessary.

  Examples of the quencher anion include the following general formula (1) or (2), or the following chemical formulas (3), (4), (5), (6), (7), (8), ( 9), (10), (11) or (12) a quencher anion (hereinafter, quencher anion (1), (2), (3), (4), (5), ( 6), (7), (8), (9), (10), (11) or (12)), 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, JP-A-11-208118, JP-A 2000-168237. Publication, JP 2002-201373, JP 002-206061, JP 2005-297407 and JP Kokoku 7-96334 and JP-quencher anions such as described in WO 98/29257 No. and the like.

（式中、Ｍ²及びＭ³は、上記一般式（III）におけるＭ¹と同じであり、Ｒ¹¹及びＲ¹²は、それぞれ独立に、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ホリノ基を表し、ｓ及びｔは、それぞれ独立に、０〜４の整数を表す。また、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶は、それぞれ独立に、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 ² and M ³ are the same as M ¹ in the general formula (III), and R ¹¹ and R ¹² are each independently a halogen atom, an alkyl group having 1 to 8 carbon atoms, carbon Represents an aryl group having 6 to 30 atoms or —SO ₂ —G group, and 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; S and t each independently represents an integer of 0 to 4. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently an alkyl group, an alkylphenyl group, an alkoxyphenyl group or a halogen atom. Represents a substituted phenyl group.)

In the general formula (II), an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a halogen atom, and a sulfonyl group represented by Z ³ Examples of the alkyl group having 1 to 8 carbon atoms that the sulfinyl group, alkylamino group and dialkylamino group have include those exemplified in the description of the general formula (I).

In the general formula (II), the hydrogen atom of the group represented by Z ³ may be substituted with a halogen atom, and the methylene group of the group represented by Z ³ is —O—, —CO—, — It may be interrupted by OCO- or -COO-, the substitution position of the halogen atom and the interruption position of -O-, -CO-, -OCO- or -COO- are arbitrary, -O-, -CO- , -OCO- or -COO- is directly bonded to the ring. Examples of the halogen atom include fluorine, chlorine, bromine, iodine and the like.

In the general formula (III), examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{a to} R ⁱ include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, and isobutyl. Examples of the group in which the methylene group in the alkyl group is substituted with -O- include methoxy, ethoxy, propoxy, isopropoxy, methoxymethyl, ethoxymethyl, 2-methoxyethyl and the like. Examples of the group in which the methylene group in the group is interrupted by -CO- include acetyl, 1-carbonylethyl, acetylmethyl, 1-carbonylpropyl, 2-oxobutyl, 2-acetylethyl, 1-carbonylisopropyl and the like.

In the general formula (III), examples of the alkylene group having 1 to 8 carbon atoms which may have a substituent represented by Q ² include methylene, ethylene, propylene, methylethylene, butylene, and 1-methyl. Propylene, 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, and the methylene group in the alkylene group is -O-, -S-, -CO -, - COO -, - OCO -, - SO 2 -, - NH -, - CONH -, - NHCO -, - N = CH- or -CH = CH Examples of the group substituted with methyleneoxy, ethyleneoxy, oxymethylene, thiomethylene, carbonylmethylene, carbonyloxymethylene, methylenecarbonyloxy, sulfonylmethylene, aminomethylene, acetylamino, ethylenecarboxyamide, ethaneimidoyl, ethenylene And propenylene. The metal atom represented by M ¹ is Fe, Co, Ni, Ti, Cu, Zn, Zr, Cr, Mo, Os, Mn, Ru, Sn, Pd, Rh, Pt, or Ir.

Among the cyanine compounds of the present invention, in the above general formula (I), a compound in which R ² is an alkyl group having 1 to 10 carbon atoms; a compound in which X is an oxygen atom or a sulfur atom; Y ² is 1 carbon atom A compound in which E is a hydrogen atom; a compound in which Q ¹ is a direct bond or an alkylene group having 1 to 8 carbon atoms is preferable because the production cost is low and the molar extinction coefficient is large. Further, in the above general formula (I), a compound in which a is 0; a compound in which the ring formed by Z ¹ is a benzene ring can be produced easily and has appropriate light absorption characteristics as an optical recording material. preferable.

  Preferable specific examples of the cyanine compound of the present invention include the following compounds I-1 to I-42. In the following examples, cyanine cations without anions are shown. In the cyanine compound of the present invention, the methine chain may have a resonance structure.

