JP2000314904A - Optical logic element, optical logic circuit and optical oscillation circuit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an optical logic element having a simple constitution formed at a low cost. SOLUTION: This optical logic element is composed of a dielectric block 1 which is arranged so that driving light Ld is made incident on a surface 1a at the whole reflection angle via the inner part of the block, a metallic film 2 which is formed on the surface 1a of the dielectric block 1, and an optical functional film 3 which is formed on the metallic film 2 so as to be irradiated with control light Lc and whose reflective index is changed by being irradiated with light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical logic device, and more particularly, to an optical logic device which performs a logical operation by utilizing generation of surface plasmon resonance.

[0002] The present invention also relates to an optical logic circuit and an optical oscillation circuit using the above-described optical logic element.

[0003]

2. Description of the Related Art Since light has a very high transmission speed, its application to the fields of communication and arithmetic has been widely studied. In this type of field, various applications are being studied using optical circuits such as optical logic circuits.

[0004]

Conventionally, however, since there is no inexpensive optical switching element, the configuration of the optical circuit has many restrictions, and an optical circuit with a simple configuration has not been realized. More specifically, it has been extremely difficult to realize logic elements such as AND and OR as basic elements of an optical circuit, and further, an optical logic circuit and an optical oscillation circuit obtained by combining them. Further, even if an optical oscillation circuit can be realized, it has been difficult to obtain a circuit having a sufficiently high oscillation frequency.

[0005] The present invention has been made in view of the above circumstances, and an optical logic element having a simple structure and which can be formed at low cost,
Further, it is another object of the present invention to provide an optical logic circuit and an optical oscillation circuit which are inexpensive and can operate at high speed by combining such optical logic elements.

[0006]

SUMMARY OF THE INVENTION An optical logic element according to the present invention is an optical logic element for performing a logical operation on one or a plurality of input lights, wherein a driving light is incident on one surface through the inside thereof at a total reflection angle. And a metal film formed on the one surface of the dielectric block,
And a photo-functional film formed on the metal film so as to receive the control light and having a refractive index changed by the light irradiation.

In the optical logic device according to the present invention, the incident angle of the driving light on the one surface of the dielectric block is, for example, such that when the control light is irradiated on the optical functional film, surface plasmon resonance occurs on the metal film. Relatively strongly excited,
When not illuminated, the surface plasmon resonance is set to an angle that is relatively weakly excited or not excited. The optical logic element thus configured is hereinafter referred to as an a-mode optical logic element.

Alternatively, contrary to the above, the incident angle of the driving light to the one surface of the dielectric block is such that surface plasmon resonance is relatively strongly excited in the metal film when the control light is not irradiated to the optical functional film. And may be set to an angle at which surface plasmon resonance is relatively weakly excited or not excited when illuminated. The optical logic element thus configured is hereinafter referred to as a b-mode optical logic element.

According to the present invention, the a-mode optical logic element is
The present invention provides a NOT circuit using one control light, which receives one control light incident on an optical functional film of an optical logic element as input light, and is totally reflected at an interface between the dielectric block and the metal film. The driving light is emitted as output light that is a NOT operation result.

The present invention also provides an exNOR circuit using one of the a-mode optical logic elements. This circuit receives two control lights incident on the optical functional film of the optical logic element. The drive light is received as light, and the drive light totally reflected at the interface between the dielectric block and the metal film is emitted as output light which is the result of the exNOR operation.

Further, the present invention provides an AND circuit using one of the above-mentioned b-mode optical logic elements, and this circuit comprises one control light and one dielectric light incident on the optical functional film of the optical logic element. One drive light before being incident on one surface of the body block is received as two input lights, and drive light totally reflected at an interface between the dielectric block and the metal film is emitted as output light as a result of an AND operation. It is assumed that.

The present invention also provides an OR circuit using one of the above-mentioned b-mode optical logic elements. This circuit receives two control lights incident on the optical functional film of the optical logic element. The driving light is received as light, and the driving light totally reflected at the interface between the dielectric block and the metal film is emitted as output light as an OR operation result.

Although the optical logic circuit using one optical logic element of the present invention has been described above, a plurality of optical logic elements are used, and these are connected to the interface between the dielectric block of one optical logic element and the metal film. By combining the drive light totally reflected by the above so as to be incident on the other optical logic elements as the control light, various optical logic circuits and flip-flops for performing other logical operations can be formed. .

More specifically, the present invention provides an exOR circuit using two a-mode optical logic elements.
In this circuit, one a-mode optical logic element is arranged as a preceding-stage optical logic element that receives two control lights incident on the optical functional film as input light, and another a-mode optical logic element is provided. One is arranged as a subsequent optical logic element that receives drive light totally reflected at the interface between the dielectric block of the preceding optical logic element and the metal film as one control light,
The driving light totally reflected at the interface between the dielectric block and the metal film of the subsequent optical logic element is emitted as output light which is the result of the exOR operation.

