JP2000314860A - Surface plasmon optical modulating device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a fast modulation and to deal with lights of various wavelengths in a surface plasmon optical modulating device. SOLUTION: This surface plasmon optical modulating device is obtd. by forming a metal film 12 on one face 11a of a dielectric block 11 arranged in such a manner that the light 10 to be modulated propagates in the block to be incident on the face 11a at the total reflection angle, and forming an optical functional film 13 which changes its refractive index by irradiation of light on the film 12, and the optical functional film 13 is irradiated with modulation driving light 14 emitted from a driving light source 15. The optical functional film 13 is formed by using dyes containing an electron donating material and an electron accepting material in which photoelectrons can move.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a surface plasmon light modulation device that modulates light by utilizing generation of surface plasmons.

[0002]

2. Description of the Related Art In a metal, free electrons vibrate collectively to generate a compression wave called a plasma wave. And, the quantization of this compression wave generated on the metal surface is
It is called surface plasmon.

[0003] Also, in the past, the literature Kyoichi Sasaki an
d Toshihiko Nagamura: “Ultrafastwide range all-opt
ical switch using complex refractive-index changes
ina composite film of silver and polymer containi
ng photochromic dye ”, Journal of Applied Physics,
As described in Vol.83, No.6, pp.72-78 (1998), a surface plasmon light modulator that modulates light by utilizing the phenomenon that surface plasmons are excited by light waves is considered. Have been. FIG. 4 shows a basic configuration of a conventionally considered surface plasmon light modulation device. As shown in the figure, the light modulating element basically has a dielectric block 11 arranged so that the modulated light 10 is incident on one surface 11a through the inside thereof at a total reflection angle, and on the dielectric block 11, A formed metal film 12, an optical functional film 13 formed on the metal film 12, the refractive index of which is changed by light irradiation, and a driving light source for irradiating the optical functional film 13 with modulation driving light 14. It is composed of 15 and.

In the above structure, the incident angle θ of the modulated light 10 on one surface 11a of the dielectric block 11 is, for example, the surface plasmon resonance angle of the metal film 12 when the optical functional film 13 is irradiated with the modulation driving light 14. Are excited relatively strongly, and when not illuminated, the surface plasmon resonance is excited relatively weakly or set at an angle that is not excited.

In this way, when the optically functional film 13 is not irradiated with the modulation driving light 14, the modulated light 10 is totally reflected at the interface between the dielectric block 11 and the metal film 12 and moves in the direction A. proceed. On the other hand, when the optical functional film 13 is irradiated with the modulation drive light 14, the surface plasmon resonance is excited on the metal film 12, the total reflection is eliminated, and the reflected light amount of the modulated light 10 is remarkably reduced or becomes zero. . Thus, the modulation driving light 14
, The modulated light 10 traveling in the A direction can be modulated.

Conventionally, it has been considered that the above-mentioned optical functional film is formed by using a dye composed of a spiropyran-based photochromic compound as described in the above-mentioned document. In addition, as described in Shizuoka University Institute of Electronics, published abstracts, “Advanced Technology of Molecular Photonics” (December 11, 1997), pp. 181-187, phthalocyanine It is also considered to form using a dye.

[0007]

However, a photofunctional film formed by using a dye composed of a spiropyran-based photochromic compound has a problem that high-speed modulation cannot be performed because of a low response speed to light. On the other hand, an optically functional film formed using a phthalocyanine dye has a problem that it cannot cope with light in various wavelength ranges because of its limited absorption wavelength.

Accordingly, an object of the present invention is to provide a surface plasmon light modulation element which can perform high-speed modulation and can cope with light of various wavelengths.

[0009]

As described above, the surface plasmon light modulation device according to the present invention comprises: a dielectric block arranged such that modulated light passes through the inside thereof and enters one surface at a total reflection angle; A metal film formed on the dielectric block, an optical functional film formed on the metal film, the refractive index of which is changed by light irradiation, and irradiating the optical functional film with modulation driving light In a surface plasmon light modulation device including a driving light source, the photofunctional film is formed of a dye containing an electron donor and an electron acceptor capable of photoelectron transfer.

[0010] More specifically, as the optical functional film,
Dyes comprising a compound represented by the following general formula (I) can be suitably used.

[0011]

Embedded image[Where DYE⁺Converts the monovalent cyanine dye cation
And n represents an integer of 1 or more;₅ And R₆ Is each
Each independently represents a substituent;₇ And R₈ Are each independently
Alkyl group, alkenyl group, alkynyl group, aralkyl
Group, an aryl group or a heterocyclic group,₅When
R₆, R₅And R₇ , R₆And R₈ Or R ₇And R
₈ May be linked to each other to form a ring, and r and
s each independently represents an integer of 0 to 4;
In the case of two or more, a plurality of r and s are the same as each other.
May be different. In the present invention, the cyanine dye cation of the general formula (I)
Is a cation represented by the following general formula (I-1).
Preferably.

[0012]

Embedded image [Wherein, Za and Zb each independently represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring,
¹ and R ² each independently represent an alkyl group or an aryl group, and L ¹ , L ² , L ³ , L ⁴ and L ⁵
Each independently represents a substituted or unsubstituted methine group (however, when there is a substituent on L ^{1 to} L ⁵ , they may be linked to each other to form a ring), and j is 0, 1 or 2
k represents 0 or 1. Examples of the 5- or 6-membered nitrogen-containing heterocycle (nucleus) represented by Za and Zb include, for example, a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a thiazoline nucleus, an oxazole nucleus, a benzooxazole nucleus, and a naphthoxazole nucleus. , Oxazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, selenazoline nucleus, tellurazole nucleus, benzotellurazole nucleus, naphthotellurazole nucleus, tellurazoline nucleus, imidazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, pyridine nucleus, Examples include a quinoline nucleus, an isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.

Among them, benzothiazole nucleus, imidazole nucleus, naphthoimidazole nucleus, quinoline nucleus, isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus are preferable.

A benzene ring and a naphthoquinone ring may be further fused to these rings.

The above 5- or 6-membered nitrogen-containing heterocyclic ring may have a substituent. Examples of preferred substituents (atoms) include a halogen atom, a substituted or unsubstituted alkyl group,
An aryl group can be mentioned. As the halogen atom, a chlorine atom is preferable. The alkyl group has 1 carbon atom.
~ 6 linear alkyl groups are preferred. Examples of the substituent of the alkyl group include an alkoxy group (eg, methoxy) and an alkylthio group (eg, methylthio). As the aryl group, phenyl is preferred.

The alkyl group represented by R ¹ and R ² may have a substituent, and is preferably a straight-chain having 1 to 18 carbon atoms (more preferably 1 to 8, especially 1 to 6). A cyclic, cyclic or branched alkyl group.

The aryl group represented by R ¹ and R ² may have a substituent, and preferably has 6 carbon atoms.
And aryl groups which may have 18 to 18 substituents.

Preferred examples of the substituents on the alkyl group or the aryl group represented by R ¹ and R ² include the following.

A substituted or unsubstituted aryl group having 6 to 18 carbon atoms (for example, phenyl, chlorophenyl, anisyl, toluyl, 2,4-di-t-amyl, 1-naphthyl), an alkenyl group (for example, vinyl, 2-methylvinyl), alkynyl group (eg, ethynyl, 2-methylethynyl, 2-phenylethynyl), halogen atom (eg, F, Cl, Br, I), cyano group, hydroxyl group, carboxyl group, acyl group ( For example, acetyl, benzoyl, salicyloyl, pivaloyl), alkoxy group (eg, methoxy, butoxy, cyclohexyloxy), aryloxy group (eg, phenoxy, 1-naphthoxy), alkylthio group (eg, methylthio, butylthio, benzylthio, 3- Methoxypropylthio), arylthio groups (eg, , Phenylthio, 4-chlorophenylthio), an alkylsulfonyl group (e.g.,
Methanesulfonyl, butanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl, paratoluenesulfonyl), carbamoyl group having 1 to 10 carbon atoms,
An amide group having 1 to 10 carbon atoms, an acyloxy group having 2 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, a heterocyclic group (for example, pyridyl, thienyl,
Heteroaromatic rings such as furyl, thiazolyl, imidazolyl, and pyrazolyl, and aliphatic heterocycles such as pyrrolidine, piperidine, morpholine, pyran, thiopyran, dioxane, and dithiolane rings).

In the present invention, the above R ¹ and R ²
Is an unsubstituted carbon atom having 1 to 8 carbon atoms (preferably,
A linear alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, or an alkoxy group (particularly, methoxy)
Alternatively, it is preferably a linear alkyl group having 1 to 8 carbon atoms (preferably 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms) substituted with an alkylthio group (particularly methylthio).

The methine groups represented by L ^{1 to} L ⁵ may have a substituent. Examples of preferred substituents include
Examples of the preferred substituents of the alkyl group having 1 to 18 carbon atoms, the aralkyl group, and the alkyl group or the aryl group represented by R ¹ and R ² can be given. Among them, an alkyl group (eg, methyl), an aryl group (eg, phenyl), a halogen atom (eg, Cl, Br), and an aralkyl group (eg, benzyl) are preferable.

In the present invention, j and k are each independently 0
Or 1 is preferable.

The substituents on L ^{1 to} L ⁵ may be linked to each other to form a ring. The preferred number of ring members is a 5- or 6-membered ring, and two or more of these rings may be condensed. The linking position depends on the number of methine chains formed. For example, when the methine chain formed by L ^{1 to} L ⁵ is a pentamethine chain, the preferred linking position is L
¹ and L ³ , L ² and L ⁴ , and L ³ and L ⁵ . When a double condensed ring is formed, the linking position is L ¹
To be ^{L 3} and ^{L 5.} Also in this case, L ¹ and R
¹ , L ⁵ and R ² , and further L ³ and R ² may be linked to each other to form a ring, and the number of ring members is preferably 5
It is a membered or six-membered ring.

In the present invention, the ring formed by the substituents on L ^{1 to} L ⁵ is preferably a cyclohexene ring.

Among the cyanine dye cations represented by the general formula (I-1), the cations represented by the following general formula (I-2) are more preferable.

[0026]

Embedded image [Wherein, Z ¹ and Z ² each independently represent an atomic group necessary for forming an indolenine nucleus or a benzoindolenine nucleus, and R ¹ and R ² each independently represent an alkyl group or an aryl group. And R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group, and L ¹ , L ² ,
L ³ , L ⁴ and L ⁵ each independently represent a substituted or unsubstituted methine group (however, when there is a substituent on L ^{1 to} L ⁵ , they may be linked to each other to form a ring) ), J represents 0, 1 or 2, and k represents 0 or 1. The indolenine nucleus or benzoindolenine nucleus represented by Z ¹ and Z ² may have a substituent.
Examples of the substituent (atom) include a halogen atom and an aryl group. As the halogen atom, a chlorine atom is preferable. As the aryl group, phenyl is preferable.

The above R³ , R⁴ , R⁵ And R⁶ In table
The alkyl group preferably has 1 to 18 carbon atoms.
It is a linear, branched, or cyclic alkyl group. Ma
R ³ And R⁴ , And R⁵ And R⁶ Are connected to each other
A ring may be formed.

The alkyl group represented by R ³ , R ⁴ , R ⁵ and R ⁶ may have a substituent. Preferred examples of the substituent include those exemplified as preferred substituents of the alkyl group or aryl group represented by R ¹ and R ² .

