JPH11167937A - Photoelectric transfer element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an element having high transfer efficiency by adsorbing organic pigment such that the pigment coloring groups exist in a plurality in the vertical direction to surfaces of semiconductor particulates, and forming a metallic polynuclear complex part as a single coloring group. SOLUTION: Semicondcutor particulates, sensitized by simultaneously using at least one kind of methine pigment of formula I and at least one kind of methine pigment of formula II, are preferably used. In formulas I and II, Z1 and Z2 represent an atomic group required to form a nitrogen-containing heterocycle, and R1 and R2 represent an alkyl group or an aryl group, and Q1 and Q2 represent a methine group or a polymethine group required to form methine pigment by a compound respectively expressed by formulas I and II, and L1 to L4 represent a methine group, and p1 and p2 represent 0 or 1. Here, Z1 , R1 and Q1 have a substitutional group becoming cation pigment by methine pigment expressed by formula I, and Z2 , R2 and Q2 have a substitutional group becoming anion pigment by methine pigment of the formula II. M1 and M2 represent respectively electric charge balanced anion and cation. Symbols m1 and m2 represent the number 0 to 10 required to neutralize electric charge of a molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photoelectric conversion device, and more particularly, to a photoelectric conversion device using semiconductor fine particles sensitized with a dye.

[0002]

2. Description of the Related Art Photoelectric conversion elements are used in various optical sensors, copying machines, and photovoltaic devices. Various types of photoelectric conversion elements have been put into practical use, such as those using metals, those using semiconductors, those using organic pigments and dyes, and those combining these. US Patent 49277
No. 21, 4684537, 5084365, 535
Nos. 0644, 5463057, 5525440 and JP-A-7-249790 disclose a photoelectric conversion element using semiconductor fine particles sensitized with a dye (hereinafter abbreviated as a dye-sensitized photoelectric conversion element), or Materials and manufacturing techniques for making are disclosed. A first advantage of this method is that an inexpensive oxide semiconductor such as titanium dioxide can be used without purification to a high degree of purity, so that a relatively inexpensive photoelectric conversion element can be provided.
The second advantage is that the absorption of the dye used is broad,
It is capable of converting light in almost all visible wavelength regions into electricity. These features are advantageous when applied to a photoelectric conversion element (a so-called photochemical battery) for converting solar energy into electricity, and therefore applications to this area are being actively studied.

One of the demands for improvement of dye-sensitized photoelectric conversion elements is to use expensive ruthenium complex dyes as sensitizing dyes. The development of a photoelectric conversion element sensitized by an inexpensive organic dye was desired, but the organic dye had a low adsorptivity to titanium dioxide and a small amount of adsorption did not allow high sensitization efficiency to be obtained. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a dye-sensitized photoelectric conversion element having high conversion efficiency.

[0005]

In order to obtain high sensitization efficiency, it is necessary to improve the light absorption rate per unit surface area. For that purpose, it is necessary to increase the adsorption density of the sensitizing dye. As a result of the research, we have developed a method to increase the adsorption density of the sensitizing dye. That is, the object of the present invention has been achieved by the following (1) to (6). (1) A photoelectric conversion element using semiconductor fine particles sensitized by an organic dye, wherein the organic dye is adsorbed such that a plurality of dye chromophores are present in a direction perpendicular to the surface of the semiconductor fine particles. Photoelectric conversion element. However, the polynuclear metal complex is one chromophore.

(2) The photoelectric conversion element according to (1), wherein semiconductor fine particles sensitized by simultaneously using at least one kind of cationic dye and at least one kind of anionic dye are used.

(3) Semiconductor fine particles sensitized by simultaneously using at least one methine dye represented by the following general formula (I) and at least one methine dye represented by the following general formula (II) (1) or (2). General formula (I)

[0008]

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In the formula, Z ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. R ₁ is an alkyl group or an aryl group. Q ₁ represents a methine group or a polymethine group necessary for the compound represented by the formula (I) to form a methine dye. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. Wherein Z ₁ , R ₁ and Q ₁ are of the general formula (I)
It is assumed that the methine dye represented by has a substituent which becomes a cationic dye as a whole. M ₁ represents an anion for charge balancing, and m ₁ represents 0 required to neutralize the charge of the molecule.
Represents a number from 10 to 10. General formula (II)

[0010]

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In the formula, Z ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. R ₂ is an alkyl group or an aryl group. Q ₂ represents a methine group or a polymethine group necessary for the compound represented by the general formula (II) to form a methine dye. L ₃ and L ₄ represent a methine group. p ₂ represents 0 or 1. Wherein Z ₂ , R ₂ and Q ₂ are represented by the general formula (II)
It is assumed that the methine dye represented by has a substituent which becomes an anion dye as a whole. M ₂ represents a cation for charge balancing, and m ₂ represents a cation necessary to neutralize the molecular charge.
Represents a number from 10 to 10.