The groups represented by R ¹ and R ² are bonded to the cyanine compound of the present invention represented by the general formula (I) and the indolenium compound of the present invention represented by the general formula (IV) described later. There may be optical isomers such as enantiomers, diastereomers, and racemates with chiral centers at asymmetric atoms, but any of these optical isomers may be isolated and used as a mixture thereof. It may be used.

  The cyanine compound of the present invention represented by the above general formula (I) is not limited by the production method thereof. For example, as shown in the following reaction formula, the cyanine compound of the present invention represented by the following general formula (IV) is used. It can be produced by reacting an indolenium compound and an azolium compound in the presence of a base.

（式中、Ｒ¹、Ｒ²、Ｘ、Ｅ、Ｙ¹、Ｙ²、Ｚ¹、Ｚ²、ａ、ｂ、ｐ及びＡｎ^q-は、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , X, E, Y ¹ , Y ² , Z ¹ , Z ² , a, b, p and An ^q− are the same as those in the general formula (I).)

  The cyanine compound of the present invention is suitably used as an optical element such as an optical recording material and an optical filter described later, as well as synthetic intermediates such as pharmaceuticals, agricultural chemicals, fragrances, and dyes, or various polymer raw materials such as various functional materials, pigments Sensitization type solar cell, photoelectrochemical cell, nonlinear optical device, electrochromic display, hologram, organic semiconductor, organic EL, silver halide photographic material, photosensitizer, printing ink, inkjet, electrophotographic color toner, makeup It is used for coloring materials such as paints, plastics, dyes for proteins, and luminescent dyes for substance detection. However, the present invention is not limited by these applications.

Next, the indolenium compound of the present invention represented by the general formula (IV) will be described.
The indolenium compound of the present invention represented by the above general formula (IV) is a useful intermediate for producing the cyanine compound of the present invention represented by the above general formula (I). As the intermediate, an indolenium compound represented by the following general formula (V), which is an equivalent thereof, can be used in addition to the indolenium compound represented by the above general formula (IV).

（式中、Ｒ¹、Ｒ²、Ｅ、Ｙ¹、Ｚ¹、ａ及びｐは、上記一般式（Ｉ）と同じである。）

(In the formula, R ¹ , R ² , E, Y ¹ , Z ¹ , a and p are the same as those in the general formula (I).)

  Moreover, the following compound IV-1 to compound IV-29 are mentioned as a preferable specific example of the indolenium compound of this invention. In the following examples, cyanine cations without anions are shown.

Among the indolenium compounds of the present invention, in the above general formula (IV), R ² is an alkyl group having 1 to 10 carbon atoms; E is a hydrogen atom; Q ¹ in the above general formula (II) Is a direct bond or an alkylene group having 1 to 8 carbon atoms, and is preferable because the production cost is low and the molar extinction coefficient of a cyanine compound produced using the compound as an intermediate is large. ), A compound in which the ring formed by Z ¹ is a benzene ring is more preferable because it can be easily produced and has appropriate light absorption characteristics as an optical recording material.

  The indolenium compound of the present invention represented by the above general formula (IV) is a useful intermediate for producing the cyanine compound of the present invention represented by the above general formula (I), and is limited by the production method. However, it can be produced by reacting an indole derivative with an N-bromomethylphthalimide derivative in the presence of sodium iodide as shown in the following reaction formula.

（式中、Ｒ²、Ｅ、Ｙ¹、Ｚ¹、ａ、ｐ及びＡｎ^q-は、上記一般式（Ｉ）と同じであり、Ｑ¹、Ｚ³及びｃは、上記一般式(II)と同じである。）

(Wherein R ² , E, Y ¹ , Z ¹ , a, p and An ^q− are the same as those in the general formula (I), and Q ¹ , Z ³ and c are the same as those in the general formula (II). Is the same.)

Next, the optical recording material and the optical recording medium of the present invention will be described.
The optical recording material of the present invention contains at least one cyanine compound of the present invention and is used for forming the optical recording layer of an optical recording medium having an optical recording layer formed on a substrate. The optical recording medium of the present invention is obtained by forming an optical recording layer made of the optical recording material on a substrate.