In the present invention, R ³ , R ⁴ , R ⁵
And the alkyl group represented by R ⁶ is preferably a linear unsubstituted alkyl group having 1 to 6 carbon atoms (particularly, methyl or ethyl).

In the general formula (I-2), R ¹ and R
² , L ¹ , L ² , L ³ , L ⁴ and L ⁵ , j and k, and X ⁿ⁻ and n are each represented by the general formula (I-1)
Have the same meanings as those described above. Preferred examples thereof are also the same as those described in the formula (I-1).

[DYE ⁺ ]-(SO ₃ ⁻ ) _{n + 1} (SO ₃ ⁻ ) group is represented by the general formula (I-1) or the general formula (I
It is preferable to bond to the terminals of R ¹ and R ² of -2).

Hereinafter, [D] in the general formula (I) of the present invention will be described.
YE ⁺ ]-(SO ₃ ⁻ ) Specific examples of the ( _{n + 1} ) portion are listed.

[0033]

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Embedded image The following partial structure in general formula (I) (general formula (I-3)
Will be described in detail.

[0034]

Embedded image In the formula, R ₅ and R ₆ each independently represent a substituent,
R ₇ and R ₈ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or a heterocyclic group, and R ₅ and R ₆ , R ₅ and R ₇ , R ₆ and
R ₈ or R ₇ and R ₈ may be linked to each other to form a ring, r and s each independently represent an integer of 0 to 4, and when r and s are 2 or more, Multiple r and s
May be the same or different from each other.

The alkyl group represented by R ₇ and R ₈ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, more preferably a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms. is there. These may be linear, branched, or cyclic. Examples of these include methyl, ethyl, n-propyl, isopropyl,
n-butyl, isobutyl, t-butyl, n-hexyl,
Neopentyl, cyclohexyl, adamantyl, cyclopropyl and the like.

Examples of the substituent of the alkyl group include the following.

Having 2 to 18 carbon atoms (preferably having 2 to 2 carbon atoms)
8) a substituted or unsubstituted alkenyl group (eg, vinyl); a substituted or unsubstituted alkynyl group having 2 to 18 (preferably 2 to 8) carbon atoms (eg, ethynyl); A substituted or unsubstituted aryl group (eg,
Phenyl, naphthyl); halogen atom (eg, F, Cl,
Br, etc.); C1-18 (preferably C1-8)
A substituted or unsubstituted alkoxy group (eg, methoxy,
Ethoxy); a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms (eg, phenoxy, p-methoxyphenoxy); a substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (Eg, methylthio, ethylthio); a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms (eg, phenylthio); 2 carbon atoms
To 18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted acyl group (eg, acetyl, propionyl); 1 to 18 (preferably 1 to 8 carbon atoms) substituted or unsubstituted alkylsulfonyl group Or an arylsulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl); a substituted or unsubstituted acyloxy group having 2 to 18 (preferably 2 to 8) carbon atoms (eg, acetoxy,
A substituted or unsubstituted alkoxycarbonyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms) (eg, methoxycarbonyl, ethoxycarbonyl); a substituted or unsubstituted aryloxy group having 7 to 11 carbon atoms A carbonyl group (eg, naphthoxycarbonyl); an unsubstituted amino group or a substituted amino group having 1 to 18 (preferably 1 to 8) carbon atoms (eg, methylamino, dimethylamino, diethylamino, anilino, methoxyphenyl) Amino, chlorophenylamino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, ethylthiocarbamoylamino, phenylcarbamoylamino, acetylamino, ethylcarbonylamino, ethylthio Carbamoylamino, cyclohexyl carbonylamino, benzoylamino, chloroacetyl amino, methylsulfonylamino); 1 the number of carbon atoms
18 (preferably 1 to 8 carbon atoms) substituted or unsubstituted carbamoyl group (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidino) Carbamoyl); an unsubstituted sulfamoyl group, or having 1 to 1 carbon atoms
18 (preferably 1 to 8 carbon atoms) substituted sulfamoyl group (eg, methylsulfamoyl, phenylsulfamoyl); cyano group; nitro group; carboxy group; hydroxyl group; heterocyclic group (eg, oxazole ring, benzoxazole) Ring, thiazole ring, benzothiazole ring, imidazole ring, benzimidazole ring, indolenine ring, pyridine ring, piperidine ring, pyrrolidine ring, morpholine ring, sulfolane ring, furan ring, thiophene ring, pyrazole ring, pyrrole ring, chroman ring, Coumarin ring). The alkenyl group represented by R ₇ and R ₈ is preferably a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms. , Vinyl, allyl, 1-propenyl, 1,3-butadienyl and the like.

As the substituent for the alkenyl group, those mentioned above as the substituent for the alkyl group are preferable.

The alkynyl group represented by R ₇ and R ₈ is preferably a substituted or unsubstituted alkynyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkynyl group having 2 to 8 carbon atoms. Yes, for example, ethynyl, 2-propynyl and the like.

As the substituent for the alkynyl group, those described above as the substituent for the alkyl group are preferable.

The aralkyl group represented by R ₇ and R ₈ is preferably a substituted or unsubstituted aralkyl group having 7 to 18 carbon atoms, for example, benzyl, methylbenzyl and the like.

The aryl group represented by R ₇ and R ₈ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, such as phenyl and naphthyl.

The substituents of the aryl group are preferably those described above as the substituents of the alkyl group. In addition to these,
Alkyl groups (eg, methyl, ethyl, etc.) are also preferred.

The heterocyclic group represented by R ₇ and R ₈ is a 5- or 6-membered saturated or unsaturated heterocyclic ring composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, Examples of these include an oxazole ring, a benzoxazole ring, a thiazole ring, a benzothiazole ring, an imidazole ring, a benzimidazole ring, an indolenine ring, a pyridine ring, a piperidine ring, a pyrrolidine ring, a morpholine ring, a sulfolane ring, a furan ring, and thiophene. Ring, pyrazole ring, pyrrole ring, chroman ring, and coumarin ring. The heterocyclic group may be substituted, and in this case, the substituent is preferably those exemplified as the substituent for the alkyl group.

The substituents represented by R ₅ and R ₆ have the same meaning as the above-mentioned substituents for the alkyl group. In addition to these, an alkyl group (eg, methyl, ethyl, etc.) can also be mentioned.

In the present invention, the substituent represented by R ₅ and R ₆ is preferably a hydrogen atom or an alkyl group. Particularly preferred is a hydrogen atom.

The partial structure represented by the general formula (I-3) is
It is particularly preferably represented by the following general formula (I-4) or (I-5).

[0048]

Embedded image In the formula, R ₁₇ and R ₁₈ have the same meanings as the substituents represented by R ₅ and R ₆ described above, respectively, and their preferred ranges are also the same. R _{1 9} and R ₂₀ are the same as the substituents represented by R ₇ and R ₈ which are mentioned above, also for each of their preferred scopes are identical. r and s are each independently 0 to
And when r and s are 2 or more, a plurality of r and s may be the same or different from each other.

[0049]

Embedded image In the formula, R ₂₁ and R ₂₂ have the same meanings as the substituents represented by R ₅ and R ₆ described above, respectively, and their preferred ranges are also the same. R _{2 1} and R
₂₂ are also preferably linked to each other to form a carbocyclic or heterocyclic ring, and particularly preferably, R ₂₁
And R ₂₂ are each a condensed aromatic ring with a pyridine ring bonded thereto. r and s each independently represent an integer of 0 to 4, and when r and s are 2 or more, a plurality of r and s
May be the same or different from each other.

Specifically described in the following example of a ^- (indicated by "B") [0050] Formula moiety represented by (I-3) of the dye compound represented by the general formula (I) used in the present invention I do.

[0051]

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Embedded image Preferred specific examples of the compounds used in the present invention are shown in Tables 1 and 2 below. In Tables 1 and 2, the compound example is a combination of an anion part represented by [DYE ⁺ ]-(SO ₃ ⁻ ) _{n + 1} and a cation part represented by the general formula (I-3). For example, the following
This will be described with reference to the example of No. 1. Examples of compounds represented by compound No. 1 [anion part (A-1) / cation part (B-5)] are represented by the following formulas.

[0052]

Embedded image The same applies to the compound No. 2 and subsequent compounds.

[0053]

[Table 1]

[Table 2] The compound represented by the above general formula (I) used in the present invention is
They may be used alone or in combination of two or more.

The compound represented by formula (I) used in the present invention can be easily synthesized with reference to the description of the following known literatures.

These documents include, for example, F.
M. Hammer, "The Cyanine Soybeans and Related Compounds 5 (Interscience Publishers, NY, 1964), p. 55 et seq .; Nikolai Tuturkov, Jurgen Fabian, Akim Meerhorn, Filitz・ Diets Aria Tadzières (Nikolai Tyutyulkov, Jurgen Fabian, Achim U
lehlhorn, Fritz Dietz, Alia Tadjer) co-authored "Polymethine soybean", St. Kliment Ohridski University Press, Sofia (St. Kliment Ohridski Uni)
versity Press, Sophia), pp. 23-38;
DMSturmer, "Heterocyclic Compounds-Special Topics in.
Heterocyclic chemistry
pounds-Special topics in heterocyclic chemistr
y) ", Chapter 18, Section 14, pp. 482-515, John Wiley & Sons
Co., New York, London, (1977); "Rodd's Chemistry of Carbon Compounds", (2nd.
Ed. Vol.IV, part B, 1977), Chapter 15, Chapter 3
69-422, (2nd. Ed. Vol. IV, part B, 1985
Annual, Chapter 15, Chapters 267-296, Elsbyer Science Public Company, Inc.
svier Science Public Company Inc.), New York, and the like.

More specifically, [DYE ⁺ ]-(SO ₃
⁻ ) _{N + 1} (M ⁺ ) _n , where M is a sodium ion, potassium ion, ammonium ion, pyridinium ion, triethylammonium ion, N−
A salt represented by a cation such as ethylpyridinium ion) and a cation represented by the general formula (I-3) in combination with an anion such as Cl ⁻ , Br ⁻ , I ⁻ , and paratoluenesulfonate. The resulting salt can be obtained by mixing in a suitable solvent, for example, methanol, water, or a mixture thereof, followed by precipitation as crystals.

As one example, compound 41 is A-28
N-ethylpyridinium salt in methanol and B-5
Crystals precipitated by mixing with a bromide methanol solution of No. 4 are collected by filtration, washed with methanol, and dried to obtain a faded powder having a melting point of 213-217 °.

In the present invention, the following general formula (II)
Photofunctional films formed individually or in combination of the dye compounds represented by -1) and (II-2) can also be suitably used.

[0059]

Embedded image In the formula, A ¹ , A ² , B ¹ and B ² represent a substituent,
L ¹ , L ² , L ³ , L ⁴ and L ⁵ represent a methine group;
¹ represents ＝ O, ＮＲNR, ＣC (CN) ₂ (where R represents a substituent), and X ² represents —O, —NR, —C (CN) _2.
(Where R represents a substituent), and m and n each represent an integer of 0 to 2. Y ¹ and E each represent an atom or a group of atoms necessary to form a carbocyclic or heterocyclic ring, and Z ¹ and G each represent an atom or a group of atoms necessary to form a carbocyclic or heterocyclic ring. x and y each independently represent 0 or 1. M
^{k +} represents an onium ion. k represents the number of charges.

Hereinafter, the dye compound used in the present invention will be described.