The present invention also provides an a-mode optical logic element and b-mode optical logic element.
The present invention provides a NAND circuit using one optical logic element of each mode, wherein one b-mode optical logic element has one control light and one dielectric block incident on the optical functional film. One driving light before entering one surface is 2
One a-mode optical logic element is arranged as a preceding optical logic element receiving as one input light, and one a-mode optical logic element receives one drive light totally reflected at the interface between the dielectric block and the metal film of the preceding optical logic element. It is arranged as a subsequent optical logic element that receives as control light, and emits driving light totally reflected at the interface between the dielectric block and the metal film of the subsequent optical logic element as output light that is a NAND operation result. Is what you do.

Further, the present invention provides a NOR circuit using one a-mode optical logic element and one b-mode optical logic element. This circuit comprises one b-mode optical logic element. The optical logic element is arranged as a preceding optical logic element that receives two control lights incident on the optical functional film as input light, and one a-mode optical logic element is provided with a dielectric block of the preceding optical logic element, a metal film, The driving light totally reflected at the interface between the dielectric block of the latter optical logic element and the metal film is NOR-arranged as a subsequent optical logic element receiving the driving light totally reflected at the interface as one control light. It is characterized in that it is emitted as the output light as a result.

In the above-described optical logic circuit of the present invention, it is desirable that light having different wavelengths be used as a plurality of lights to be incident on one optical logic element.

Further, according to the present invention, the optical logic element of the present invention is
One or more optical oscillation circuits are provided. Specifically, one optical oscillation circuit according to the present invention includes one a-mode optical logic element and driving light totally reflected at the interface between the dielectric block and the metal film of the optical logic element, And an optical system for entering the optical functional film.

In another optical oscillation circuit according to the present invention, one b-mode optical logic element and driving light totally reflected at an interface between a dielectric block and a metal film of the optical logic element are received by the optical functional film. An a-mode optical logic element arranged as follows,
An optical system for making the drive light totally reflected at the interface between the dielectric block of the a-mode optical logic element and the metal film incident on the optical functional film of the b-mode optical logic element.

In the optical oscillation circuit of the present invention described above, a plurality of lights to be incident on one optical logic element are:
It is desirable that lights having different wavelengths be used.

In the present invention, the dielectric block is formed of a dielectric that is transparent to the wavelength of the light to be modulated. 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.

The thickness of the metal film used in the present invention is 3
This is a film thickness at which surface plasmon resonance occurs with light having any wavelength in the range of 50 nm to 2000 nm, and is usually 10 n.
A range from m to 70 nm is preferred. In order to obtain good adhesion between the dielectric block and the metal film, C
r, Ge, etc., a thin layer (preferably 5
nm or less).

As the optical functional film constituting the optical logic element of the present invention, a film composed of a compound represented by the following general formula (I) can be suitably used.

[0024]

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.

[0025]

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.

Of these, 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.

These rings may be further condensed with a benzene ring and a naphthoquinone ring.

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, particularly 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.

Examples of preferred 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.

[0039]

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) and 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.

[0046]

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

[0047]

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.

C2 to C18 (preferably C2 to C2
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, and examples thereof include 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 meanings as those mentioned above 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).

[0061]

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.

[0062]

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.

Examples of the portion represented by the general formula (I-3) (represented by “B ⁻ ”) in the dye compound represented by the general formula (I) used in the present invention are specifically described below. I do.

[0064]

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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.

[0065]

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

[0066]

[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 represented by 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.

[0072]

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 O, 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.

[0086]

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

The heterocyclic ring formed by Y ¹ and W 1, and Z ¹ and W 2 includes, for example, the following.
In the examples, Ra, Rb and Rc each independently represent a hydrogen atom or a substituent.

[0088]

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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 preferred 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).

[0095]

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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, for example, phenyl, naphthyl and the like.

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

[0110]

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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, examples of compounds are those obtained by combining an anion part and a cation part. 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.

[0112]

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

[0113]

[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.).

[0114]

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.

[0115]

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 compounds represented by the general formula (II-9) and the general formula (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) Compound No. 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).

[0121]

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 comprising an organic dye represented by the following general formula (III) can also be suitably used.

[0123]

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,
M1 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.

[0125]

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, such as 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 (preferably 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). 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, cyclooctenedione. , Cyclooctadienedione and dibenzocyclooctenedione.

The ring in which L ¹ and L ² are jointly formed 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).

[0164]

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 .

Preferably, X ¹¹ and X ²² each independently represent an oxygen atom or a ＣＲCR ⁹ R ¹⁰ group, more preferably an oxygen atom or a ＣＲCR 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.

The most preferred combination is
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:

[0172]

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).

[0174]

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 formula (IV-3) is particularly preferably a compound represented by the following formula.

[0179]

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.

[0181]

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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.

Synthesis Example According to the following formula, the exemplified compound (A-22) according to the present invention was synthesized.

[0183]

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.

[0187]

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 added was determined based 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 having 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 optionally substituted aryl group having 6 to 10 carbon atoms, 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 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 having 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 includes, for example, 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 examples thereof include 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 having 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 having 1 to 8 carbon atoms), for example, thioureido, methylthioureido, 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 examples thereof include 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 examples thereof include 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.

Preferably, 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 chloride 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 the 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 combining two kinds on any carbon atom.

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

[0233]

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.

[0237]

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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.

As the photofunctional film of the present invention, a film comprising a metal complex of an azo dye represented by the following formula (V) can be suitably used.

[0239]

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.

Among the compounds of the general formula (V), the compounds represented by the following general formula (V-1) are preferred.