  The method for producing the optical recording medium of the present invention, characterized in that the optical recording material of the present invention is prepared and the optical recording layer made of the optical recording material is formed on the substrate, is not particularly limited. . Generally, lower alcohols such as methanol and ethanol; ether alcohols such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and butyl diglycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol; ethyl acetate, Esters such as butyl acetate and methoxyethyl acetate; Acrylic esters such as ethyl acrylate and butyl acrylate; Fluorinated alcohols such as 2,2,3,3-tetrafluoropropanol; benzene, toluene, xylene and the like Hydrocarbons: The organic compound such as chlorinated hydrocarbons such as methylene dichloride, dichloroethane, chloroform, etc. are dissolved in the cyanine compound of the present invention and various compounds described below as necessary to prepare a solution optical recording material. , Spin coating an optical recording material on a substrate, spraying, wet coating method is used to apply in dipping. Other methods include vapor deposition and sputtering. When using the said organic solvent, it is preferable that the usage-amount is made into the quantity from which content of the cyanine compound of this invention in the optical recording material of this invention will be 0.1-10 mass%.

  The optical recording layer is formed as a thin film, and the thickness is usually 0.001 to 10 μm, preferably 0.01 to 5 μm.

  Further, in the optical recording material of the present invention, the content of the cyanine compound of the present invention is preferably 10 to 100% by mass in the solid content contained in the optical recording material of the present invention. The optical recording layer is preferably formed so that the cyanine compound is contained in the optical recording layer in an amount of 50 to 100% by mass. To form an optical recording layer having such a cyanine compound content, the present invention is used. The optical recording material further preferably contains 50 to 100% by mass of the cyanine compound based on the solid content contained in the optical recording material of the present invention.

  The solid content contained in the optical recording material of the present invention is a component obtained by removing components other than the solid content such as an organic solvent from the optical recording material, and the content of the solid content is in the optical recording material. 0.01-100 mass% is preferable, and 0.1-10 mass% is more preferable.

  In addition to the cyanine compound of the present invention, the optical recording material of the present invention includes, as necessary, an azo compound, a phthalocyanine compound, an oxonol compound, a squarylium compound, an indole compound, a styryl compound, a porphine compound, and azulium. Compounds, croconic methine compounds, pyrylium compounds, thiopyrylium compounds, triarylmethane compounds, diphenylmethane compounds, tetrahydrocholine compounds, indophenol compounds, anthraquinone compounds, naphthoquinone compounds, xanthene compounds, thiazines Compounds commonly used in optical recording layers, such as polyethylene compounds, acridine compounds, oxazine compounds, spiropyran compounds, fluorene compounds, rhodamine compounds; polyethylene, polyester, poly Resins such as Tylene and polycarbonate; surfactants; antistatic agents; lubricants; flame retardants; radical scavengers such as hindered amines; pit formation accelerators such as ferrocene derivatives; dispersants; antioxidants; cross-linking agents; An agent or the like may be contained. Furthermore, the optical recording material of the present invention may contain an aromatic nitroso compound, an aminium compound, an iminium compound, a bisiminium compound, a transition metal chelate compound, etc. as a quencher such as singlet oxygen. In the optical recording material of the present invention, these various compounds are used in an amount ranging from 0 to 50% by mass in the solid content contained in the optical recording material of the present invention.

  The optical recording material of the present invention may contain a diimonium compound. By containing the dimonium compound, it is possible to more effectively prevent a decrease in the residual absorbance with time of the optical recording medium of the present invention. The content when the immonium compound is contained is preferably in the range of 0 to 99 mass%, more preferably 50 to 95 mass%, in the solid content contained in the optical recording material of the present invention. .

  Examples of the diimonium compound include compounds represented by the following general formula (VI).

（式中、Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁷及びＲ⁴⁸は、それぞれ独立に、水素原子又は炭素原子数１〜８のアルキル基を表し、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³及びＲ⁵⁴は、それぞれ独立に、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。Ｒ⁴¹、Ｒ⁴²、Ｒ⁴³、Ｒ⁴⁴、Ｒ⁴⁵、Ｒ⁴⁶、Ｒ⁴⁷、Ｒ⁴⁸、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³及びＲ⁵⁴で表される炭素原子数１〜８のアルキル基、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³及びＲ⁵⁴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の数を表す。）

^{(Wherein, R 41, R 42, R} 43, R 44, R 45, R 46, R 47 and R ⁴⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an amino group, R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ^45. R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ , an alkyl group having 1 to 8 carbon atoms, represented by R ⁵¹ , R ⁵² , R ⁵³ and R ⁵⁴ 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 a number of ~ 4.)

  The material of the substrate on which such an optical recording layer is provided is not particularly limited as long as it is substantially transparent to writing (recording) light and reading (reproducing) light. For example, polymethyl methacrylate, A resin such as polyethylene terephthalate or polycarbonate, glass, or the like is used. Moreover, the shape can use arbitrary shapes, such as a tape, a drum, a belt, a disk, according to a use.