The dye compound used in the present invention comprises an anion part (dye component) and a cation part (onium component).

First, the anion portion will be described in detail.

In the above formula, examples of the substituent represented by A ¹ , A ² , B ¹ and B ² include the following.

C1 to C18 (preferably C1 to C1)
8) a substituted or unsubstituted linear, branched or cyclic alkyl group (eg, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl,
t-butyl, cyclohexyl, methoxyethyl, ethoxycarbonylethyl, cyanoethyl, diethylaminoethyl, hydroxyethyl, chloroethyl, acetoxyethyl, trifluoromethyl, etc.); substituted or unsubstituted one having 7 to 18 carbon atoms (preferably 7 to 12 carbon atoms). A substituted aralkyl group (eg, benzyl, carboxybenzyl, etc.); an alkenyl group having 2 to 18 carbon atoms (preferably, 2 to 8 carbon atoms) (eg, vinyl, etc.); 8) an alkynyl group (eg, ethynyl, etc.);
To 18 (preferably 6 to 10 carbon atoms) substituted or unsubstituted aryl group (eg, phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-carboxyphenyl,
3,5-dicarboxyphenyl, etc.);
(Preferably 2 to 8 carbon atoms) substituted or unsubstituted acyl group (eg, acetyl, propionyl, butanoyl, chloroacetyl, etc.); substituted or unsubstituted 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) An alkyl or aryl sulfonyl group (e.g., methanesulfonyl, p-toluenesulfonyl, etc.); having 1 to 18 carbon atoms (preferably 1 carbon atom)
To 8) alkylsulfinyl groups (eg, methanesulfinyl, ethanesulfinyl, octanesulfinyl, etc.); alkoxycarbonyl groups having 2 to 18 (preferably 2 to 8 carbon atoms) (eg, methoxycarbonyl, ethoxycarbonyl, etc.); An aryloxycarbonyl group having 7 to 18 (preferably 7 to 12) carbon atoms (eg, phenoxycarbonyl, 4-methylphenoxycarbonyl,
4-methoxyphenylcarbonyl, etc.);
(Preferably 1 to 8 carbon atoms) substituted or unsubstituted alkoxy group (for example, methoxy, ethoxy, n-butoxy, methoxyethoxy, etc.); substituted or substituted with 6 to 18 carbon atoms (preferably 6 to 10 carbon atoms) An unsubstituted aryloxy group (eg, phenoxy, 4-methoxyphenoxy, etc.); an alkylthio group having 1 to 18 (preferably 1 to 8) carbon atoms (eg, methylthio, ethylthio, etc.); Arylthio (eg, phenylthio etc.); a substituted or unsubstituted acyloxy group having 2 to 18 (preferably 2 to 8 carbons) (eg, acetoxy, ethylcarbonyloxy, cyclohexylcarbonyloxy, benzoyloxy, chloroacetyloxy, etc.) ); Having 1 to 1 carbon atoms
18 (preferably 1 to 8 carbon atoms) substituted or unsubstituted sulfonyloxy group (eg, methanesulfonyloxy etc.); 2 to 18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted carbamoyloxy Groups (eg, methylcarbamoyloxy, diethylcarbamoyloxy, etc.); substituted or unsubstituted amino groups having 0 to 18 (preferably 0 to 8) carbon atoms (eg, unsubstituted amino, methylamino, dimethylamino, Diethylamino, anilino, methoxyphenylamino, chlorophenylamino,
Morpholino, piperidino, pyrrolidino, pyridylamino, methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, phenylcarbamoylamino, ethylthiocarbamoylamino, methylsulfamoylamino,
Phenylsulfamoylamino, acetylamino, ethylcarbonylamino, ethylthiocarbonylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methanesulfonylamino, benzenesulfonylamino, etc.); having 1 to 18 carbon atoms (preferably 1 carbon atom) To 8) substituted or unsubstituted carbamoyl groups (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl, etc.); ~
18 (preferably 0 to 8 carbon atoms) substituted or unsubstituted sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, etc.); halogen atom (eg, fluorine, chlorine, bromine, etc.) A hydroxyl group; a nitro group; a cyano group; a carboxyl group; a heterocyclic group (eg,
Oxazole, benzoxazole, thiazole, benzothiazole, imidazole, benzimidazole, indolenine, pyridine, sulfolane, furan, thiophene, pyrazole, pyrrole, chroman, coumarin, etc.).

The substituents represented by A ¹ and A ² preferably have a Hammett's substituent constant (σp) value of 0.2 or more. Hammett's substituent constant is, for example, Ch
em. Rev .. 91, 165 (1991). Particularly preferred substituents are cyano, nitro, alkoxycarbonyl, acyl, carbamoyl, sulfamoyl, alkylsulfonyl and arylsulfonyl groups.

The substituent represented by B ¹ and B ² is preferably an alkyl group, an aryl group, an alkoxy group, or an amino group.

[-C (= L ¹ )-which binds to Y ^{1
(E) x -C (= X} 1) - ] (hereinafter, for convenience, W1
Called. ) And Z ¹ [-C (-L ⁵ ) =
(G) y = C (-X 2 -) - ] (hereinafter, for convenience, W
2) are in a conjugate state, and therefore Y ¹
And a carbocyclic or heterocyclic ring formed by W1 and Z ¹
And the carbocycle or heterocycle formed by W2 are each considered as one of the resonance structures.

The carbocyclic or heterocyclic ring formed by Y ¹ and W 1, and Z ¹ and W 2 is preferably a 4- to 7-membered ring, particularly preferably a 5- or 6-membered ring. These rings may further form a condensed ring with another 4- to 7-membered ring. These may have a substituent. Examples of the substituent include those described as the substituents represented by A ¹ , A ² , B ¹ and B ² . Preferred as hetero atoms forming a heterocyclic ring are B, N,
O, S, Se, and Te. Particularly preferably, N,
O and S.

X and y are each independently 0 or 1, and preferably both are 0.

X ¹ is ＝ O, ＮＲNR or ＣC (CN)
₂ is represented. X ² represents —O, —NR or —C (C
N) represents ₂ . R represents a substituent. Examples of the substituent represented by R include those described above as the substituents represented by A ¹ , A ² , B ¹ and B ² . R is preferably an aryl group. Particularly preferred is phenyl.

In the present invention, X ¹ is preferably ＯO, and X ² is preferably —O.

Examples of the carbon ring formed by Y ¹ and W 1 and Z ¹ and W 2 include the following.
In the examples, Ra and Rb each independently represent a hydrogen atom or a substituent.

[0073]

Embedded image Preferred carbocycles are those represented by A-1 and A-4.

Examples of the heterocyclic ring formed by Y ¹ and W 1 and Z ¹ and W 2 include the following.
In the examples, Ra, Rb and Rc each independently represent a hydrogen atom or a substituent.

[0075]

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Embedded image Preferred heterocycles are the heterocycles represented by A-5, A-6, and A-7.

The substituents represented by Ra, Rb and Rc are
It has the same meaning as the substituents represented by A ¹ , A ² , B ¹ and B ² .

Further, Ra, Rb and Rc may be linked to each other to form a carbocyclic or heterocyclic ring.

The methine groups represented by L ¹ , L ² , L ³ , L ⁴ and L ⁵ are each independently a methine group which may have a substituent. Examples of the substituent include those described above as the substituents represented by A ¹ , A 2, B ¹ and B 2. Preferred substituents are an alkyl group, an aralkyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
A halogen atom, an amino group, a carbamoyl group and a heterocyclic group. The substituents are linked to form a 5- to 7-membered ring (eg, a cyclopentene ring, 1-dimethylaminocyclopentene ring, 1-diphenylaminocyclopentene ring, cyclohexene ring, 1-chlorocyclohexene ring, isophorone ring, 1-morpholinocyclopentene ring) , A cycloheptene ring).

In the present invention, it is preferable that both m and n are 1, or that m is 0 and n is 2, or m is 2 and n is 0.

Next, the cation portion will be described in detail.

The onium ion represented by M ^{k +} is most preferably represented by the following formula (II-3) or (II-4).

[0082]

Embedded image

Embedded imageWhere R¹ , R² , R⁵And R⁶Are each independently
Alkyl, alkenyl, alkynyl or aryl
Represents a hydroxyl group. R³ , R⁴ , R⁷ And R⁸ Is German
Stands for a substituent (including a substituent atom). R¹ And R² ,
R³ And R⁴ , R⁵ And R⁶ And R⁷ And R⁸ Is
Each may be linked together to form a ring, or
Is also R¹And R³ , R² And R⁴ , R⁵ And R⁷,
And R ⁶And R⁸Is a ring connected to each other
May be formed. q1 and q2, and r1 and r2
Represents an integer of 0 to 4; q1, q2, r1 and
And when each of r2 is 2 or more,
³ , R⁴ , R⁷And R⁸Are the same as each other
Or different.

The alkyl group represented by R ¹ , R ² , R ⁵ and R ⁶ is preferably a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, more preferably 1 to 18 carbon atoms.
8 is a substituted or unsubstituted alkyl group, for example,
Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl and the like.

Examples of the substituent of the alkyl group include the following.

A halogen atom (eg, F, Cl, Br, etc.);
A substituted or unsubstituted alkoxy group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (eg, methoxy, ethoxy); a substituted or unsubstituted aryloxy having 6 to 10 carbon atoms (eg, phenoxy, p- Methoxyphenoxy);
A substituted or unsubstituted alkylthio group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) (eg, methylthio, ethylthio); a substituted or unsubstituted arylthio group having 6 to 10 carbon atoms (eg, phenylthio); 2 to 18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted acyl group (eg, acetyl, propionyl); 1 to 18 (preferably 1 to 8 carbon atoms) substituted or unsubstituted alkylsulfonyl Group or arylsulfonyl group (eg, methanesulfonyl, p-toluenesulfonyl);
18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted acyloxy group (eg, acetoxy, propionyloxy); 2 to 18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted alkoxycarbonyl group (Eg, methoxycarbonyl, ethoxycarbonyl);
8 (preferably 2 to 8 carbon atoms) substituted or unsubstituted alkenyl group (eg, vinyl); 2 to 18 (preferably 2 to 8 carbon atoms) substituted or unsubstituted alkynyl group (eg, ethynyl) A substituted or unsubstituted aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl); a substituted or unsubstituted aryloxycarbonyl group having 7 to 11 carbon atoms (eg, naphthoxycarbonyl); 18
(Preferably having 0 to 8 carbon atoms) a substituted or unsubstituted amino group (eg, unsubstituted amino, methylamino, dimethylamino, diethylamino, anilino, methoxyphenylamino, chlorophenylamino, morpholino, piperidino, pyrrolidino, pyridylamino, Methoxycarbonylamino, n-butoxycarbonylamino, phenoxycarbonylamino, methylcarbamoylamino, ethylthiocarbamoylamino, phenylcarbamoylamino,
Acetylamino, ethylcarbonylamino, ethylthiocarbamoylamino, cyclohexylcarbonylamino, benzoylamino, chloroacetylamino, methylsulfonylamino); a substituted or unsubstituted carbamoyl group having 1 to 18 (preferably 1 to 8) carbon atoms (Examples: unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl, n-butylcarbamoyl, t-butylcarbamoyl, dimethylcarbamoyl, morpholinocarbamoyl, pyrrolidinocarbamoyl);
8 (preferably 0 to 8 carbon atoms) substituted or unsubstituted sulfamoyl group (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl); cyano group; nitro group; carboxy group; hydroxyl group; Groups (eg, oxazole, benzoxazole, thiazole, benzothiazole, imidazole, benzimidazole, indolenine, pyridine, sulfolane, furan,
Thiophene, pyrazole, pyrrole, chroman, coumarin).