[0241]

Embedded image In the formula, M represents iron, cobalt, nickel, copper, zinc, palladium, platinum, or gold, and R21 represents an alkylsulfonyl group, an arylsulfonyl group, and having 1 to 1 carbon atoms.
2 represents an alkyl group which may have a substituent or a phenyl group or a naphthyl group which may have a substituent having 6 to 16 carbon atoms, and Y represents an oxygen atom, a sulfur atom, or =
It represents NR ^22, R ^{22, R 23} and ^{R 24} each independently represent an alkyl group which may have a substituent having 1 to 12 carbon ^{atoms, R 23} and ^{R 24} combine with each other to form a ring may form a, each independently R ²⁵ and R ²⁶ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cyano group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group,, R ^27, the R ²⁸ and R ^{2 9} are each independently a hydrogen atom, an alkyl group, an aryl group, hydroxy group, an alkoxy group, an aryloxy group, an amino group, a carbonamido group, a sulfonamido group, a cyano group,
Represents a halogen atom, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.

Among the general formula (V-1), the following general formula (V-1)
The compound represented by -2) is preferable.

[0243]

Embedded imageWherein M is iron, cobalt or nickel
Is preferable, and nickel is particularly preferable. R²¹Is
Alkyl sulfone having 1 to 4 carbon atoms which may have a substituent
A phonyl group, or a carbon number of 6 to 6 which may have a substituent;
And preferably 10 arylsulfonyl groups.
1 to 1 carbon atoms unsubstituted or substituted with a fluorine atom
4 alkylsulfonyl groups (for example, methylsulfonyl
Group, trifluoromethylsulfonyl group) or unsubstituted
Arylsulfonyl groups having 6 to 10 carbon atoms (e.g.,
Phenylsulfonyl group). R
²², R²³And R²⁴Each independently have a substituent
May be an alkyl group having 1 to 4 carbon atoms
preferable. Preferred examples of this substituent include halogen
Atom, hydroxy group, cyano group, alkoxy group, alkyl
Luthio, arylthio, acyl, alkylsulfo
And an arylsulfonyl group.
You. More preferably, R²², R²³And R²⁴Is
Each independently represents an unsubstituted alkyl group having 1 to 4 carbon atoms
is there. Also R²³And R²⁴Are connected to each other by a ring (eg,
(For example, a pyrrolidine ring or a morpholine ring).
Good. R ²⁵And R²⁶Are each independently a cyano group, an acyl group
Group, alkylsulfonyl group, or arylsulfonyl group
And particularly preferably both cyano groups.
Group. R²⁷, R²⁸And R²⁹Are each independently
Hydrogen atom, alkyl group, aryl group, hydroxy group,
Lucoxy group, aryloxy group, amino group, carboxyl group
Amide group, sulfonamide group, and
Preferably it is a hydrogen atom.

Specific examples of the azo dye metal complex used in the present invention are described below.

[0245]

Embedded image A method for synthesizing the metal complex of the azo dye represented by the general formula (V) is described in JP-A-9-277703, particularly in Examples 1 to 3.

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

[0247]

Embedded image In the formula, k and M have the same meanings as k and M in the formula (II-1) or (II-2), respectively.
Z ^{11, Z 12 X} in the general formula ^{(V), Z 1 1,} Z
Synonymous with ¹² .

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

[0249]

Embedded image The azo compound represented by the general formula (VI) 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.

The optical functional film of the present invention has the general formula (I)
~ (VI) any of the compounds represented by spin coating,
It is obtained by applying it on a metal film by a known method such as vapor deposition and sputtering. The film thickness is 350 nm
The control is performed so as to include a condition in which surface plasmon resonance occurs for light having any wavelength in the range of ２０００2000 nm, but a range of 10 nm to 1000 nm is usually preferable.

[0252]

According to the present invention, free electrons vibrate collectively in a metal, and a compression wave called a plasma wave is generated. And, the quantization of this compression wave generated on the metal surface is
It is called surface plasmon.

Conventionally, a light modulation element that modulates light by utilizing the phenomenon that surface plasmons are excited by light waves has been considered. FIG. 3 shows a basic configuration of the light modulation element. The light modulating element is basically formed on a dielectric block 1 arranged such that the modulated light 5 enters the surface 1a through the inside thereof at a total reflection angle, and formed on the surface 1a of the dielectric block 1. Metal film 2, an optical functional film 3 formed on the metal film 2, the refractive index of which changes by light irradiation, and a driving light source 7 for irradiating the optical functional film 3 with modulation driving light 6. It is composed of

In the above configuration, the incident angle θ of the modulated light 5 with respect to one surface 1a of the dielectric block 1 is, for example, the surface plasmon resonance of the metal film 2 when the optically functional film 3 is irradiated with the modulation driving light 6. Is set to an angle at which surface plasmon resonance is not excited when not irradiated.

In this way, when the optically functional film 3 is not irradiated with the modulation driving light 6, the modulated light 5 is totally reflected at the interface between the dielectric block 1 and the metal film 2 and is moved in the direction A. proceed. On the other hand, when the optically functional film 3 is irradiated with the modulation driving light 6, surface plasmon resonance is excited on the metal film 2 and total reflection is eliminated, and the amount of reflected light of the modulated light 5 is remarkably reduced or becomes zero. . Thus, the modulation driving light 6
, The modulated light 5 traveling in the A direction can be modulated.