  On the optical recording layer, a reflective film can be formed by vapor deposition or sputtering using gold, silver, aluminum, copper, etc., and a protective layer is formed by acrylic resin, ultraviolet curable resin, or the like. You can also

  The optical recording material of the present invention is suitable for an optical recording medium using a semiconductor laser for recording and reproduction, and particularly known high-speed recording types such as CD-R, DVD ± R, HD-DVD-R, and BD-R. Suitable for single-layer, double-layer, and multilayer optical disks.

Next, the color correction material of the present invention will be described.
The color correction material of the present invention contains at least one cyanine compound of the present invention represented by the above general formula (I). Each of the cyanine compounds has an absorption maximum wavelength in the range of 450 to 620 nm or in the vicinity thereof, and can selectively absorb and block a part of visible light.

  The content of the cyanine compound of the present invention in the color correction material of the present invention is preferably 50 to 100% by mass, more preferably 90 to 100% by mass in the solid content contained in the color correction material of the present invention.

  The color correction material of the present invention may be used in combination of one or more known pigment compounds such as cyanine compounds and diimonium compounds used in conventional color correction materials. The content of the dye compound in the color correction material of the present invention is not particularly limited, but is preferably 100 parts by mass or less with respect to 100 parts by mass of the cyanine compound of the present invention.

  Examples of the dye compound include compounds described as light absorbers other than the color correction material (cyanine compound) of the present invention described later.

  The color correction material of the present invention may contain an organic solvent. In this case, the solid content in the color correction material of the present invention is preferably 0.01 to 10% by mass, more preferably 0.5 to 5.0% by mass. Further, the color correction material of the present invention further requires an adhesion imparting agent; a softening agent; a light resistance imparting agent; an ultraviolet absorber; an antioxidant; a plasticizer; an antifoaming agent; a leveling agent; It can be contained in an amount. The content of these additives can be appropriately determined according to the use of the color correction material of the present invention and is not particularly limited, but is preferably 70% by mass or less in the solid content.

  The color correction material of the present invention includes a liquid crystal display (LCD), a plasma display panel (PDP), an electroluminescence display (ELD), a cathode ray tube display (CRT), a CCD image sensor, a CMOS sensor, a fluorescent display tube, a field emission. It is used for applications such as image display devices such as type displays, analysis devices, semiconductor device manufacturing, astronomical observation, optical communication, eyeglass lenses, and windows. In particular, the color correction material of the present invention is suitably used by blending a binder resin with this to form a film-forming composition and producing an optical filter using the film-forming composition.

Next, the film forming composition of the present invention and the optical filter using the film forming composition will be described.
The film forming composition of the present invention contains the color correction material of the present invention. A binder resin is usually blended in the film-forming composition of the present invention. Examples of the binder resin 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 polyester, polyether, polycarbonate, polyamide, polyimide, polyurethane, melamine resin, and cyclic olefin resin, and pressure-sensitive adhesives.

  Examples of the pressure-sensitive adhesive include silicone-based, urethane-based, and acrylic-based pressure-sensitive adhesives, polyvinyl butyral-based pressure-sensitive adhesives, polyvinyl ether-based pressure-sensitive adhesives, ethylene-vinyl acetate-based pressure-sensitive adhesives, polyolefin-based pressure-sensitive adhesives, and SBR-based pressure-sensitive adhesives. In addition, known transparent adhesives for laminated glass, such as rubber adhesives, can be used, among which acrylic adhesives, particularly acidic acrylic adhesives are preferably used.

  The acrylic pressure-sensitive adhesive is not particularly limited, and a homopolymer or a plurality of monomers having a reactive functional group such as a carboxyl group, a hydroxyl group, an amide group, an amino group, and an epoxy group and an ethylenically unsaturated double bond Copolymers combining species, or monomers having the above reactive functional groups and ethylenically unsaturated double bonds, and ethylenically unsaturated compounds such as (meth) acrylic monomers and vinyl monomers A copolymer with a monomer having a double bond can be used, and a metal chelate compound, an isocyanate compound, a melamine compound, Those containing a crosslinking agent such as an epoxy compound, an amine compound, an aziridine compound, and an oxazoline compound can be used.

  As the acrylic pressure-sensitive adhesive, commercially available ones can be used. For example, Davy Bond 5541 (Diabond), SK Dyne AS-1925, KP-2230, SK-1811L (Soken Chemical), DX2- Examples thereof include PDP-19 (manufactured by Nippon Shokubai Co., Ltd.), AT-3001 (manufactured by Seiden Chemical Co., Ltd.), Olivevine BPS5896 (manufactured by Toyo Ink Co., Ltd.), CS-9611 (manufactured by Nitto Denko Corporation), and the like.