(4) The photoelectric conversion according to (1), wherein semiconductor fine particles sensitized by at least one compound having two or more dye moieties covalently linked by a divalent linking group are used. element.

(5) The photoelectric conversion device according to (1) or (4), wherein semiconductor fine particles sensitized by at least one compound represented by the following general formula (III) are used. General formula (III)

[0014]

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In the formula, D represents a sensitizing dye moiety adsorbed on semiconductor fine particles. L represents a divalent linking group or a single bond.
A represents a luminescent dye moiety linked to D by a linking group L. n is an integer of 1 or more, and when it is 2 or more, a plurality of L and A contained therein may be different linking groups and luminescent dye portions, respectively.

(6) (1), (2), (3), (4),
Or a photochemical cell using the photoelectric conversion element of (5).

[0017]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to a photoelectric conversion element using semiconductor fine particles sensitized by an organic dye, wherein an organic dye is adsorbed so that a plurality of dye chromophores exist in a direction perpendicular to the surface of the semiconductor fine particles. This is a photoelectric conversion element characterized in that: That the organic dye is adsorbed so that a plurality of dye chromophores are present in the direction perpendicular to the surface of the semiconductor fine particles means that the surface of the semiconductor fine particles is covered with the dye chromophore in multiple layers. Such an adsorption state may be formed by any method. The chromophores mentioned here are the Dictionary of Silica Chemistry (4th edition, Iwanami Shoten, 1987
Year), pp. 985-986.

The present invention further shows two methods for realizing such a dye adsorption state. One is a method using a combination of a cationic dye and an anionic dye. The dye used in this method may be any positively charged organic dye and any negatively charged organic dye. As organic dyes, spiro compounds, metallocene, fluorenone, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo compound, disazo compound, quinone, indigo, diphenylmethane, triphenylmethane, polymethine, acridine, acridinone, carbostyril, coumarin, Diphenylamine, quinacridone,
Examples include quinophthalone, phenoxazine, phthaloperylene, porphine, chlorophyll, phthalocyanine, squarium, diazobenzene, and bipyridine metal complexes (examples of metal polynuclear complexes). Preferably, an azo compound,
Diphenylmethane, triphenylmethane, polymethine,
Porfin, phthalocyanine, squarium, bipyridine metal complex and the like can be mentioned. More preferably, the cationic dye is a polymethine dye represented by the general formula (I). More preferably, the general formula (I) is represented by the following general formula (IV). General formula (IV)

[0019]

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In the general formula (IV), L ₅ , L ₆ , L ₇ ,
L ₈ , L ₉ , L ₁₀ and L ₁₁ represent a methine group. p ₃ ,
And p ₄ represents 0 or 1. n ₁ represents 0, 1, 2, or 3. Z ₃ and Z ₄ each represent an atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₃ and R ₄ represent an alkyl group or an aryl group. At least one of R ₃ and R ₄ represents an aryl group or an alkyl group substituted with an aryl group or a heterocyclic group. However, R ₃ and R ₄ also have no anionic substituent. Z ₃ , Z
₄ , L ₃ , L ₄ , and L ₅ may be substituted, and their substituents have no anionic substituent. M ₃ represents an anion for charge balancing, and m ₃ represents a number from 0 to 10 required to neutralize the charge of the molecule.

The anionic dye is more preferably a polymethine dye represented by the general formula (II). More preferably, the general formula (II) is represented by the following general formula (V). General formula (V)

[0022]

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In the general formula (V), L ₁₂ , L ₁₃ , L ₁₄ ,
L ₁₅ , L ₁₆ , L ₁₇ and L ₁₈ represent a methine group. p ₅ ,
And p ₆ represents 0 or 1. n ₂ represents 0, 1, 2, or 3; Z ₅ and Z ₆ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₅ and R ₆ represent an alkyl group or an aryl group. At least one of R ₅ and R ₆ represents an aryl group or an alkyl group substituted with an aryl group or a heterocyclic group. However, R ₅ and R ₆ have an anionic substituent. M ₄ represents an anion for charge balancing, and m ₄ represents a number from 0 to 10 required to neutralize the charge of the molecule.