The alkenyl group represented by R ¹ , R ² , R ⁵ and R ⁶ is preferably a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, more preferably a substituted or unsubstituted alkenyl group having 2 to 8 carbon atoms. It is a substituted alkenyl group, for example, vinyl, allyl, 1-propenyl, 1,3-butadienyl and the like.

As the substituent for the alkenyl group, those mentioned above as the substituent for the alkyl group are preferable.

The alkynyl group represented by R ¹ , R ² , R ⁵ and R ⁶ is preferably a substituted or unsubstituted alkenyl group having 2 to 18 carbon atoms, more preferably 2 alkenyl groups.
To 8 substituted or unsubstituted alkenyl groups such as ethynyl and 2-propynyl.

As the substituent for the alkynyl group, those described above as the substituent for the alkyl group are preferable.

The aryl group represented by R ¹ , R ² , R ⁵ and R ⁶ is preferably a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, such as phenyl and naphthyl.

The substituents of the aryl group are preferably those described above as the substituents of the alkyl group. In addition to these,
Alkyl groups (eg, methyl, ethyl, etc.) are also preferred.

R³ , R⁴ , R⁷ And R⁸Represented by
Substituent is the above-mentioned A¹ , A², B ¹ And B² In table
Has the same meaning as the substituents mentioned above.

In the present invention, R ³ , R ⁴ , R ⁷
And the substituent represented by R ⁸ is preferably a hydrogen atom or an alkyl group. Particularly preferred is a hydrogen atom.

In the present invention, it is preferred that R ⁵ and R ⁶ are linked to each other to form a ring. The formed ring is preferably a 5- to 7-membered ring, more preferably a 6-membered ring.

It is also preferred that R ³ and R ⁴ , and R ⁷ and R ⁸ are connected to each other to form a carbocyclic or heterocyclic ring. More preferably, it is a carbocyclic ring, and particularly preferably a condensed aromatic ring with a pyridine ring to which R ³ , R ⁴ , R ⁷ and R ⁸ are bonded.

The anion part and the cation part of the dye compound represented by formula (II-1) or (II-2) used in the present invention will be specifically described below.

[0097]

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Embedded image Preferred specific examples of the compounds used in the present invention are shown in Table 3 below.

In Table 3, compound examples are those obtained by combining an anion portion and a cation portion. For example,
In the following, no. This will be described with reference to an example of No. 3. Compound No.
3 [anion part (B-3) / cation part (C-20)]
Is represented by the following formula.

[0099]

Embedded image In addition, Compound No. The same applies to compound examples 4 and following.

[0100]

[Table 3]

Embedded image The compounds represented by the general formulas (II-1) and (II-2) are represented by the following general formulas (II-9) and (II-
10) an alkali metal salt of the dye compound represented by (eg, Li
Salt, Na salt, K salt, etc.), ammonium salt (NH
⁴⁺ salt) or triethylammonium salt (Et ₃
NH ⁺ salt) and a compound represented by the following general formula (II-11)
Can be easily synthesized by a salt exchange reaction with an onium salt represented by the following formula in water or an organic solvent (methanol, ethanol, isopropanol, dimethylformamide, etc.).

[0101]

Embedded imageWhere A⁵ And A⁶ , B⁵ And B⁶ , Y³ And Z
³, And L¹¹, L¹², L¹³, L¹⁴And L
^Fifteen, X³ And X4, E1 and G1, m3 and n3,
And x1 and y1 each represent the aforementioned general formula (II-
1) or A in the general formula (II-2)¹ , A²,
B¹ And B² , Y¹ And Z¹ , L ¹ , L²,
L³ , L⁴ And L⁵ , X¹ And X² , E and G,
It is synonymous with m and n, and x and y, respectively.

[0102]

Embedded image In the formula, X ^r− represents an anion, and r represents an integer (preferably an integer of 1 to 4, more preferably an integer of 1 to 2).

Examples of the anion include halide ions (Cl ⁻ , Br ⁻ , I ⁻ ), sulfonate ions (CH 3 SO 3 ⁻ , p-toluene sulfonate ion, and naphthalene-1,5-disulfonate ion). C
lO ₄ ^-, BF ₄ ^-, and PF ₆ ^- and the like.

The formulas (II-9) and (II-1)
The dye compound represented by (0) generally includes a methine group or a polymethine group introduced into the corresponding active methylene compound (eg, pyrazolone, thiobarbituric acid, barbituric acid, indandione, hydroxyphenaleon) and a methine dye. By a condensation reaction with a methine source. Details of this type of compound are described in JP-B-39-22069, JP-B-43-3504, and JP-B-52-3504.
No. 38056, No. 54-38129, No. 55-100
No. 59, 58-35544, JP-A-49-9962.
No. 0, No. 52-92716, No. 59-16834,
JP-A-63-316853 and JP-A-64-40827, as well as British Patent No. 11333986, U.S. Pat. Nos. 3,247,127, 4042397, and 41812.
25, 5213956 and 5260179 can be referred to.

Specifically, ortho-esters such as ethyl orthoformate and ethyl orthoacetate or N, N-diphenylformamidine hydrochloride are used for introducing a monomethine group, and trimethoxypropene is used for introducing a trimethine chain. ,
1,1,3,3-tetramethoxypropane or malonaldehyde dianyl hydrochloride (or derivatives thereof)
Glutaconaldehyde dianyl hydrochloride or 1- (2,4-dinitrophenyl) -pyridinium chloride (or a derivative thereof) is used to introduce a pentamethine chain.

In the following, formula (II-1) or formula (II
A synthesis example of the dye compound represented by -2) will be described.

(Synthesis Example 1) Synthesis of 5 1 g of the following compound a was added to 20 mL of a 0.1 N aqueous sodium hydroxide solution at room temperature, followed by stirring. To this solution, an aqueous solution in which 0.5 g of the following compound b was dissolved in 5 mL of water was added. After stirring at the same temperature for 30 minutes, the precipitated crystals were filtered, washed with water and ethanol, and dried to obtain the desired product, 0.2
3 g were obtained. .lambda.max = 654 nm (in methanol).

[0108]

Embedded image The compound represented by the general formula (II-1) and the compound represented by the general formula (II-2) may be used alone or in combination of two or more. Also,
The compound represented by the general formula (II-1) and the compound represented by the general formula (II-
The compounds shown in 2) may be used in combination.

Further, in the present invention, as the optical functional film, a film composed of an organic dye represented by the following general formula (III) can be preferably used.

[0110]

Embedded image In the formula, Z ¹ and Z ² each represent an atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, R ³⁰ and R ³¹ each independently represent an alkyl group, and L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ each represent a methine group, n1 and n2 each represent an integer of 0 to 2, p and q each independently represent an integer of 0 to 2,
M represents a charge balancing counter ion.

In the present invention, the compound represented by the general formula (III)
The optical functional film composed of a combination of the organic dye represented by the formula (1) and an organic oxidant represented by the following formula (IV) is more preferable.

[0112]

Embedded image In the formula, m and n each independently represent an integer of 0 to 2, and X ¹ ,
X ² represents ＮＲNR ¹ or ＣＲCR ² R ³ (R ¹ ,
R ² and R ³ represent a substituent), L ¹ and L ² each independently represent a divalent linking group.

Hereinafter, the organic oxidizing agent and the organic dye used in the present invention will be described.

First, the organic oxidizing agent will be described. In the general formula (IV), it is preferable that m and n are both 1.

X ¹ and X ² are ＮＲNR ¹ or ＣＲCR ²
Representing the R ^3. The substituent represented by R ¹ , R ² and R ³ is a halogen atom, a carbon atom, an oxygen atom,
A substituent formed by combining a nitrogen atom or a sulfur atom, specifically, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, a nitro group, a mercapto group, and a hydroxy group , Alkoxy group, aryloxy group, alkylthio group, arylthio group, acyloxy group, amino group, alkylamino group,
Amide group, sulfonamide group, sulfamoylamino group, alkoxycarbonylamino group, alkoxysulfonylamino group, ureido group, thioureido group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, alkylsulfinyl group, sulfamoyl group, Examples thereof include a carboxyl group (including a salt) and a sulfo group (including a salt). These may be further substituted with these substituents.

Examples of the substituents represented by R ¹ , R ² and R ³ will be described in more detail.

The alkyl group is an alkyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms) which may have a linear, branched or cyclic substituent.
Ethyl, propyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 3
-Hydroxypropyl, 4-hydroxybutyl, 3-methoxypropyl, 2-aminoethyl, acetamidomethyl, 2-acetamidoethyl, carboxymethyl, 2-
Examples thereof include carboxyethyl, 2-sulfoethyl, ureidomethyl, 2-ureidoethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, pentyl, hexyl, octyl, decyl, undecyl, dodecyl, hexadecyl, and octadecyl.

The alkenyl group is a linear, branched or cyclic alkenyl group having 2 to 18 carbon atoms (preferably having 2 to 6 carbon atoms), for example, vinyl, allyl, 1-propenyl, 2-pentenyl, , 3-butadienyl, 2-octenyl and 3-dodecenyl.

The aralkyl group is an aralkyl group having 7 to 10 carbon atoms, for example, benzyl.

The aryl group is an aryl group having 6 to 10 carbon atoms which may have a substituent, and examples thereof include phenyl, naphthyl, p-dibutylaminophenyl and p-methoxyphenyl.

The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. One or more kinds of elements may be used, for example, furyl, benzofuryl, pyranyl, pyrrolyl, imidazolyl, isoxazolyl, pyrazolyl, benzotriazolyl, pyridyl, pyrimidyl, pyridazinyl, thienyl, indolyl, quinolyl, phthalazinyl,
Examples thereof include quinoxalinyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl, piperidyl, piperazinyl, indolinyl, and morpholinyl.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

The alkoxy group is an alkoxy group which may have a substituent having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, -Methoxyethoxy, 2-methanesulfonylethoxy, pentyloxy,
Hexyloxy, octyloxy, undecyloxy,
Dodecyloxy, hexadecyloxy and octadecyloxy can be mentioned.

The aryloxy group is an aryloxy group which may have a substituent having 6 to 10 carbon atoms, and examples thereof include phenoxy and p-methoxyphenoxy.

The alkylthio group is an alkylthio group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include methylthio, ethylthio, octylthio, undecylthio, dodecylthio, hexadecylthio, and octadecylthio.

The arylthio group is an arylthio group having 6 to 10 carbon atoms which may have a substituent, and examples thereof include phenylthio and 4-methoxyphenylthio. The acyloxy group is an acyloxy group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), for example, acetoxy,
Examples include propanoyloxy, pentanoyloxy, octanoyloxy, dodecanoyloxy, and octadecanoyloxy.

The alkylamino group is an alkylamino group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), for example, methylamino, dimethylamino, diethylamino, dibutylamino, octylamino, dioctylamino, undecyl Amino can be mentioned.

The amide group is an amide group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), for example, acetamido, acetylmethylamino, acetyloctylamino,
Examples include acetyldecylamino, acetylundecylamino, acetyloctadecylamino, propanoylamino, pentanoylamino, octanoylamino, octanoylmethylamino, dodecanoylamino, dodecanoylmethylamino, and octadecanoylamino.