  The film-forming composition of the present invention may further contain a necessary amount of optional components such as an organic solvent described later, a light absorber other than the color correction material (cyanine compound) of the present invention, and various stabilizers.

  In the production of an optical filter, when the film-forming composition of the present invention is applied by coating, the film-forming composition of the present invention contains an organic solvent and the film-forming composition of the present invention is applied as a coating liquid. To do. Concentration (solid content) of a coating liquid containing optional components such as a cyanine compound, an organic solvent, and a light correction agent other than the color correction material of the present invention (cyanine compound), various stabilizers, etc. ) Is preferably 0.1 to 5 mass%, more preferably 1 to 3 mass%.

  In the film-forming composition of the present invention, the amounts of the color correction material of the present invention and the binder resin are not limited, but are usually used as follows. For example, when producing the optical filter of the present invention having the pressure-sensitive adhesive layer composed of the film-forming composition of the present invention, the solid content of the pressure-sensitive adhesive as the binder resin is 100 parts by mass of the present invention. 0.0001 to 50 parts by mass, preferably 0.001 to 5.0 parts by mass of the cyanine compound of the present invention which is a component of the color correction material, and 0.1 to 1000 parts by mass of a solvent such as methyl ethyl ketone, preferably 1 A pressure-sensitive adhesive solution was prepared so as to be from 0 to 500 parts by mass, and this pressure-sensitive adhesive solution was applied to a transparent support such as a PET film subjected to easy adhesion treatment, and then dried to a thickness of 2 to 400 μm, preferably Obtain the optical filter of the present invention having a pressure-sensitive adhesive layer of 5 to 40 μm. Further, when the film forming composition of the present invention contains optional components such as other light absorbers and various stabilizers other than the color correction material (cyanine compound) of the present invention, What is necessary is just to follow the above-mentioned mixture ratio.

  In the production of the optical filter of the present invention having the pressure-sensitive adhesive layer, the color correction material (cyanine compound) and binder resin of the present invention, other light absorbers other than the color correction material of the present invention (cyanine compound), various In the case of adopting a method in which an optional component such as a stabilizer is contained in an adhesive layer between any two adjacent members selected from a transparent support and an arbitrary layer, the cyanine compound of the present invention is used as an adhesive. The film-forming composition of the present invention may be contained in the film, and then the film-forming composition may be used as a pressure-sensitive adhesive to bond the transparent support and any two adjacent layers. Furthermore, a well-known separator film such as an easily adhered polyethylene terephthalate film can be provided on the surface of the pressure-sensitive adhesive layer.

The optical filter of the present invention uses the film forming composition of the present invention, and has a layer composed of the film forming composition. The layer constituted by the film-forming composition may be any of the layers described later. In the optical filter of the present invention, particularly in the optical filter for image display, the amount of the cyanine compound that is a component of the color correction material of the present invention is usually 1 to 1000 mg / m ² , preferably 5 to 5 per unit area of the optical filter. The range is 100 mg / m ² . If the amount used is less than 1 mg / m ² , the light absorption effect cannot be sufficiently exerted, and if it is used in excess of 1000 mg / m ² , the color of the filter becomes too strong and the display quality is lowered. There is also a fear that the brightness may be lowered. When the cyanine compound of the present invention is a mixture of a plurality of types, the amount of the cyanine compound of the present invention used is the total amount.

  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.

  As a typical configuration of the optical filter of the present invention, there may be mentioned a transparent support provided with various layers such as an undercoat layer, an antireflection layer, a hard coat layer, a lubricating layer, and an adhesive layer as necessary. . For example, the color correction material of the present invention may be contained in an undercoat layer, an antireflection layer, a hard coat layer, a lubricating layer, an adhesive layer, etc., and the film forming composition of the present invention is used separately from these layers. A configuration having a color correction layer formed in this manner may be used. As a configuration of the optical filter of the present invention, the one in which the color correction material of the present invention is contained in an adhesive layer can be reduced, and the laminated optical filter can be manufactured at low cost.