The optical logic element according to the present invention is obtained by paying attention to the optical switching action of the above-mentioned optical modulation element. Among them, the optical logic element 10a of the a mode shown in FIG.
Is when the incident angle θ of the driving light Ld with respect to the one surface 1a of the dielectric block 1 is such that the surface plasmon resonance is relatively strongly excited in the metal film 2 when the optical functional film 3 is irradiated with the control light Lc, and is not irradiated. The surface plasmon resonance is set at an angle that is relatively weakly excited or not excited.

In the a-mode optical logic element 10a, the control light Lc is applied to the optical functional film 3 as shown in FIG.
Is not irradiated, the driving light Ld is strongly totally reflected at the interface between the dielectric block 1 and the metal film 2. On the other hand,
When the control light Lc is irradiated on the optical functional film 3 as shown in FIG. 2B, the phenomenon of eliminating total reflection occurs, and the drive light Ld is not reflected at all at the interface, or is reflected only slightly.

The b-mode optical logic element 10 shown in FIG.
b is the driving light Ld for one surface 1a of the dielectric block 1.
When the optical functional film 3 is not irradiated with the control light Lc, the surface plasmon resonance is relatively strongly excited in the metal film 2, and when irradiated, the surface plasmon resonance is relatively weakly excited or excited. Not set to an angle.

Therefore, in the b-mode optical logic element 10b, the control light Lc is applied to the optical functional film 3 as shown in FIG.
Is not irradiated, a total reflection elimination phenomenon occurs, and the driving light Ld is not reflected at all or only slightly reflected at the interface, whereas the driving light Ld is reflected on the optical functional film 3 as shown in FIG. When the control light Lc is applied, the driving light Ld is strongly totally reflected at the interface.

As described above, in the a-mode optical logic element 10a and the b-mode optical logic element 10b, the emission state of the driving light Ld from the element changes depending on whether the control light Lc is incident or not. If the control light Lc or the drive light Ld before being incident on one surface 1a of the dielectric block 1 is used as input light for logical operation and the drive light Ld emitted from the element is used as output light, an optical logic element Various logical operations can be performed singly or in combination of a plurality.

Further, as described above, the emission state of the driving light Ld from the element changes according to the incidence and non-incidence of the control light Lc. Therefore, the driving light Ld emitted from one optical logic element is transmitted to the element itself. It is possible to automatically switch between a state in which the drive light Ld is emitted from a certain optical logic element and a state in which the drive light Ld is not emitted, by causing the light to enter the optical functional film of another element or the optical functional film of another element. . In other words, an optical oscillation circuit that oscillates self-excited can be configured by using the optical logic element alone or by combining a plurality of optical logic elements.

The optical logic device according to the present invention having the above-described structure can be formed at a low cost because the structure is extremely simple. Therefore, the optical logic circuit and the optical oscillation circuit of the present invention using this optical logic device are also inexpensive. It can be formed into.

The optical logic device according to the present invention performs an optical switching action by utilizing a high-speed reaction of a chemical substance by light. Therefore, the optical logic circuit of the present invention using the optical logic device has a high speed operation. The optical oscillation circuit of the present invention using this optical logic element has an extremely short oscillation period and can oscillate at a very high frequency.

[0264]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows a schematic side view of an optical logic element 10a according to a first embodiment of the present invention. This optical logic element 10a is of the a-mode type described above, and the driving light Ld passes through the inside of the
, A prism-shaped dielectric block 1 arranged so as to be incident at an angle of total reflection, a metal film 2 formed on one surface 1a of the dielectric block 1, and a metal film 2 formed on the metal film 2. And an optical functional film 3 whose refractive index changes by light irradiation.

In this example, the driving light Ld has a wavelength of 680 n.
m, and the dielectric block 1 has one surface 1a
The driving light Ld is disposed so as to enter as P-polarized light. The dielectric block 1 is made of a high refractive index glass, and has a refractive index of 2.05 for a wavelength of 680 nm. On the other hand, the metal film 2 is made of Au as an example, and has a thickness of 15 nm.

The optical functional film 3 can be formed, for example, by suitably using any of the materials described in detail above. In this embodiment, the refractive index n for a wavelength of 680 nm
However, when the control light Lc having a wavelength of 532 nm is not irradiated, the dye is 1.60, and when the control light Lc is irradiated, the dye is 1.61.

The operation of the optical logic element 10a will be described below. As described above, the refractive index n of the optical functional film 3 at a wavelength of 680 nm is 1.60 and 1.61, respectively, when the control light Lc is not irradiated and when the control light Lc is irradiated. Driving light Ld for the interface between the dielectric block 1 and the metal film 2
The relationship between the incident angle θ and the reflectance at that time is as shown by the broken line and the solid line in FIG. 12 when the refractive index n of the optical functional film 3 is 1.60 and 1.61, respectively.