Another method for realizing an adsorption state in which the surface of the semiconductor fine particles is coated with a dye chromophore in multiple layers is a method in which a divalent linking group is used to form a covalent bond.
This is a method using a dye compound having two or more dye chromophore moieties. Any dye chromophore can be used. Dye chromophores include spiro compounds,
Metallocene, fluorenone, fulgide, imidazole,
Perylene, phenazine, phenothiazine, polyene, azo compound, disazo compound, quinone, indigo, diphenylmethane, triphenylmethane, polymethine, acridine, acridinone, carbostyril, coumarin, diphenylamine, quinacridone, quinophthalone, phenoxazine, phthaloperylene, porphine, chlorophyll,
Examples include phthalocyanine, squarium, diazobenzene, and bipyridine metal complexes. Preferably, azo compounds, diphenylmethane, triphenylmethane, polymethine, porphine, phthalocyanine, squarium, bipyridine metal complexes and the like are mentioned.

A more preferred linking dye is a polymethine dye represented by the formula (III).
More preferably, in the general formula (III), D and A are each independently a methine dye represented by the following general formula (VI), (VII) or (VIII). General formula (VI)

[0026]

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In the formula (VI), L ₁₉ , L ₂₀ , L ₂₁ , L ₂₂ ,
L ₂₃ , L ₂₄ and L ₂₅ represent a methine group. p ₇ and p
₈ represents 0 or 1. n ₃ represents 0, 1, 2, or 3. Z ₇ and Z ₈ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring. M ₅ represents a charge-balancing counter ion, and m ₅ represents 0 required to neutralize the molecular charge.
Represents a number from 4 to 4. R ₇ and R ₈ represent an alkyl group. General formula (VII)

[0028]

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In the formula (VII), L₂₆, L₂₇, L₂₈, And L₂₉
Represents a methine group. p₉Represents 0 or 1. n_FourIs 0,
Represents 1, 2, or 3. Z₉And Z_TenIs a 5 or 6 member
Represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. M
₆Represents a charge-balancing counter ion, m₆Neutralizes molecular charge
Represents a number from 0 to 4 required to perform R₉And R _Ten
Represents an alkyl group, an aryl group, or a heterocyclic group. General formula (VIII)

[0030]

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In the formula (VIII), L ₃₀ , L ₃₁ , L ₃₂ , L ₃₃ ,
_{L 34, L 35, L 36} , L 37 and L ₃₈ each represents a methine group. p
₁₀ and p ₁₁ each represents 0 or 1. n ₅ and n ₆ are 0, 1,
Represents 2 or 3. Z ₁₁ , Z ₁₂ and Z ₁₃ represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring.
M ₇ represents a charge-balancing counter ion, and m ₇ represents a number from 0 to 4 required to neutralize the charge of the molecule. R ₁₁ and R
₁₃ represents an alkyl group. R ₁₂ represents an alkyl group, an aryl group, or a heterocyclic group.