  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; Polycarbonate; Polysulfone Polyethersulfone; polyetherketone; polyetherimide; polymer materials such as polyoxyethylene and norbornene resin. 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 color correction material (cyanine compound) of the present invention, infrared absorbers, ultraviolet absorbers, fluorescence quenchers, phenol-based, phosphorus-based, sulfur-based antioxidants, etc. Agents, flame retardants, lubricants, antistatic agents, inorganic fine particles, light resistance-imparting agents, aromatic nitroso compounds, aminium compounds, iminium compounds, transition metal chelate compounds, viscosity minerals, etc. Various surface treatments can be applied to the body.

  As other light absorbers other than the color correction material (cyanine compound) of the present invention, for example, when an optical filter is used for an image display device, a light absorber for color tone adjustment, reflection or reflection of external light, and the like. In the case where the image display device is a plasma display, an infrared remote control malfunction preventing light absorber 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 450 to 620 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.

  As a light absorber for preventing reflection of external light and reflection (corresponding to a wavelength of 480 to 500 nm), a trimethine indolium compound, a trimethine oxazolium compound, a trimethine thiazolium compound, an indolidene trimethine thiazonium Trimethine cyanine derivatives such as compounds; phthalocyanine derivatives; naphthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds.

  As a light absorber for preventing infrared remote control malfunction (corresponding to a wavelength of 750 to 1100 nm), a diimonium compound; a pentamethine benzoindolium compound, a pentamethine benzoxazolium compound, a pentamethine benzothiazolium compound, etc. Pentamethine cyanine derivatives; heptamethine indolium compounds, heptamethine benzoindolium compounds, heptamethine oxazolium compounds, heptamethine benzoxazolium compounds, heptamethine thiazolium compounds, heptamethine benzothiazolium compounds, etc. Methinecyanine derivatives; squarylium derivatives; nickel complexes such as bis (stilbenedithiolato) compounds, bis (benzenedithiolato) nickel compounds, bis (camphagethiolato) nickel compounds; Conductor; azo dye derivatives; phthalocyanine derivatives; porphyrin derivatives; dipyrromethene metal chelate compounds, and the like.

  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 polymer binder is used, an organic solvent can be used at the same time, and the organic solvent is not particularly limited, and various known solvents can be appropriately used. For example, alcohol such as isopropanol Ethers such as methyl cellosolve, ethyl cellosolve, butyl cellosolve and butyl diglycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and diacetone alcohol, esters such as ethyl acetate, butyl acetate and methoxyethyl acetate Acrylates 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, di Roroetan, chlorinated hydrocarbons such as chloroform and the like. These organic solvents can be used alone or in combination.
Is preferred.

  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.

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

  The following Examples 1-1 to 1-4 show production examples of iodides of the indolenium compounds IV-1 to IV-4 of the present invention represented by the above general formula (IV), and the following Example 2-1 ˜2-8 are tetrafluoroborate, iodide, quencher anion (3) salt and quencher anion of the cyanine compounds I-1 to I-4 of the present invention represented by the above general formula (I) The production example of the ion (4) salt is shown. In addition, Examples 3-1 to 3-8 shown below are tetrafluoroborate, iodide, quencher anion of compounds I-1 to I-4 obtained in Examples 2-1 to 2-8 ( 3) Preparation of optical recording material of the present invention containing salt and quencher anion (4) salt, and optical recording medium No. 1 of the present invention using the optical recording material. 1-No. 8 production examples are shown.

  Comparative Examples 1-1 and 1-2 described below are comparative optical recording materials prepared using a tetrafluoroborate salt of a cyanine compound having a structure different from that of the cyanine compound of the present invention, and compared using the comparative optical recording material. Optical recording medium No. 1 and no. 2 shows a production example.

  The following Examples 4-1 and 4-2 and Comparative Examples 2-1 and 2-2 are optical recording medium Nos. Obtained in Example 3-1 and Example 3-6. 1 and no. 6 and comparative optical recording media No. 1 obtained in Comparative Examples 1-1 and 1-2. 1 and no. The light resistance of 2 was evaluated by measuring the residual absorbance at the maximum absorption wavelength (λmax) of the UV absorption spectrum.

  The following Examples 5-1 to 5-3 are the tetrafluoroborate salt of the compound I-1 obtained in Example 2-1, and the compound I-3 obtained in Examples 2-5 and 2-6. The production example of the optical filter containing the iodide of I-4 is shown.

[Examples 1-1 to 1-4] Production of indolenium salt 50 mmol of 1,2,3-trialkylindole derivative, 60 mmol of N-bromomethylphthalimide, 60 mmol of sodium iodide and 40 g of ethanol were charged at 60 ° C. for 3 hours. Stir. The precipitated solid was separated by filtration and dried under reduced pressure to obtain iodides of the target indolenium compounds IV-1 to IV-4 of the present invention. The obtained compound was identified by ¹ H-NMR analysis. [Table 1] shows the yield and identification data of the obtained compounds.