The incident angle θ is set to 52.2 ° in this example. Therefore, when the optical functional film 3 is not irradiated with the control light Lc (when the refractive index n is 1.60), the reflectance becomes almost 100%, and the control light Lc is applied to the optical functional film 3.
Is irradiated (when the refractive index n is 1.61), the reflectance is almost 0%, so that the drive light Ld is reflected or non-reflected according to the non-incidence and incidence of the control light Lc. .
Note that FIG. 1A shows a state in which the optical functional film 3 is not irradiated with the control light Lc at all, and FIG. 1B shows a state in which the optical functional film 3 is irradiated with the control light Lc. .

Therefore, the control light Lc or the drive light Ld before entering the one surface 1a of the dielectric block 1 is used as input light for logical operation, and the drive light Ld emitted from the optical logic element 10a is used as output light. Then, various logic operations can be performed by using the optical logic element 10a alone or by combining a plurality of logic logic elements.

The present inventors have prepared an optical logic element having the structure shown in FIG. 1 in which the following compound is provided as an optical functional film by spin coating to a thickness of 160 nm, and confirmed that logical operation is possible.

[0271]

[Table 4] Next, a second embodiment of the present invention will be described. FIG.
Shows a schematic side view of an optical logic element 10b according to a second embodiment of the present invention. This optical logic element 10b is of the b-mode type described above, and includes a dielectric block 1, a metal film 2, and an optical functional film 3 similar to those in FIG.

Also in this case, the wavelength of the optical functional film 3 is 680 nm.
Is the refractive index n when the control light Lc is not irradiated.
When irradiated, they are 1.60 and 1.61, respectively.
The relationship between the incident angle θ of the driving light Ld with respect to the interface between the dielectric block 1 and the metal film 2 and the reflectance thereat is such that the refractive index n of the optical functional film 3 is 1.60 and 1.61. In case,
The characteristics are indicated by broken lines and solid lines in FIG. 12, respectively.

The incident angle θ is set to 51.8 ° in this example. Therefore, when the optical functional film 3 is not irradiated with the control light Lc (when the refractive index n is 1.60), the reflectance becomes almost 0%, and the optical functional film 3 is irradiated with the control light Lc ( (When the refractive index n is 1.61), the reflectance is almost 100%, so that the driving light Ld is non-reflective and reflected according to the non-incidence and incidence of the control light Lc.
2A shows a state in which the optical functional film 3 is not irradiated with the control light Lc at all, and FIG. 2B shows a state in which the optical functional film 3 is irradiated with the control light Lc. .

Therefore, the control light Lc or the drive light Ld before entering the one surface 1a of the dielectric block 1 is used as input light for logical operation, and the drive light Ld emitted from the optical logic element 10b is used as output light. Then, various logic operations can be performed by using the optical logic element 10b alone or by combining a plurality of logic elements.

Next, an embodiment of an optical logic circuit using the above-described optical logic element 10a or 10b will be described.
This will be described with reference to FIGS.

In FIGS. 4 to 7, the detailed configuration of the optical logic elements 10a and 10b is the same as that shown in FIGS. 1 and 2, respectively. 10a and 10b are indicated by simple isosceles triangles (similarly in FIGS. 8 to 11 showing the optical oscillation circuit). 4 to 7, the input light is a circle I, I1, or I1.
2, and the output light is also indicated by a circled O character.

First, the NOT circuit shown in FIG. 4 will be described. Here, an a-mode type optical logic element 10a is used, and the driving light Ld is incident thereon (specifically, on one surface 1a of the dielectric block 1; the same applies hereinafter). In addition, the control light Lc is incident on the optical logic element 10a (specifically, on the optical functional film 3; the same applies hereinafter) so as to be cut off.

In this embodiment, the control light Lc is only one.
Act as two input lights I. As described above, in the a-mode optical logic element 10a, when the input light I is not incident as shown in FIG. 1A, the output light O (the totally reflected driving light Ld) is emitted. When the input light I is incident as in 2), the output light O is not emitted. That is, if the existence of the input light I or the output light O is indicated as “1” and the absence thereof is indicated as “0”, the output state becomes “1” when the input state is “0”,
NOT when output state is "0" when input state is "1"
The circuit is configured.

Next, the exNOR circuit shown in FIG. 5 will be described. Here, an a-mode type optical logic element 10a is used, and the driving light Ld enters there. Also, two control lights Lc enter the optical logic element 10a in a manner that can be cut off.

In this embodiment, the two control lights Lc act as input lights I1 and I2, respectively. As described above, in the a-mode optical logic element 10a, when the input lights I1 and I2 do not enter as shown in FIG. 1A, the output light O (the totally reflected drive light Ld) is emitted. One input light I1 or I2 as shown in FIGS.
Does not emit the output light O. Further, when both the input lights I1 and I2 are incident as shown in FIG. 4D, the intensity of the control light is too strong, the state of eliminating total reflection is broken, and the output light O is emitted.

That is, if the existence of the input light I1, I2 or the output light O is indicated as "1" and the absence thereof is indicated as "0", the output state becomes "1" when the input state is "0" or "0", When the input state is "1" or "0", the output state is "0". When the input state is "0" or "1", the output state is "0". When the input state is "1" or "1". An exNOR circuit whose output state is “1” is configured.

Next, the AND circuit shown in FIG. 6 will be described. Here, a b-mode type optical logic element 10b is used, into which the driving light Ld and one control light Lc are incident, respectively, which can be cut off.