The sulfonamide group is a sulfonamide group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), for example, methanesulfonamide, ethanesulfonamide, propylsulfone Amide,
Examples thereof include 2-methoxyethylsulfonamide, 3-aminopropylsulfonamide, 2-acetamidoethylsulfonamide, octylsulfonamide, and undecylsulfonamide.

The alkoxycarbonylamino group is an alkoxycarbonylamino group having 2 to 18 carbon atoms (preferably having 2 to 6 carbon atoms), for example, methoxycarbonylamino, ethoxycarbonylamino, octyloxycarbonylamino, undecyloxycarbonyl Amino can be mentioned.

The alkoxysulfonylamino group is an alkoxysulfonylamino group having 1 to 18 carbon atoms (preferably having 1 to 6 carbon atoms), for example, methoxysulfonylamino, ethoxysulfonylamino, octyloxysulfonylamino, undecyloxysulfonyl. Amino can be mentioned.

The sulfamoylamino group has 0 to 1 carbon atoms.
8 (preferably 0 to 6 carbon atoms) sulfamoylamino group, for example, methylsulfamoylamino, dimethylsulfamoylamino, ethylsulfamoylamino, propylsulfamoylamino, octylsulfamoylamino And undecylsulfamoylamino.

The ureido group is a ureido group which may have a substituent having 1 to 18 carbon atoms (preferably, 1 to 6 carbon atoms). Examples thereof include ureido, methylureido, N,
N-dimethylureide, octylureide and undecylureide can be mentioned.

The thioureido group is a thioureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), for example, thioureido, methylthioureido, N, N-dimethylthioureido. Octylthioureido and undecylthioureide.

The acyl group is an acyl group having 1 to 18 carbon atoms (preferably 1 to 6 carbon atoms), and examples thereof include acetyl, benzoyl, octanoyl, decanoyl, undecanoyl and octadecanoyl.

The alkoxycarbonyl group has 2 to 1 carbon atoms.
It is an alkoxycarbonyl group having 8 (preferably 2 to 6 carbon atoms), and examples thereof include methoxycarbonyl, ethoxycarbonyl, octyloxycarbonyl, and undecyloxycarbonyl.

The carbamoyl group is a carbamoyl group which may have a substituent having 1 to 18 carbon atoms (preferably, 1 to 6 carbon atoms), for example, carbamoyl, N, N-
Dimethylcarbamoyl, N-ethylcarbamoyl, N-
Octylcarbamoyl, N, N-dioctylcarbamoyl and N-undecylcarbamoyl can be mentioned.

The alkylsulfonyl group has 1 to 18 carbon atoms.
It is an alkylsulfonyl group (preferably having 1 to 6 carbon atoms) which may have a substituent, and examples thereof include methanesulfonyl, ethanesulfonyl, 2-chloroethanesulfonyl, octanesulfonyl, and undecanesulfonyl.

The alkylsulfinyl group has 1 to 1 carbon atoms.
It is an alkylsulfinyl group having 8 (preferably 1 to 6 carbon atoms), and examples thereof include methanesulfinyl, ethanesulfinyl and octanesulfinyl.

The sulfamoyl group is a sulfamoyl group which may have a substituent having 0 to 18 carbon atoms (preferably 0 to 6 carbon atoms), for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, Octylsulfamoyl, dioctylsulfamoyl and undecylsulfamoyl can be mentioned.

L¹ And L² Is independently divalent concatenation
Represents a group. Here, the divalent linking group means a carbon atom, nitrogen
Atom, oxygen atom or sulfur atom, X
¹ , X ²Is a 4- to 8-membered ring in cooperation with the carbon atom to which is attached
Is configured.

L¹ , And L² Is a specific example of -C
(R⁴) (R⁵)-, -C (R⁶) =, -N (R⁷) −, −
2 constituted by combining N =, -O-, and -S-
And a valent linking group. Where R⁴ , R
⁵ , R⁶ And R⁷ Are each independently a hydrogen atom or
And the details thereof are described in the above R.¹ , R² , R³At
Synonymous with what was described. Also, this 4- to 8-membered ring
It may form a saturated or unsaturated condensed ring.
Examples of the fused ring include a cycloalkyl ring, an aryl ring and
May be a heterocyclic ring.¹
 , R² , R ³ This is synonymous with the one described in.

The 4- to 8-membered ring will be described in more detail.

Examples of the four-membered ring include cyclobutanedione, cyclobutenedione and benzocyclobutenequinone.

Examples of the 5-membered ring include cyclopentanedione, cyclopentenedione, cyclopentanedione,
Cyclopentenetrione, indandione, indantrione, tetrahydrofurandion, tetrahydrofurantrione, tetrahydropyrroledione, tetrahydropyrroletrione, tetrahydrothiophenedione,
Tetrahydrothiophenetrione can be mentioned.

Examples of the 6-membered ring include benzoquinone, quinomethane, quinodimethane, quinoneimine, quinonediimine, thiobenzoquinone, dithiobenzoquinone, naphthoquinone, anthraquinone, dihydrochromementione, dihydropyridinedione, dihydropyrazinedione, dihydropyrimidinedione, dihydropyridazinedione, Examples thereof include dihydrophthalazinedione, dihydroisoquinolinedione, and tetrahydroquinolinetrione.

Examples of the 7-membered ring include cycloheptanedione, cycloheptanetrione, azacycloheptanetrione, diazacycloheptanetrione, oxocycloheptanetrione, dioxocycloheptanetrione, and oxoazacycloheptanetrione. it can.

Examples of the 8-membered ring include cyclooctanedione, cyclooctanetrione, azacyclooctanetrione, diazacyclooctanetrione, oxocyclooctanetrione, dioxocyclooctanetrione, oxoazacyclooctanetrione, and cyclooctenedione. , Cyclooctadienedione and dibenzocyclooctenedione.

The ring formed by L ¹ and L ² together with the carbon atom to which X ¹ and X ² are bonded is preferably a 6-membered ring.

The organic oxidizing agent is more preferably a compound represented by the following formula (IV-1).

[0151]

Embedded imageWhere X¹¹, X²²= NR represented by⁸ , And = C
R⁹ R¹⁰Is X in the general formula (IV).
¹ , X² = NR represented by¹ , And = CR²R³ When
It has the same meaning, and the preferred range is also the same. Also R⁸
 , R⁹And R ¹⁰The substituent represented by the general formula
R in (IV)¹ , R² And R³Replace with
It has the same meaning as the group, and its preferred range is also the same.

Each of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ independently represents a hydrogen atom or a substituent. When R ¹¹ and R ¹² or R ¹³ and R ¹⁴ simultaneously serve as a substituent, they may be connected to each other to form an unsaturated condensed ring. The unsaturated condensed ring may have a substituent, and examples of the substituent include the same ones as described in the above R ^{1 to} R ³ .

It is preferable that X ¹¹ and X ²² each independently represent an oxygen atom or a ＝ CR ⁹ R ¹⁰ group, more preferably an oxygen atom or a ＝ CR ⁹ R ¹⁰ group at the same time. Here, R ⁹ and R ¹⁰ are preferably each independently a halogen atom, a cyano group, an acyl group, an alkoxycarbonyl group or an alkylsulfonyl group.

The case where X ¹¹ and X ²² are simultaneously oxygen atoms will be described.

X¹¹, X²²Are simultaneously oxygen atoms
If R¹¹, R¹², R¹³And R ¹⁴At least 2
More preferably, one is an electron-withdrawing group. Here
A child-withdrawing group is a substituent having a positive Hammett σp value.
Means, specifically, halogen atom, cyano group, nitro
Group, acyl group, alkoxycarbonyl group, carbamoyl
Group, alkylsulfonyl group, and alkylsulfinyl
Groups.

When X ¹¹ and X ²² are simultaneously an oxygen atom, a particularly preferred combination is R ¹¹ ,
R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group, a nitro group, an alkoxy group, an alkylthio group, an amino group, an alkylamino group, an amide group, a sulfonamide group, a sulfa Moylamino group, alkoxycarbonylamino group, alkoxysulfonylamino group, ureido group, thioureido group, acyl group, alkoxycarbonyl group, carbamoyl group, alkylsulfonyl group, alkylsulfinyl group, and sulfamoyl group, at least two of which are This is the case with an electron-withdrawing group.

As the most preferable combination,
R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, an alkylthio having 1 to 6 carbon atoms. Group, amide group having 1 to 6 carbon atoms, 1 to 6 carbon atoms
A sulfonamide group, a ureido group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group having 1 to 6 carbon atoms, and a 1 to 6 carbon atoms
And at least two of them are a halogen atom, a cyano group, an alkylsulfonyl group or an alkylsulfinyl group.

X ¹¹ and X ²² simultaneously = CR ⁹ R ¹⁰
When it is a group, the organic oxidizing agent has the following general formula (IV-2)
Particularly preferred is a compound represented by the formula:

[0159]

Embedded image In the formula, R ¹⁵ , R ¹⁶ , R ¹⁷ , and R18 each independently have the same meaning as that described for R ^{11 to} R ¹⁴ .

The organic oxidizing agent is most preferably a compound represented by the following formula (IV-3) or (IV-4).

[0161]

Embedded image

Embedded image In Formula (IV-3), R ¹⁹ represents a halogen atom, a cyano group, an alkoxy group, an alkylthio group, an amide group, a sulfonamide group, a ureido group, an acyl group, or an alkoxycarbonyl group. R ²⁰ has the same meaning as described for R ^{1 to} R ³ . m4 represents an integer of 1 to 4, and when m4 or 4-m4 represents an integer of 2 or more, a plurality of R ³¹ and a plurality of R ³² may be the same or different.

In the general formula (IV-4), R ²¹ represents a hydrogen atom or a substituent. Here, the substituent means the above R ¹ to
It means the same as those described in R ^3. m5 represents an integer of 0 to 6, and when m5 represents an integer of 2 or more,
A plurality of R ²¹ may be the same or different.

In the general formula (IV-3), R ¹⁹ and R
^Twenty preferred combinations will be described.

R ¹⁹ is a halogen atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 1 to 8 carbon atoms, or an alkoxycarbonyl group having 2 to 6 carbon atoms, and R ²⁰ is a hydrogen atom, A combination that is an alkyl group having 1 to 6 is preferable, and a most preferable combination is that R ¹⁹ is an alkoxy group having 1 to 6 carbon atoms and R ²⁰ is a hydrogen atom.

The organic oxidizing agent represented by the general formula (IV-3) is particularly preferably a compound represented by the following formula.

[0166]

Embedded image In the general formula (IV-4), R ²¹ is preferably a hydrogen atom, an alkyl group, a halogen atom, a cyano group, an alkoxy group, an alkylthio group, an amide group, a sulfonamide group,
A ureido group or an acyl group, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, Amide group of number 1 to 6, carbon number 1
A sulfonamide group of 6, a ureido group of 1 to 6 carbon atoms, and an acyl group of 1 to 6 carbon atoms, particularly preferably a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, and a bromine atom. , A cyano group or an alkoxy group having 1 to 6 carbon atoms, most preferably a hydrogen atom.

Specific examples of the organic oxidizing agent used in the present invention are described below.

[0168]

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Embedded image The compound represented by the general formula (IV) is described, for example, in J. Chem. S
oc.Perkin Trans. 1,611 (1992), Synthesis, 546 (197
It can be easily synthesized according to a general synthesis method such as 1).
In addition, the following synthesis examples and methods based thereon can also be used.