[Examples 2-1 to 2-8] Preparation of tetrafluoroborate, iodide, quencher anion (3) salt and quencher anion (4) salt of compounds I-1 to I-4

<Step 1> Production of inorganic salt of cyanine compound 10 mmol of indolenium compound obtained in Examples 1-1 to 1-4, 13 mmol of 1-methyl-2-methylthiobenzoxazole salt, 20 mmol of triethylamine and 10 g of acetonitrile The mixture was stirred and stirred at room temperature for 4 hours. The precipitated solid was separated by filtration and dried under reduced pressure to obtain the objective inorganic salt of the cyanine compound of the present invention.

<Step 2> Production of quencher anion salt of cyanine compound 0.50 mmol of inorganic salt of cyanine compound obtained in <Step 1> above, 0.50 mmol of quencher anion triethylamine salt and 3.6 g of pyridine were charged, The mixture was stirred at 60 ° C. for 2 hours, 8 g of methanol was added, and the mixture was cooled to room temperature. The precipitated solid was separated by filtration and dried under reduced pressure to obtain the quencher anionic salt of the cyanine compound of the present invention, which was the target product.

The obtained compound was identified by ¹ H-NMR analysis. [Table 2] shows the yield and characteristic values of the compound obtained [measurement results of light absorption characteristics in solution (λmax and ε at λmax), decomposition point], and [Table 3] shows identification data. In [Table 2], the decomposition point is the mass decrease starting temperature of differential thermal analysis at a heating rate of 10 ° C./min.

[Examples 3-1 to 3-8]
Tetrafluoroborate, iodide, quencher anion (3) salt and quencher anion (4) salt of compounds I-1 to I-4 obtained in Examples 2-1 to 2-8 above, Each of the optical recordings of the present invention was dissolved in 2,2,3,3-tetrafluoropropanol so that the concentration of the cyanine compound was 1.0% by mass to obtain a 2,2,3,3-tetrafluoropropanol solution. Obtained material. Titanium chelate compound (T-50: manufactured by Nippon Soda Co., Ltd.) is applied, hydrolyzed, and the above optical recording material is applied by spin coating onto a 12 cm diameter polycarbonate disk substrate provided with a base layer (0.01 μm). Then, an optical recording layer having a thickness of 100 nm was formed. 1-No. 8 were obtained respectively. The UV absorption spectrum of the obtained optical recording medium was measured. The results are shown in [Table 4].

[Comparative Examples 1-1 and 1-2]
In place of the cyanine compound of the present invention, the following Comparative Compound No. 1 or No. A comparative optical recording material was prepared in the same manner as in Examples 3-1 to 3-8 except that the tetrafluoroborate salt No. 2 was used. 1 and no. 2 was obtained.

[Examples 4-1 and 4-2 and Comparative Examples 2-1 and 2-2]
The optical recording media No. 1 obtained in Examples 3-1 and 3-6. 1 and no. 6 and comparative optical recording media No. 1 obtained in Comparative Examples 1-1 and 1-2. 1 and no. 2 was evaluated for light resistance. The evaluation was performed by irradiating the optical recording medium with light of 55000 lux, irradiating for 5 hours and 24 hours, and then measuring the remaining absorbance at λmax of the UV absorption spectrum before irradiation. The results are shown in [Table 5].

  As apparent from [Table 5], the optical recording medium having the optical recording layer formed of the optical recording material of the present invention had a high residual rate even after irradiation for 24 hours. On the other hand, a comparative optical recording medium having an optical recording layer formed of a comparative optical recording material containing a comparative compound showed a significant decrease in the residual rate, and the light resistance was not good.

[Examples 5-1 to 5-3]
1 wt% methyl ethyl ketone solution of tetrafluoroborate salt of compound I-1 obtained in Example 2-1 or iodide of compound I-3 or I-4 obtained in Example 2-5 or 2-6 .2 g and 3.0 g of a 25 wt% toluene solution of polymethyl methacrylate (hereinafter also referred to as “PMMA”) were mixed and subjected to ultrasonic irradiation for 15 minutes to prepare a coating solution.
The obtained coating solution was applied to a 188 μm-thick polyethylene terephthalate film that had been subjected to easy adhesion treatment, and then the coating solution was applied by a bar coater # 30, followed by drying at 70 ° C. for 15 minutes, and a film layer having a thickness of 7 to 8 μm. An optical filter of the present invention having the following was prepared. About this optical filter, the absorption spectrum was measured with the JASCO Corporation ultraviolet visible near-infrared spectrophotometer V-570. The results are shown in [Table 6].