In the present embodiment, the control light Lc acts as one input light I1, and the drive light Ld acts as another input light I2.
Act as In the b-mode optical logic element 10b, as described above, as shown in FIG.
The output light O (the totally reflected drive light Ld) is emitted only when both I and I2 are incident, and one of the input lights I1 and I2 is also incident as shown in FIGS. 1 (1), (3) and (4). Otherwise, no output light O is emitted.

That is, if the existence of the input light I1, I2 or the output light O is indicated as “1” and the non-existence thereof is indicated as “0”, when the input state is “0” or “0”, “0” or “1” An AND circuit is formed in which the output state becomes "0" when the input state is "1" or "1" when the output state is "1" or "0".

Next, the OR circuit shown in FIG. 7 will be described. Here, a b-mode type optical logic element 10b is used.
The driving light Ld enters there. Also, two control lights Lc enter the optical logic element 10a in a manner that can be cut off.

In this embodiment, the two control lights Lc act as input lights I1 and I2, respectively. As described above, in the b-mode optical logic element 10b, when the input lights I1 and I2 are not incident as shown in FIG. 1A, the output light O (the totally reflected drive light Ld) is not emitted. One input light I1 or I2 as shown in FIGS.
Is output, the output light O is emitted. Also, when both the input lights I1 and I2 enter as shown in FIG. 4D, the state of eliminating total reflection is broken and the output light O is emitted.

That is, if the existence of the input light I1, I2 or the output light O is indicated as “1”, and the absence thereof is indicated as “0”, when the input state is “1” or “1”, “1” or “0” An OR circuit is provided in which the output state becomes "1" when the input state is "0" or "0", and when the input state is "0" or "0".

The exNOR circuit shown in FIG. 5, the AND circuit shown in FIG. 6, and the OR circuit shown in FIG. 7 are connected to the NOT circuit so that each output light O enters the NOT circuit shown in FIG. When combined with the circuit, each exO
An R circuit, a NAND circuit, and a NOR circuit are obtained.

Here, in the optical logic circuit of the present invention, 1
It is desirable that lights having different wavelengths be used as the plurality of lights to be incident on one optical logic element. For example, FIG.
In the NOT circuit, the optical logic element 10a is controlled by the control light Lc.
Changes state. Since the response of the optical logic element 10a has wavelength dependence, it is preferable to use light having a wavelength that improves the response characteristics of the optical logic element 10a as the control light Lc. On the other hand, even if a configuration is adopted in which the driving light Ld does not reach the optical functional film 3, a part of the leakage light may reach there. Therefore, an optical logic element is used as the driving light Ld.
If light having a wavelength at which the response characteristic of 10a is relatively low is used, the influence on the optical logic element 10a can be reduced even if there is leakage light.

Next, an embodiment of an optical oscillation circuit using the optical logic element 10a or 10b will be described with reference to FIGS. First, the light oscillation circuit of FIG. 8 will be described. This optical oscillation circuit includes one b-mode optical logic element 10b, one a-mode optical logic element 10a, and a mirror.
And an optical system including 21, 22, and 23. The a-mode optical logic element 10a receives the drive light Ld1 totally reflected at the interface (see FIG. 2) between the dielectric block 1 and the metal film 2 of the b-mode optical logic element 10b by the optical functional film 3. It is arranged in.

The operation of this optical oscillation circuit will be described below. As shown in FIG. 8A, driving light Ld1 and Ld2 are incident on the b-mode optical logic element 10b and the a-mode optical logic element 10a, respectively. Control light Lc is incident on the b-mode optical logic element 10b as trigger light. When the control light Lc is incident on the b-mode optical logic element 10b, the driving light Ld1
Is totally reflected, and the driving light Ld1 is an a-mode optical logic element.
It is incident on 10a as control light.

Then, the phenomenon of eliminating total reflection occurs in the a-mode optical logic element 10a, and the driving light Ld2 is not totally reflected there. In the case where the a-mode optical logic element 10a does not cause the elimination of total reflection, the driving light Ld2 is totally reflected by the optical logic element 10a and then mirrors 21, 22, and 23.
, And enters the b-mode optical logic element 10b as control light by following the optical path shown by the broken line in FIG. 8 (2).

Next, when the control light Lc, which is the trigger light, is cut off, the phenomenon of eliminating total reflection occurs in the b-mode optical logic element 10b, and the driving light Ld1 is not totally reflected there. Then, the driving light Ld1 is changed to the a-mode optical logic element 10a.
Is not incident on the driving light L
d2 is totally reflected by the optical logic element 10a and enters the b-mode optical logic element 10b as control light.

Then, the driving light Ld1 is totally reflected in the b-mode optical logic element 10b, and this driving light Ld1 is incident on the a-mode optical logic element 10a as control light. As a result, the phenomenon of eliminating total reflection occurs in the a-mode optical logic element 10a, and the driving light Ld2 is not totally reflected there.

By repeating the above operation, b
Emission and non-emission of drive light Ld1 from mode-type optical logic element 10b, and drive light L from a-mode optical logic element 10a
Emission and non-emission of d2 are automatically and continuously switched. When such a self-excited oscillation state is obtained, if a part of the driving light Ld2 is extracted from between the mirror 22 and the mirror 23 by a beam splitter or the like, very high speed can be obtained.
Light that is ON / OFF can be extracted. To stop the oscillation, the drive light Ld1 or the drive light Ld2 may be cut off.