Synthetic Example The exemplified compound (A-22) according to the present invention was synthesized according to the following formula.

[0170]

Embedded image Synthesis of (A-22a) 1,4-dibromo-2,5-difluorobenzene 2.7
2 g, potassium iodide 24.9 g, copper iodide 9.53 g, and HMPA (hexamethylphosphoric triamide) 3
0 ml were mixed and heated to 150-160 ° C under nitrogen. After completion of the reaction, a diluted hydrochloric acid solution and ether were poured into the reaction solution, and a copper salt was filtered, followed by extracting an organic layer. The organic layer was washed with aqueous sulfite, dried over sodium sulfate, filtered, and the filtrate was concentrated under reduced pressure to obtain 2.93 g of (A-22a) as yellow crystals.

Synthesis of (A-22b) 3.66 g of (A-22a), 2.64 of malononitrile
g, sodium hydride 1.44 g, and bistriphenylphosphine palladium chloride 0.21 g in THF.
(Tetrahydrofuran) (60 ml) was added, and the mixture was refluxed under heating for 12 hours. After completion of the reaction, the reaction solution was poured into 1N hydrochloric acid, and the white precipitate was separated by filtration and dried to obtain 2.68 g of a white solid (A-22b).

Synthesis of (A-22) To 3.36 g of (A-22b), 100 ml of water was added, and an excessive amount of bromine water was slowly added dropwise to the suspension. After standing overnight, the resulting red precipitate was filtered off, washed with cold water and dissolved in 60 ml of methylene chloride. The solution was dried over sodium sulfate, treated with activated carbon, and the solvent was distilled off. As a result, yellow crystals 3.11 of the target compound (A-22) were obtained.
g was obtained.

The exemplified compound (A-58) according to the present invention was synthesized according to the following formula.

[0174]

Embedded image Synthesis of (A-58a) 25.0 g of chloranil was dissolved in 60 ml of acetonitrile, and ammonia gas was continuously introduced into the suspension. The obtained tea solid was collected by filtration, water and then acetonitrile 100
and then dried under reduced pressure (A-58a) 19.6
g was obtained.

Synthesis of (A-58) 2.1 g of (A-58a), 4.4 g of lauric chloride
g, and 2.8 ml of triethylamine in 100 ml of DMF.
Then, the mixture was heated at 70 ° C. After heating for 7 hours, the mixture was poured into 300 ml of cold water and extracted with ethyl acetate. After drying over sodium sulfate, the mixture was concentrated, and recrystallized from acetonitrile to obtain 1.7 g of yellow crystals of the target compound (A-58).

The organic oxidizing agent represented by the general formula (IV) may be used alone or in combination with another known quencher.

A typical example of the quencher to be combined is a compound represented by the general formula (II) described in JP-A-3-224793.
Metal complexes, diimmonium salts, aminium salts represented by I), (IV) or (V);
And the nitroso compounds described in JP-A-7-300 and JP-A-2-300288. Particularly preferred quenchers to be combined are metal complexes (for example, PA-1006 (Mitsui Toatsu Fine Co., Ltd.)) or diimmonium salts (for example, IRG-
023 and IRG-022 (Nippon Kayaku Co., Ltd.), and the most preferred are diimmonium salts. These quenchers can be used in combination of two or more depending on the purpose.

The amount of the organic oxidizing agent represented by the general formula (IV) is preferably in the range of 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, based on 100 parts by weight of the organic dye. More preferably, it is particularly preferably in the range of 1 to 25 parts by weight, most preferably 1 to 10 parts by weight.

The amount of the quencher to be added depends on the amount of the organic dye 1
It is preferably in the range of 1 to 100 parts by weight, more preferably in the range of 1 to 50 parts by weight, particularly preferably in the range of 1 to 25 parts by weight, most preferably in the range of 1 to 25 parts by weight, per 100 parts by weight. The range is 10 parts by weight.

Next, the organic dye used in the present invention will be described.

Examples of usable organic dyes include cyanine dyes, merocyanine dyes, phthalocyanine dyes, oxonol dyes, pyrylium dyes, thiopyrylium dyes, triarylmethane dyes, polymethine dyes, and squarium dyes. , Azulenium dyes,
Examples include naphthoquinone dyes, anthraquinone dyes, indophenol dyes, indoaniline dyes, aminium / diimmonium dyes, and pyran dyes.

Next, the symmetric or asymmetric cyanine dye represented by formula (III) will be described. In the general formula (III), the nucleus formed by Z ¹ and Z ² includes a 3,3-dialkylindolenine nucleus and a 3,3-
Dialkyl benzoindolenine nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, thiazoline nucleus,
Oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, oxazoline nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, selenazoline nucleus, tellurazole nucleus, benzotellurazole nucleus, naphthotellurazole nucleus, tellrazoline nucleus, imidazole nucleus, benzo Imidazole nucleus, naphthoimidazole nucleus, pyridine nucleus, quinoline nucleus, isoquinoline nucleus, imidazo [4,5-
b] A quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, a pyrimidine nucleus and the like. The 5- or 6-membered nitrogen-containing heterocyclic ring mentioned here may have a substituent, if possible, and the substituent may be, for example, R 1 described in the aforementioned general formula (IV). ^The same ones as ¹ , R ² and R ³ can be mentioned.

Examples of the above substituents will be described in more detail.

The alkyl group is an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms) which may have a linear, branched or cyclic substituent.
Ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, 2-hydroxyethyl, 4-carboxybutyl, hexyl, octyl, benzyl and phenethyl.

The alkenyl group is a linear, branched or cyclic alkenyl group having 2 to 18 carbon atoms (preferably 2 to 8 carbon atoms), for example, vinyl, allyl, 1-propenyl, 2-pentenyl, , 3-butadienyl, and 2-
Octenyl can be mentioned.

The aralkyl group is an aralkyl group having 7 to 10 carbon atoms, such as benzyl.

The aryl group is an aryl group having 6 to 10 carbon atoms which may have a substituent, for example, phenyl, naphthyl, 4-carboxyphenyl, 3-carboxyphenyl, 3,5-dicarboxyphenyl , 4-methanesulfonamidophenyl, and 4-butanesulfonamidophenyl.

The heterocyclic group is a 5- or 6-membered saturated or unsaturated heterocyclic group composed of a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom. One or more kinds of elements may be used, for example, an oxazole ring, a benzoxazole ring,
5-carboxybenzoxazole ring, thiazole ring,
Examples include an imidazole ring, a pyridine ring, a sulfolane ring, a furan ring, a thiophene ring, a pyrazole ring, a pyrrole ring, a chroman ring, and a coumarin ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

The alkoxy group is an alkoxy group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms), and examples thereof include methoxy, ethoxy, propoxy and butoxy.

The aryloxy group is an aryloxy group which may have a substituent having 6 to 10 carbon atoms, and examples thereof include phenoxy and p-methoxyphenoxy.

The alkylthio group is an alkylthio group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methylthio and ethylthio.

The arylthio group is an arylthio group having 6 to 10 carbon atoms, such as phenylthio.

The acyloxy group is an acyloxy group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include acetoxy, propanoyloxy, pentanoyloxy and octanoyloxy.

The alkylamino group is an alkylamino group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) and includes, for example, methylamino, dimethylamino, diethylamino, dibutylamino and octylamino.

The amide group is an amide group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms), for example, acetamido, propanoylamino, pentanoylamino, octanoylamino, octanoylmethylamino, and Benzamide can be mentioned.

The sulfonamide group is a sulfonamide group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms), for example, methanesulfonamide, ethanesulfonamide,
Mention may be made of propylsulfonamide, butanesulfonamide, and benzenesulfonamide.

The alkoxycarbonylamino group is an alkoxycarbonylamino group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include methoxycarbonylamino and ethoxycarbonylamino.

The alkoxysulfonylamino group is an alkoxysulfonylamino group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and includes, for example, methoxysulfonylamino and ethoxysulfonylamino.

The sulfamoylamino group has 0 to 1 carbon atoms.
8 (preferably having 0 to 8 carbon atoms) a sulfamoylamino group which may have a substituent, for example, methylsulfamoylamino, dimethylsulfamoylamino, ethylsulfamoylamino, propylsulfamoyl Amino and octylsulfamoylamino can be mentioned.

The ureido group is a ureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), for example, ureido, methylureido, N, N
-Dimethylureide and octylureide.

The thioureido group is a thioureido group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and examples thereof include thioureido, methylthioureido, and N, N-dimethylthioureido. And octylthioureido.

The acyl group is an acyl group having 1 to 18 carbon atoms (preferably having 1 to 8 carbon atoms) and includes, for example, acetyl, benzoyl and propanoyl.

The alkoxycarbonyl group has 1 to 1 carbon atoms.
It is an alkoxycarbonyl group having 8 (preferably 1 to 8 carbon atoms), and examples thereof include methoxycarbonyl, ethoxycarbonyl, and octyloxycarbonyl.

The carbamoyl group is a carbamoyl group which may have a substituent having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), and includes, for example, carbamoyl, N, N-dimethylcarbamoyl and N- Ethylcarbamoyl can be mentioned.

The alkyl or arylsulfonyl group is an alkyl or arylsulfonyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms), for example, methanesulfonyl,
Ethane sulphonyl and benzene sulphonyl can be mentioned.

The alkylsulfinyl group has 1 to 1 carbon atoms.
It is an alkylsulfinyl group having 8 (preferably 1 to 8 carbon atoms), and examples thereof include methanesulfinyl, ethanesulfinyl, and octanesulfinyl.

The sulfamoyl group is a sulfamoyl group which may have a substituent having 0 to 18 carbon atoms (preferably 0 to 8 carbon atoms), and includes, for example, sulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, Butylsulfamoyl, octylsulfamoyl, and phenylsulfamoyl can be mentioned.

Z ¹ and Z ² are preferably a substituted or unsubstituted 3,3-dialkylindolenine nucleus or 3,3-dialkylbenzoindolenine nucleus.

R ³⁰ and R ³¹ each independently represent an alkyl group.

The alkyl group represented by R ³⁰ and R ³¹ is
A substituted or unsubstituted straight-chain, branched-chain or cyclic alkyl group having 1 to 18 carbon atoms (preferably 1 to 8 carbon atoms); And the preferred range is also the same. Preferably, it is an unsubstituted alkyl group or an alkyl group substituted with an aryl group, a halogen atom, a hydroxy group, an alkoxy group, an acyloxy group, an amide group, a sulfonamide group, an alkoxycarbonyl group, a carboxyl group, or a sulfo group. Examples of these include methyl, ethyl, propyl, butyl, isobutyl, 2-ethylhexyl, octyl, benzyl, 2-phenylethyl, 2-hydroxyethyl, 3-hydroxypropyl,
2-carboxyethyl, 3-carboxypropyl, 4-
Carboxybutyl, carboxymethyl, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl,
-Sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl, 2-acetoxyethyl, carbomethoxymethyl, and 2-methanesulfonylaminoethyl. .

The methine groups represented by L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ are each independently an unsubstituted or substituted methine group. The substituent has the same meaning as that described above, and the preferred range is also the same. When the compound has a substituent, the substituents may be connected to each other to form a 5- to 7-membered ring, or a ring may be formed with an auxiliary chromophore. Here, as the 5- to 7-membered ring, for example, a cyclopentene ring, 1-
Examples thereof include a dimethylaminocyclopentene ring, a 1-diphenylaminocyclopentene ring, a cyclohexene ring, a 1-chlorocyclohexene ring, an isophorone ring, a 1-morpholinocyclopentene ring, and a cycloheptene ring.