Hereinafter, the methine compounds represented by formulas (I) and (II) will be described in detail. In the general formulas (I) and (II), Q ₁ and Q ₂ represent a methine group or a polymethine group necessary for forming a methine dye. The number of methines in the polymethine group is preferably 0 to 9, more preferably 1 to 7, particularly preferably 3 to 7. (When a methine group is incorporated into a heterocycle, the methine group may be apparently 0. For example, simple merocyanine (zero methine merocyanine) may be mentioned.) Q ₁ and Q ₂ form a methine dye As long as it is any, it is preferably a substituted methine group or a polymethine group necessary for forming a methine dye, and examples of such a substituent include an aromatic group, a heterocyclic group, an amino group, and a cyano group. , An alkoxycarbonyl group, an alkylsulfonyl group,
Acyl groups and the like. Specifically, examples of the aromatic group include a substituted or unsubstituted aromatic group (for example, 4-dimethylaminophenyl, 4-methoxyphenyl, phenyl, 4-dimethylaminonaphthyl) and the like.
Examples of the heterocycle of the heterocyclic group include known basic nuclei and acidic nuclei when forming a dye, and specifically include a thiazoline nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus, and a benzoxazole nucleus. , Selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,
3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus,
Benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxalin nucleus, oxadiazole nucleus, Examples thereof include a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus. Examples of the amino group include a substituted or unsubstituted amino group (for example, amino and dimethylamino). Examples of the alkoxycarbonyl group include a substituted or unsubstituted alkoxycarbonyl group (for example, ethoxycarbonyl). Examples of the alkylsulfonyl group include a substituted or unsubstituted alkylsulfonyl group (for example, methanesulfonyl). Examples of the acyl group include a substituted or unsubstituted acyl group (for example, acetyl). The compounds represented by the general formulas (I) and (II) are represented by Q ₁ and Q ₂
Can form any methine dye, preferably a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, a styryl dye, and the like. In this case, the cyanine dyes include those in which the substituent on the methine chain forming the dye forms a squarium ring or a croconium ring. For more information on these dyes, see
FM Harmer, Heterocyclic Compounds-Cyanin
e Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, D.M.
(DMSturmer), Heterocyclic Compounds-Special topi in Heterocyclic Compounds
cs in heterocyclic chemistry) ", Chapter 18, Chapter 14
, Pp. 482-515. The general formulas of cyanine dyes, merocyanine dyes and rhodacyanine dyes are preferably those shown in (XI), (XII) and (XIII) on pages 21, 22 of US Pat. No. 5,340,694.

Formulas (I), (II) and (I
V) and in general formula (V), Z₁, Z _Two, Z_Three, Z_Four,
Z_Five, And Z₆Is a necessary element to form a nitrogen-containing heterocycle.
Represents a child group. Z₁, Z_Two, Z_Three, Z_Four, Z_Five, And Z₆
As a nitrogen-containing heterocyclic ring formed by the thiazoline nucleus,
Thiazole nucleus, benzothiazole nucleus, oxazoline nucleus,
Oxazole nucleus, benzoxazole nucleus, selenazoline
Nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-
Dialkylindolenin nucleus (for example, 3,3-dimethyli
Drenin), imidazoline nucleus, imidazole nucleus, ben
Zoimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus,
2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline
Nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quino
Quizalin nucleus, oxadiazole nucleus, thiadiazole nucleus,
Tetrazole nucleus, pyrimidine nucleus, etc.
Benzothiazole nucleus, benzoxazo
Nucleus, 3,3-dialkylindolenine nucleus (for example,
3,3-dimethylindolenine), benzimidazole
Nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline
Nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinone
Norin nucleus, more preferably benzothiazole
Nucleus, benzoxazole nucleus, 3,3-dialkylindo
Renin nucleus (for example, 3,3-dimethylindolenine),
Nzoimidazole nucleus.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , and Z ₆
When the above substituent is V, the substituent represented by V is not particularly limited, and examples thereof include a halogen atom (for example, chlorine, bromine, iodine, and fluorine), a mercapto group, a cyano group,
Carboxyl group, phosphate group, sulfo group, hydroxy group,
A carbamoyl group having 1 to 10 carbon atoms, preferably 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms (eg, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), 0 to 10 carbon atoms, preferably 2 to 10 carbon atoms 8, more preferably a sulfamoyl group having 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl, piperidinosulfonyl), a nitro group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably Is an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy), having 6 to 20 carbon atoms, preferably having 6 to 1 carbon atoms.
2, more preferably an aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, p-methylphenoxy, p-chlorophenoxy, naphthoxy),

An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms 12, more preferably an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy, benzoyloxy);
It preferably has 2 to 12 carbon atoms, and more preferably 2 carbon atoms.
To 8 acylamino groups (eg, acetylamino), 1 to 20, preferably 1 to 10, more preferably 1 to 8 carbon atoms, sulfonyl groups (eg, methanesulfonyl, ethanesulfonyl, benzenesulfonyl), 1 to 20, preferably 1 to 1 carbon atoms
0, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl, ethanesulfinyl, benzenesulfinyl), a sulfonylamino group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 8 carbon atoms. Groups (eg, methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino),