The oscillation can be started without using the trigger light described above. For example, if the drive light Ld2 is made to enter the a-mode optical logic element 10a at a timing slightly earlier than the drive light Ld1 is made to enter the b-mode optical logic element 10b, oscillation starts.

An optical system for coupling the b-mode optical logic element 10b and the a-mode optical logic element 10a is shown in FIG.
Are not limited to those shown in FIGS. 9 and 1.
Optical systems indicated by reference numerals 0 are also applicable.

In the embodiment shown in FIG. 9, the b-mode optical logic element 10b and the a-mode optical logic element 10a are arranged so as to be slightly shifted from each other.
While the drive light Ld1 totally reflected by the mirror is reflected by the mirror 31 and enters the a-mode optical logic element 10a as control light,
The drive light Ld2 totally reflected by the mode-type optical logic element 10a is reflected by the mirror 32, and enters the b-mode optical logic element 10b as control light.

In the embodiment shown in FIG. 10, the b-mode optical logic element 10b and the a-mode optical logic element 10a are disposed so as to face each other.
The drive light Ld1 totally reflected by b is reflected by the mirror 41, and a
While entering the mode-type optical logic element 10a as control light,
The driving light Ld2 totally reflected by the a-mode optical logic element 10a is reflected by the mirror 42 and is incident on the b-mode optical logic element 10b as control light.

Next, still another embodiment of the optical oscillation circuit according to the present invention will be described with reference to FIG. This optical oscillation circuit includes one a-mode optical logic element 10a and an optical system including mirrors 51, 52, and 53. The mirrors 51, 52, and 53 serve to convert the drive light Ld totally reflected at the interface between the dielectric block 1 and the metal film 2 of the a-mode optical logic element 10a (see FIG. 1) into the optical functionality of the optical logic element 10a. It is arranged to be incident on the film 3.

The operation of the light oscillation circuit will be described below. As shown in FIG. 11A, the driving light Ld is incident on the a-mode optical logic element 10a. This driving light L
d is totally reflected by the a-mode optical logic element 10a and emitted therefrom, then reflected by the mirrors 51, 52 and 53 one after another, and enters the a-mode optical logic element 10a as control light.
Then, as shown in FIG. 2B, the total reflection elimination phenomenon occurs in the a-mode optical logic element 10a, and the driving light Ld is not totally reflected there.

When the driving light Ld is not totally reflected, the driving light Ld does not enter the a-mode optical logic element 10a as control light. Then, the state of eliminating total reflection is broken, and the driving light Ld is totally reflected by the a-mode optical logic element 10a.

By repeating the above operation, the driving light Ld from the a-mode optical logic element
Emission and non-emission are automatically and continuously switched,
A self-oscillation state is obtained.

[Brief description of the drawings]

FIG. 1 is a schematic side view showing a first embodiment of an optical logic element of the present invention.

FIG. 2 is a schematic side view showing a second embodiment of the optical logic element of the present invention.

FIG. 3 is a schematic side view showing a conventional light modulation element related to the present invention.

FIG. 4 is a schematic side view showing an embodiment of the optical logic circuit of the present invention.

FIG. 5 is a schematic side view showing another embodiment of the optical logic circuit of the present invention.

FIG. 6 is a schematic side view showing still another embodiment of the optical logic circuit of the present invention.

FIG. 7 is a schematic side view showing still another embodiment of the optical logic circuit of the present invention.

FIG. 8 is a schematic side view showing one embodiment of the light oscillation circuit of the present invention.

FIG. 9 is a schematic side view showing another embodiment of the optical oscillation circuit of the present invention.

FIG. 10 is a schematic side view showing still another embodiment of the optical oscillation circuit of the present invention.

FIG. 11 is a schematic side view showing still another embodiment of the optical oscillation circuit of the present invention.

FIG. 12 is a graph showing a relationship between an incident angle θ of driving light with respect to an interface between a dielectric block and a metal film in the optical logic element of FIG. 1, and a reflectance thereat.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Dielectric block 1a One surface of dielectric block 2 Metal film 3 Optical functional film 10a a-mode optical logic element 10b b-mode optical logic element 21, 22, 23, 31, 32, 41, 42, 51, 52, 53 Mirror Lc Control light Ld, Ld1, Ld2 Drive light I, I1, I2 Input light O Output light

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) G02F 1/355 G02F 1/355

Claims (21)