It is preferable that n1 and n2 are either n1 is 0 and n2 is 1, or n1 is 2 and n2 is 0.

M1 represents a charge balancing counter ion. M1 may be a cation or an anion.

Examples of the cation include alkali metal ions such as sodium ion, potassium ion and lithium ion, and organic ions such as tetraalkylammonium ion and pyridinium ion.

The anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, a fluorine ion, a chlorine ion, a bromine ion, an iodine ion), a sulfonate ion (eg, a methanesulfonic acid ion). , Trifluoromethanesulfonate ion,
Methyl sulfate ion, p-toluenesulfonic acid ion, p
-Chlorobenzenesulfonic acid ion, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion, etc.), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate Ion, picrate ion,
Acetate ion, a metal complex ion represented by the following formula:

Embedded image And a phosphate ion (for example, hexafluorophosphate ion, a phosphate ion represented by the following formula:

Embedded image Can be mentioned.

M1 is a number necessary to balance the charges (0
(Preferably 0 to 4), and 0 when a salt is formed in the molecule. p and q each independently represent 0 or 1. p and q are preferably both 0.

The compound represented by formula (III) may form a bis-type structure by bonding two kinds on any carbon atom.

The organic dye is preferably a cyanine dye represented by the following formula (III-1).

[0220]

Embedded image The cyanine dye compound represented by the general formula (III-1)
More preferably, the compound is a combination of the following.

X ³ and X ⁴ each independently represent an oxygen atom,
-C ( ^R34 ) ( ^R35 )-or -N ( ^R36 )-
R ³² and R ³³ are each independently an unsubstituted or alkyl group having 1 to 6 carbon atoms substituted with an alkoxy group or an alkylthio group, and R ³⁴ , R ³⁵ and R
³⁶ are each independently an unsubstituted alkyl group having 1 to 6 carbon atoms, and R ³⁷ may have a hydrogen atom or a substituent;
An alkyl group having 1 to 6 carbon atoms, a phenyl group, a pyridyl group,
A pyrimidyl group, a succinimide group, a benzoxazole group or a halogen atom; Z ¹¹ and Z ²² each independently represent an atomic group necessary for forming an unsubstituted benzene ring, a naphthalene ring or a quinoxaline ring, or a methyl group; An atomic group necessary for forming a benzene ring substituted with one or two groups selected from a chlorine atom, a fluorine atom, a methoxy group or an ethoxy group, and M2 is a perchlorate ion, a hexafluorophosphate ion A metal complex ion represented by the following formula:

Embedded image Or a sulfonate ion represented by the following formula:

Embedded image Are preferred. m2 represents the valence of M2.

In formula (III-1), the most preferred
A good combination is X³ And X ⁴Is simultaneously -C
(R³⁴) (R³⁵)-Or simultaneously -N (R³⁶)-
And R³²And R³³Are each independently an unsubstituted
Alkyl group (preferably methyl group, ethyl group, propyl
Group, isopropyl group, butyl group)³⁴, R
³⁵And R³⁶Are each independently a methyl group or an ethyl group.
R³⁷Is hydrogen atom, methyl group, ethyl group, chlorine atom
Or a bromine atom;¹¹And Z²²Is not replaced at the same time
A benzene, naphthalene or quinoxaline ring
It is an atomic group necessary to form.

Specific examples of the organic dye represented by formula (III) used in the present invention are described below.

[0224]

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Embedded image The compound represented by the general formula (III) is described in "FM Hemmer", "Heterocyclic.
Heterocyclic Compounds-Cyanine D
yes and Related Compounds), John Wiley & Sons-New York,
London, 1964; DM Sturmer, Heterocyclic.
Heterocyclic Compounds- Special Topics in Heterocyclic Compounds
Special topics in heterocyclic chemistry)
Chapter 8, section 14, pages 482-515, John Wiley & Sons, Inc.-New York, London, 1977; "Rodd's Chemistr.
y of Carbon Compounds) '' 2nd.Ed.vol.IV, partB, 19
77, Chapter 15, pages 369-422, Elsevier Science Public Company, Inc.
ir Science Publishing Company Inc.), New York, and the like.

In the present invention, the following general formula (V)
A photofunctional film made of an azo dye represented by formula (1) is also preferably used.

[0226]

Embedded image Wherein, k, M is k, respectively and M synonymous in the general formula (II-1) or general formula (II-2), X represents an oxygen atom, a sulfur atom or = ^{NR 21,, Z 11}
Represents an atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, and Z ¹² represents an atomic group necessary for completing an aromatic ring or a heteroaromatic ring.

Specific examples of the azo dye represented by formula (V) are shown below.

[0228]

Embedded image The azo compound represented by the general formula (V) can be synthesized by an azo coupling reaction of an aromatic diazonium according to a conventional method.

In the present invention, a high molecular compound may be used in combination in order to easily maintain an amorphous state without crystallizing an organic dye or the like. Examples of such a polymer compound include gelatin, dextran, rosin, natural polymer substances such as rubber, nitrocellulose, cellulose acetate, cellulose derivatives such as cellulose acetate butyrate, polyethylene, polystyrene, polypropylene, and polyisobutylene. Hydrocarbon resins, polyvinyl chloride, polyvinylidene chloride, vinyl resins such as polyvinyl chloride-polyvinyl acetate copolymer, polyether,
Initial polymerization of thermosetting resins such as acrylic resins such as polyacrylamide, polymethyl acrylate and polymethyl methacrylate, polyesters, polyurethanes, polyvinyl alcohol, chlorinated polyolefins, epoxy resins, butyral resins, rubber derivatives, and phenol-formaldehyde resins And synthetic high-molecular substances such as substances.

[0230] The dielectric block of the present invention is formed of a dielectric material that is transparent to the wavelength of the modulated light. In particular, a material made of a material having a refractive index with respect to the wavelength of the modulated light in the range of 1.2 to 3 is preferable. Specifically, BK7, high-refractive-index glass, polycarbonate and the like can be mentioned.

As the material of the metal film used in the present invention, a metal that satisfies the conditions for generating surface plasmon resonance with light having any wavelength in the range of 350 nm to 2000 nm is used. Specific examples include gold, silver, copper, and aluminum. The thickness of the metal film is 350 nm to 2000
The film thickness is such that surface plasmon resonance occurs with light having any wavelength in the range of nm, but is preferably in the range of 10 nm to 70 nm. These metal films can be provided on the dielectric block by a known method such as vapor deposition, sputtering, and plating.

A thin layer (preferably 5 nm or less) of an anchor material made of Cr, Ge, or the like may be provided between the dielectric block and the metal film in order to obtain good adhesion between the two. As described above, the term “metal film formed on one surface of the dielectric block” in the present invention means not only a film formed directly on this surface but also a metal film formed through some other thin film. Shall be included. The same applies to the “optically functional film formed on the metal film”.

The photofunctional film of the present invention can be obtained by applying any one of the above dyes onto a metal film by a known method such as spin coating, vapor deposition, sputtering and the like. The film thickness is controlled so as to include a condition in which surface plasmon resonance occurs for light having any wavelength in the range of 350 nm to 2000 nm.
The range of m is preferred.

In the surface plasmon light modulation device according to the present invention, the incident angle of the modulated light with respect to the one surface of the dielectric block is, for example, such that when the optically functional film is irradiated with the modulation driving light, the surface plasmon resonance is applied to the metal film. The surface plasmon resonance is excited relatively weakly when not illuminated and is set to an angle that is relatively weakly excited or not excited.

Alternatively, the incident angle of the modulated light is such that surface plasmon resonance is relatively strongly excited in the metal film when the optically functional film is not irradiated with the modulation driving light, and the surface plasmon resonance is relatively excited when irradiated. The angle may be set to be weakly excited or not excited.

On the other hand, when the modulated light is linearly polarized light, the dielectric block is desirably arranged so that the modulated light is incident on the one surface as P-polarized light.

As the dielectric block, one formed in a prism shape can be suitably used. Alternatively, the dielectric block is integrated with a prism having a refractive index equal to the dielectric block via a refractive index matching liquid having a refractive index equal thereto, and
The modulated light may be introduced to one surface of the dielectric block through the prism.

[0238]

According to the surface plasmon light modulation device of the present invention, the photofunctional film is formed from a dye containing an electron donor and an electron acceptor capable of photoelectron transfer, and therefore, has a higher function than a conventional device. High-speed light modulation is possible, and it is possible to respond to light in various wavelength ranges.
Further, the modulation operation can be performed with the lower power modulation driving light.

The angle of incidence of the modulated light with respect to the one surface of the dielectric block is such that the surface plasmon resonance is excited in the metal film when the optically functional film is irradiated with the modulation driving light, and the surface plasmon resonance is excited when the light is not irradiated. When the angle is set so as not to be excited, the light modulation element is a type of a type in which the modulated light is turned off (or the light amount is reduced) by irradiation of the modulation drive light.

Conversely, the incident angle of the modulated light is set to an angle at which surface plasmon resonance is excited in the metal film when the optically functional film is not irradiated with the modulation driving light, and surface plasmon resonance is not excited when the metal film is irradiated. In this case, a light modulation element of a type in which the modulated light is turned on (or the amount of light is increased) by irradiation of the modulation drive light.

[0241]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows a side surface shape of a surface plasmon light modulation device according to a first embodiment of the present invention. The surface plasmon light modulating element has a prism-shaped dielectric block 11 arranged such that the modulated light 10 enters the surface 11a via the inside thereof at a total reflection angle, and the surface of the dielectric block 11 is provided on one surface 11a. Metal film 12 formed
And an optical functional film 13 formed on the metal film 12, and a drive light source 15 for irradiating the optical functional film 13 with modulation drive light 14.

In this example, the modulated light 10 has a wavelength of 680 n.
m, and the dielectric block 11 has one surface 11a
The modulated light 10 is disposed so as to enter as P-polarized light. The dielectric block 11 is made of high-refractive-index glass, and has a refractive index of 2.05 for a wavelength of 680 nm.

It is desirable to use a laser as the drive light source 15, and in this embodiment, a semiconductor laser that emits the modulated drive light 14 having a wavelength of 532 nm is used.

On the other hand, the metal film 12 is made of gold, and has a thickness of 15 nm as an example. The optical functional film 13 is
It is formed using any of the dyes containing an electron donor and an electron acceptor capable of photoelectron transfer described in detail above.
In this embodiment, the refractive index n with respect to the wavelength 680 nm is 1.60 when the modulation drive light 14 having the wavelength of 532 nm is not irradiated, and is 1.61 when the modulation drive light 14 is irradiated. Using a mixture obtained by mixing the compound represented by A-4 among the compounds represented by IV-4) and the compound represented by B-17 among the compounds represented by the general formula (III) in a weight ratio of 15: 100. Is formed. The film thickness is 1 nm to 10 μm,
Preferably from 5 nm to 1 μm, more preferably from 10 nm to
It is about 500 nm.