An amino group, a substituted amino group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino, benzylamino, anilino, diphenylamino), An ammonium group having a number of 0 to 15, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (eg, trimethylammonium, triethylammonium);
To 15, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, such as a trimethylhydrazino group, 1 to 15 carbon atoms, preferably 1 carbon atoms.
To 10, more preferably a ureido group having 1 to 6 carbon atoms (e.g., a ureido group, an N, N-dimethylureido group);
C1 to C15, preferably C1 to C10, more preferably C1 to C6 imide group (for example, succinimide group), C1 to C20, preferably C1 to C12, more preferably C1 to C12 1 to 8 alkylthio groups (eg methylthio, ethylthio, propylthio),
An arylthio group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio, p-chlorophenylthio, 2-pyridylthio, naphthylthio), 2 carbon atoms To 20, preferably 2 to 12, more preferably 2 to 8 alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, 2-benzyloxycarbonyl), 6 to 20 carbon atoms, preferably 6 to 20 carbon atoms 12, more preferably 6 to 10 carbon atoms
Aryloxycarbonyl group (for example, phenoxycarbonyl),

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably A substituted alkyl group having 1 to 10, more preferably 1 to 5 carbon atoms {eg, hydroxymethyl, trifluoromethyl, benzyl, carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here having 2 to 18 carbon atoms, preferably Unsaturated hydrocarbon groups having 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms (for example, vinyl group, ethynyl group 1-cyclohexenyl group, benzylidine group, benzylidene group) are also included in the substituted alkyl group. Having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, and more preferably 6 to 10 carbon atoms.換又 unsubstituted aryl group (e.g. phenyl, naphthyl, p- carboxyphenyl, p- nitrophenyl, 3,5-dichlorophenyl, p- cyanophenyl, m- fluorophenyl, p- tolyl)

A substituted or unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro Furfuryl). Further, a structure in which a benzene ring or a naphthalene ring is condensed can be used. Further, V may further substitute on these substituents. Preferred substituents are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom and benzene ring condensation, more preferably methyl group, phenyl group, methoxy group chlorine atom, bromine atom, iodine atom, and benzene ring condensation. It is.

Z ₁ , Z ₂ , Z ₃ , Z ₄ , Z ₅ , and Z ₆
Preferred examples of the substituent V include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxyl group, a phosphate group, and the like. More preferably, an aryl group, a heterocyclic group, a carboxyl group, a phosphate group, Among them, a phenyl group, a naphthyl group, a biphenyl group, a thienyl group, a furyl group, a carboxyl group, and a phosphoric acid group are more preferable, and these may be further substituted. Particularly preferred is phenyl, which may be substituted with a carboxyl group or a phosphate group.

In the general formulas (I) and (IV), R ₁ , R ₃ and R ₄ represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group, and the substituent is a substituent V And the like, and preferably represents a substituted or unsubstituted aryl group or an alkyl group substituted with an aryl group or a heterocyclic group. In addition, the dyes in the general formulas (I) and (IV) must be cationic dyes. Therefore,
Examples of the alkyl group represented by R ₁ , R ₃ , and R ₄ include, for example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl Isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), unsaturated hydrocarbon groups (eg, allyl, crotyl), hydroxyalkyl groups (eg, 2-hydroxyethyl, 3-hydroxypropyl), alkoxyalkyl groups ( For example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl), an alkoxycarbonylalkyl group (for example, ethoxycarbonylethyl, 2-benzyloxycarbonylethyl), an acyloxyalkyl group (for example, 2-acetyloxyethyl), Acylalkyl group (2-acetylethyl), As a bamoylalkyl group (for example, 2-morpholinocarbonylethyl), a sulfamoylalkyl group (for example, N, N-dimethylsulfamoylmethyl), and an alkyl group substituted with an aryl group, an aralkyl group (for example, benzyl) , 2-phenylethyl, naphthylmethyl, 2- (4-biphenyl) ethyl), an aryloxyalkyl group (for example, 2-phenoxyethyl, 2- (1-naphthoxy) ethyl, 2- (4
-Biphenyloxy) ethyl, 2- (o, m, p-halophenoxy) ethyl, 2- (o, m, p-methoxyphenoxy) ethyl), an aryloxycarbonylalkyl group (3-phenoxycarbonylpropyl, 2- (1 -Naphthoxycarbonyl) ethyl) and the like. Also,
Examples of the heterocyclic-substituted alkyl group include 2- (pyrrolidin-2-one-1-yl) ethyl and 2- (2-pyridyl)
Ethyl, 2- (4-pyridyl) ethyl, 2- (2-furyl) ethyl, 2- (2-thienyl) ethyl, 2- (2-
Pyridylmethoxy) ethyl. R ₁ , R ₃ ,
And the aryl group represented by R ₄ include phenyl, naphthyl, biphenyl and the like.