  As apparent from [Table 6], the optical filter of the present invention has steep light absorption in the wavelength region of 300 to 1100 nm, and is suitable as an optical filter for an image display device.

Claims (9)

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

(In the formula, R ¹ represents a group represented by the following general formula (II),
R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a group represented by the following general formula (II), or the following general formula ( III) represents a group represented by
X represents an oxygen atom, a sulfur atom, a selenium atom or a CR ³ R ^4,
R ³ and R ⁴ each independently represent a group represented by the alkyl group or the following formula carbon atoms 1 to 20 (II), R ³ and R ^4, 3-6 membered coupled respectively A ring alicyclic group may be formed.
Y ¹ and Y ² each independently represent an alkyl group having 1 to 20 carbon atoms, a group represented by the following general formula (II) or a group represented by the following general formula (III),
Z ¹ and Z ² each independently represent an alkyl group having 1 to 10 carbon atoms, nitro group, cyano group, C androgenic atom, a sulfonyl group or the number of carbon atoms having a hydrocarbon group having 1 to 8 carbon atoms Represents a dialkylamino group having 1 to 8 alkyl groups, the hydrogen atom of the substituent may be substituted with a halogen atom, the methylene group of the substituent may be interrupted with -O- , ¹ and Z ² may be bonded to each other to form a ring structure,
E represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 10 carbon atoms,
a and b each independently represents an integer of 0 to 4;
An ^q− represents a q-valent anion,
q represents 1 or 2,
p represents a coefficient for keeping the charge neutral. )

(Wherein, Z ³ represents an alkyl group having 1 to 10 carbon atoms, represents nitro group or a halogen atom, Z ³ each other several may form a ring structure,
Q ¹ is to display the alkylene group having 1 to 8 carbon atoms which may have a direct bond or a substituent,
c is an integer of 0-4. )

(Wherein, R ^a to R ⁱ represents a water MotoHara child,
Q ² is a direct bond or an optionally substituted alkylene group having 1 to 8 carbon atoms, a methylene group in the alkylene group - CO - may be substituted with,
M ¹ represents Fe . ) An indolenium compound represented by the following general formula (IV).

(In the formula, R ¹ represents a group represented by the following general formula (II),
R ² represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a group represented by the following general formula (II), or the following general formula ( III) represents a group represented by
Y ¹ represents a group represented by the group or the following formula represented by the alkyl group of carbon atom number of 1 to 20 the following general formula (II) (III),
Z ¹ is an alkyl group having 1 to 10 carbon atoms, a nitro group, a cyano group, c androgenic atoms, dialkyl having a sulfonyl group or an alkyl group having 1 to 8 carbon atoms having a hydrocarbon group having 1 to 8 carbon atoms an amino group, a hydrogen atom of the substituent may be substituted by a halogen atom, a methylene group of the substituent is -O - may be interrupted by, a plurality of Z ¹ together bound ring structure May be formed,
E represents a hydrogen atom, a halogen atom, a cyano group or an alkyl group having 1 to 10 carbon atoms,
a represents an integer of 0 to 4;
An ^q− represents a q-valent anion,
q represents 1 or 2,
p represents a coefficient for keeping the charge neutral. )

(Wherein, Z ³ represents an alkyl group having 1 to 10 carbon atoms, represents nitro group or a halogen atom, Z ³ each other several may form a ring structure,
Q ¹ is to display the alkylene group having 1 to 8 carbon atoms which may have a direct bond or a substituent,
c is an integer of 0-4. )

(Wherein, R ^a to R ⁱ represents a water MotoHara child,
Q ² is a direct bond or an optionally substituted alkylene group having 1 to 8 carbon atoms, a methylene group in the alkylene group - CO - may be substituted with,
M ¹ represents Fe . )   An optical recording material comprising at least one cyanine compound according to claim 1 or 2 used for forming the optical recording layer of an optical recording medium having an optical recording layer formed on a substrate.   An optical recording medium having an optical recording layer formed from the optical recording material according to claim 3 on a substrate.   A color correction material comprising at least one cyanine compound according to claim 1 or 2.   A film-forming composition comprising the color correction material according to claim 5.   An optical filter using the film-forming composition according to claim 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.