The operation of the surface plasmon light modulation device will be described below. As described above, the wavelength of the optical functional film 13
The refractive index n for 680 nm is 1.60 and 1.6 when the modulation drive light 14 is not irradiated and when it is irradiated.
It becomes 1. The relationship between the incident angle θ of the modulated light 10 with respect to the interface between the dielectric block 11 and the optical functional film 13 and the reflectance thereat is that the refractive index n of the optical functional film 13 is 1.60, 1.61. In this case, the characteristics are indicated by a broken line and a solid line in FIG. 2, respectively.

Therefore, the incident angle θ is set to, for example, 51.8 °.
When the optical functional film 13 is not irradiated with the modulation driving light 14 (when the refractive index n is 1.60), the reflectance becomes almost 0%. When the light 14 is irradiated (when the refractive index n is 1.61), the above-mentioned reflectance is almost 100%, so that the modulated light 10 traveling in the direction of arrow A in FIG. According to non-irradiation
ON-OFF modulation can be performed.

As apparent from FIG. 2, if the incident angle θ of the modulated light 10 with respect to the interface between the dielectric block 11 and the optical functional film 13 is set to 52.2 °, the optical functional Membrane 13
Is not irradiated with the modulation driving light 14 (the refractive index n is 1.60).
), The reflectance becomes almost 100%, and the optical functional film 13 is irradiated with the modulation driving light 14 (the refractive index n is 1.
61), the reflectance is about 5%, so
The modulated light 10 traveling in the direction of arrow A in FIG.
Can be modulated so that the light amount becomes small and the light amount becomes large in accordance with the irradiation and non-irradiation of light.

In the surface plasmon light modulation device of the present embodiment, since the photofunctional film 13 is formed using a dye containing an electron donor and an electron acceptor capable of photoelectron transfer, the surface plasmon light modulation device is different from the conventional device. It also enables high-speed light modulation, can cope with light in various wavelength ranges, has high repetition durability, and can perform a modulation operation with lower-power modulation driving light. The reason is as described in detail above.

In the above, a mixture of the compound of A-4 belonging to the general formula (IV-4) and the compound B-17 belonging to the general formula (III) was used as a material for the optical functional film. Similar results were obtained when the compounds in Table 4) were used.

[0250]

[Table 4] Next, a second embodiment of the present invention will be described with reference to FIG. The surface plasmon light modulation device of the second embodiment differs from the device of FIG. 1 in that a substantially rectangular parallelepiped dielectric block 30 made of glass is used instead of the prismatic dielectric block 11. Basically different. The dielectric block 30 is coupled to the upper surface of the prism 32 via a refractive index matching liquid 31.

In this apparatus, the modulated light 10 is introduced toward one surface 30a of the dielectric block 30 through the prism 32, the refractive index matching liquid 31, and the dielectric block 30. The dielectric block 30 and the prism 32 are formed of the same material as each other, and are coupled via a refractive index matching liquid 31 having the same refractive index as those, so that they are optically integrated. A structure equivalent to that using a prism is realized.

Hereinafter, a result of actually modulating light by the surface plasmon light modulation device of the second embodiment will be described. FIG. 5 shows the configuration of an apparatus used for this light modulation. Reference numeral 50 in the figure denotes a surface plasmon light modulation device including the prism 32, the refractive index matching liquid 31, the substantially rectangular parallelepiped dielectric block 30, the metal film 12, and the optical functional film 13 shown in FIG. In this case, the optical functional film 13 is made of the compound (V-1) described above. The metal film 12 is made of gold as an example, and has a thickness of 50 nm.

The surface plasmon light modulating element 50 has a rotating stage 51 so that the incident angle θ of the modulated light 10 on one surface 30a (see FIG. 3) of the dielectric block 30 can be appropriately changed.
It is installed in. The modulated light 10 in this case is linearly polarized light having a wavelength of 685 nm emitted from the semiconductor laser 52. The modulated light 10 is emitted in a diverging light state from the semiconductor laser 52, is collimated by the collimator lens 53,
The direction of the linearly polarized light is adjusted by the λ / 2 plate 54 so as to be in the direction of the arrow P (that is, incident on the one surface 30a of the dielectric block 30 as P-polarized light).

The modulated light 10 has a focal length of 50 m, for example.
m, and the light is condensed by the condensing lens 55, and is incident on one surface 30a of the dielectric block 30 so as to converge there.
The light is reflected by the one surface 30a as described above. The reflected modulated light 10 is detected by a photodetector 56 such as a pin photodiode, and the output of the photodetector 56 is input to an oscilloscope 57.

On the other hand, for example, the output
The modulation driving light 14 having a wavelength of 35 mW and a wavelength of 532 nm is intensity-modulated into a predetermined pattern by an AOM (acoustic optical modulator) 61. The modulated modulation drive light 14 has, for example, a focal length of 100 mm.
And is incident on the optical functional film 13 (see FIG. 3) of the surface plasmon light modulation element 50. The modulation driving light 14 emitted from the AOM 61 in a direction other than the direction of use is blocked by the light shielding plate 63.

FIG. 6 shows the waveform of the modulated drive light 14 intensity-modulated as described above and the waveform of the modulated light 10 measured by the oscilloscope 57 together. As shown here, the modulated light 10 can be satisfactorily modulated by following the waveform of the modulation driving light 14.

Although the embodiment in which the modulated light 10 as one beam is modulated has been described above, the surface plasmon light modulation device of the present invention has a two-dimensional spread like the light projected from various projectors. It is also possible to receive light carrying image information as modulated light and use the light in such a manner that its optical path is switched by a modulation operation.

[Brief description of the drawings]

FIG. 1 is a schematic side view of a surface plasmon light modulation device according to a first embodiment of the present invention.

FIG. 2 is a graph showing the relationship between the incident angle of the modulated light on one surface of a dielectric block and the reflectance in the surface plasmon light modulation device of FIG.

FIG. 3 is a schematic side view of a surface plasmon light modulation device according to a second embodiment of the present invention.

FIG. 4 is a schematic side view showing an example of a conventional surface plasmon light modulation device.

FIG. 5 is a side view of an apparatus for measuring characteristics of the surface plasmon light modulation device of FIG.

FIG. 6 is a graph showing the modulation characteristics of the surface plasmon light modulation device measured by the device of FIG. 5;

[Explanation of symbols]

 10 Modulated light 11 Dielectric block 11a One surface of the dielectric block 12 Metal film 13 Optical functional film 14 Modulation drive light 15 Drive light source 30 Dielectric block 30a One surface of the dielectric block 31 Refractive index matching liquid 32 Prism 50 Surface plasmon light Modulation element 51 Rotation stage 52 Semiconductor laser 53 Collimator lens 54 λ / 2 plate 55 Condensing lens 56 Photodetector 57 Oscilloscope 60 Laser 61 AOM 62 Condensing lens

Claims (11)

[Claims] 1. A dielectric block arranged such that modulated light is incident on one surface thereof through the inside thereof at a total reflection angle; a metal film formed on the dielectric block; An optical functional film whose refractive index changes by light irradiation and a driving light source that irradiates the optical functional film with modulation driving light are formed on the surface plasmon light modulation element. A surface plasmon light modulation device comprising a dye containing an electron donor and an electron acceptor capable of photoelectron transfer. 2. The surface plasmon light modulation device according to claim 1, wherein said optical functional film is made of a compound represented by the following general formula (I). Embedded image In the formula, DYE ⁺ represents a monovalent cyanine dye cation, n represents an integer of 1 or more, and R ₅ and R ₆ each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group or R ₅ and R ₆ , R ₅ and R ₇ , R ₆ and R ₈ or R ₇ and R ₈ may be linked to each other to form a ring, and r and s are each independently Represents an integer of 0 to 4, and when r and s are 2 or more, even when a plurality of r and s are each the same as each other,
It may be different. 3. The photofunctional film according to claim 1, wherein the photofunctional film has the following general formula (II-
The surface plasmon light modulation device according to claim 1, wherein the dye compound represented by 1) and the dye compound represented by formula (II-2) are formed alone or in combination. Embedded image In the formula, A ¹ , A ² , B ¹ and B ² represent a substituent,
L ¹ , L ² , L ³ , L ⁴ and L ⁵ represent a methine group;
¹ represents ＝ O, ＮＲNR, ＣC (CN) ₂ (where R represents a substituent), and X ² represents —O, —NR, —C (CN) _2.
(Where R represents a substituent), and m and n each represent an integer of 0 to 2. Y ¹ and E each represent an atom or a group of atoms necessary to form a carbocyclic or heterocyclic ring, and Z ¹ and G each represent an atom or a group of atoms necessary to form a carbocyclic or heterocyclic ring. x and y each independently represent 0 or 1. M
^{k +} represents an onium ion. k represents the number of charges. 4. The photofunctional film according to the following general formula (III)
2. An organic dye represented by the formula:
The surface plasmon light modulation device according to any one of the preceding claims. Embedded image In the formula, Z ¹ and Z ² each represent an atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring, R ³⁰ and R ³¹ each independently represent an alkyl group, and L ³ , L ⁴ , L ⁵ , L ⁶ and L ⁷ each represent a methine group, n1 and n2 each represent an integer of 0 to 2, p and q each independently represent an integer of 0 to 2,
M represents a charge balancing counter ion. 5. The optical functional film according to claim 4, wherein the optical functional film comprises a combination of an organic dye represented by the general formula (III) and an organic oxidant represented by the following general formula (IV). The surface plasmon light modulation device according to any one of the preceding claims. Embedded image In the formula, m and n each independently represent an integer of 0 to 2, and X ¹ ,
X ² represents ＮＲNR ¹ or ＣＲCR ² R ³ (R ¹ ,
R ² and R ³ represent a substituent), L ¹ and L ² each independently represent a divalent linking group. 6. The surface plasmon light modulation device according to claim 1, wherein said optical functional film is made of an organic dye represented by the following general formula (V). Embedded image In the formula, M represents a metal atom, X represents an oxygen atom, a sulfur atom,
Or = NR ²¹ , wherein R ²¹ is a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkylsulfonyl group,
Or an arylsulfonyl group, Z ¹¹ represents an atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, and Z ¹² represents an atom required for completing an aromatic ring or a heteroaromatic ring. Represents a group. 7. The incident angle of the modulated light with respect to the one surface of the dielectric block is such that when the optically functional film is irradiated with the modulation driving light, the surface plasmon resonance is relatively strongly excited in the metal film and is not irradiated. 7. The surface plasmon light modulation device according to claim 1, wherein the surface plasmon resonance is set at an angle at which the surface plasmon resonance is excited relatively weakly or not. 8. When the incident angle of the modulated light on the one surface of the dielectric block is not irradiated with the modulation driving light on the optical functional film, surface plasmon resonance is relatively strongly excited and irradiated on the metal film. 7. The surface plasmon light modulation device according to claim 1, wherein the surface plasmon resonance is set at an angle at which the surface plasmon resonance is excited relatively weakly or not. 9. The device according to claim 1, wherein the modulated light is linearly polarized light, and the dielectric block is arranged such that the modulated light is incident on the one surface as P-polarized light.
The surface plasmon light modulation device according to claim 1. 10. The apparatus according to claim 1, wherein the dielectric block is formed in a prism shape.
The surface plasmon light modulation device according to claim 1. 11. The dielectric block is integrated with a prism having a refractive index equal to the dielectric block through a refractive index matching liquid having a refractive index equal thereto, and the modulated light passes through the prism. 10. The method according to claim 1, wherein the dielectric block is provided on one surface of the dielectric block.
The surface plasmon light modulation device according to claim 1.