[Claims] 1. An optical logic element for performing a logical operation on one or a plurality of input lights, comprising: a dielectric block arranged such that driving light is incident on one surface thereof through the inside thereof at a total reflection angle. A metal film formed on the one surface of the dielectric block; and an optical functional film formed on the metal film so as to be irradiated with control light and having a refractive index changed by light irradiation. Optical logic element. 2. The photofunctional film according to the following general formula (I)
2. The compound according to claim 1, wherein the compound is
Optical logic element. Embedded imageWhere DYE⁺Represents the monovalent cyanine dye cation
And n represents an integer of 1 or more;₅ And R₆ Are each
Independently represents a substituent;₇ And R₈ Are independent
Alkyl, alkenyl, alkynyl, aralkyl
Group, an aryl group or a heterocyclic group,₅When
R₆, R₅And R₇ , R₆And R₈ Or R₇ And R₈
 May be linked to each other to form a ring, and r and s
Represents each independently an integer from 0 to 4, and r and s are 2
In the above case, a plurality of r and s are the same as each other.
Or different. 3. The photofunctional film according to claim 1, wherein the photofunctional film has the following general formula (II-
2. The optical logic 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:
An optical logic element according to claim 1. 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). An optical logic element according to claim 1. 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 optical logic device according to claim 1, wherein the 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 optical logic device according to claim 1, wherein the optical functional film is made of an organic dye represented by the following general formula (VI). Embedded image In the formula, k and M have the same meanings as k and M in the formula (II-1) or (II-2), respectively.
Z ¹¹ and Z ¹² represent X in the general formula (V),
It is synonymous with Z ¹¹ and Z ¹² respectively. 8. An incident angle of drive light with respect to the one surface of the dielectric block is set such that when the control light is irradiated on the optical functional film, surface plasmon resonance is relatively strongly excited on the metal film and is not irradiated. The optical logic device according to claim 1, wherein the surface plasmon resonance is set to an angle that is excited relatively weakly or is not excited. 9. An incident angle of drive light to the one surface of the dielectric block is set such that when the control light is not irradiated to the optical functional film, surface plasmon resonance is relatively strongly excited and irradiated to the metal film. The optical logic device according to claim 1, wherein the surface plasmon resonance is set to an angle that is excited relatively weakly or is not excited. 10. An optical logic circuit using one of the optical logic elements according to claim 8, wherein one control light incident on the optical functional film is received as input light, and the dielectric block and the metal film are received. An optical logic circuit which emits drive light totally reflected at an interface with the output light as output light as a NOT operation result. 11. An optical logic circuit using one optical logic element according to claim 8, wherein two control lights incident on the optical functional film are received as input light, and the dielectric block and the metal film are provided. An optical logic circuit that emits drive light totally reflected at an interface with the output light as output light as a result of an exNOR operation. 12. An optical logic circuit using one of the optical logic elements according to claim 9, wherein one control light incident on the optical functional film and one control light incident on one surface of the dielectric block. An optical logic circuit which receives two driving lights as two input lights and emits the driving light totally reflected at an interface between the dielectric block and the metal film as output light which is a result of an AND operation. 13. An optical logic circuit using one optical logic element according to claim 9, wherein two control lights incident on the optical functional film are received as input light, and the dielectric block and the metal film are provided. An optical logic circuit which emits, as output light, an OR operation result, driving light totally reflected at an interface with the optical logic circuit. 14. The driving light totally reflected by a plurality of optical logic elements according to any one of claims 1 to 9 at an interface between a dielectric block and a metal film of one optical logic element, and the other optical logic element. An optical logic circuit which is combined with the control light so as to be incident as the control light. 15. An optical logic element according to claim 8, wherein one of the optical logic elements is arranged as a preceding optical logic element that receives two control lights incident on the optical functional film as input light. One optical logic element is arranged as a subsequent optical logic element that receives drive light totally reflected at an interface between the dielectric block of the preceding optical logic element and the metal film as one control light; An optical logic circuit, wherein driving light totally reflected at an interface between a dielectric block of a logic element and a metal film is emitted as output light as an exOR operation result. 16. An optical logic device according to claim 9, wherein one control light incident on the optical functional film and one drive light before being incident on one surface of the dielectric block are input into two input lights. 9. A single optical logic element according to claim 8, wherein the driving light is totally reflected at an interface between a dielectric block and a metal film of the preceding optical logic element. It is arranged as a subsequent optical logic element that receives as light, and emits driving light totally reflected at an interface between the dielectric block and the metal film of the latter optical logic element as output light that is a NAND operation result. Optical logic circuit. 17. The optical logic element according to claim 9, wherein one of the optical logic elements is arranged as a preceding optical logic element that receives two control lights incident on the optical functional film as input light. One optical logic element is arranged as a subsequent optical logic element that receives drive light totally reflected at an interface between the dielectric block of the preceding optical logic element and the metal film as one control light; An optical logic circuit, wherein drive light totally reflected at an interface between a dielectric block of a logic element and a metal film is emitted as output light as a result of a NOR operation. 18. The optical logic circuit according to claim 10, wherein light having different wavelengths is used as a plurality of lights to be incident on one optical logic element. 19. The optical logic element according to claim 8, wherein drive light totally reflected at an interface between the dielectric block and the metal film of the optical logic element is incident on the optical functional film of the optical logic element. An optical oscillation circuit comprising an optical system for causing 20. An optical logic device according to claim 9, wherein the optical functional film receives driving light totally reflected at an interface between the dielectric block and the metal film of the optical logic device. 9. An optical logic element according to claim 8, wherein drive light totally reflected at an interface between the dielectric block and the metal film of the latter optical logic element is made incident on the optical functional film of the former optical logic element. An optical oscillation circuit composed of an optical system. 21. The optical oscillation circuit according to claim 19, wherein light having different wavelengths is used as a plurality of lights to be incident on one optical logic element.