The substituent represented by R ₁ , R ₃ and R ₄ is preferably the above-mentioned substituted or unsubstituted aryl group or an alkyl group substituted with an aryl group or a heterocyclic group. Those substituted with an ammonium group having a cationic charge such as a trialkylammonio group are more preferable. Preferred ammonio groups include unsubstituted trialkylammonio groups having 1 to 7 carbon atoms (for example, trimethylammonio group, triethylammonio group, tripropylammonio group, tributylammonio group, dimethylethylammonio group, dibutylammonium group, dibutylammonium group). (Ethylammonio group), and a substituted trialkylammonio group having 1 to 7 carbon atoms ｛substituents include those represented by the aforementioned V. For example, a trichloromethylammonio group,
Tri (2-methoxy) ethylammonio group, tri (3,3
3-dichloropropyl) ammonium group, dibutyl (2-
Hydroxyethyl) ammonio group), having 1 to 18 carbon atoms
Nitrogen-containing heterocyclic nitrogen quaternary salts (e.g., 1-pyridinio, 1-methyl-4-pyridinio, 1-quinolinio, and 3-thiazolinio groups, which are further substituted with the aforementioned substituent V and the like). May be performed). More preferred ammonio groups are unsubstituted trialkylammonio groups having 1 to 4 carbon atoms (for example, trimethylammonio group, triethylammonio group, tripropylammonio group, tributylammonio group), and 1-pyridinio group. And particularly preferably a trimethylammonio group, a triethylammonio group, and a 1-pyridinio group.

In the general formulas (II) and (V), R_Two, R
_Five, And R₆Represents an alkyl group or an aryl group and is substituted
Examples of the group include the substituents described in the description of the substituent V and the like.
I can do it. Preferably a substituted or unsubstituted aryl group
Or alkyl substituted with an aryl group or a heterocyclic group
Represents a group. Moreover, in the general formulas (II) and (V)
Must be an anionic dye. Follow
And R_Two, R_Five, And R ₆As an alkyl group represented by
Is, for example, from 1 to 15 carbon atoms, preferably from 1 to 15 carbon atoms.
10, particularly preferably an alkyl group having 1 to 5 carbon atoms.
Rufo, phosphate, and / or carboxyl groups substituted
(Eg, sulfomethyl, sulfoethyl, 2,2
-Difluoro-2-carboxyethyl, 2-phosphoethyl
Group), sulfo group, phosphate group and / or carboxyl group
Is substituted with an unsaturated hydrocarbon group (for example, 3-sulfo-
2-propenyl), a sulfo group, a phosphate group, and / or
An alkoxyalkyl group substituted by a boxyl group (for example,
2-sulfomethoxyethyl), a sulfo group, a phosphate group,
Or carboxy-substituted alkoxycarbonyl
Alkyl group (for example, sulfoethoxycarbonyl
Tyl, 2-sulfobenzyloxycarbonylethyl),
Sulfo, phosphate, and / or carboxyl groups are substituted
Acyloxyalkyl group (for example, 2-phosphoacetyl)
Ruoxyethyl), an acylalkyl group (2-sulfone
Cetylethyl). The aryl group is substituted
As a sulfo group, a phosphate group, or
An aralkyl group substituted with a carboxyl group (for example, 2-
Sulfobenzyl, 4-sulfobenzyl, 4-sulfofe
Netyl, 3-phenyl-3-sulfopropyl, 3-phenyl
Enyl-2-sulfopropyl, 4,4-diphenyl-
3-sulfobutyl, 2- (4'-sulfo-4-bifu
Enyl) ethyl, 4-phosphobenzyl), sulfo group,
Aryloxy substituted with an acid group or a carboxyl group
Cicarbonylalkyl group (3-sulfophenoxycal
Carbonyl)), a sulfo group, a phosphate group, or
An aryloxyalkyl group substituted by a boxyl group (eg,
For example, 2- (4-sulfophenoxy) ethyl, 2- (2
-Phosphophenoxy) ethyl, 4,4-diphenoxy-
3-sulfobutyl), and the like. Also, complex
Examples of the alkyl group substituted with a ring group include 3- (2-pyridyl)
(Zyl) -3-sulfopropyl, 3- (2-furyl) -3
-Sulfopropyl, 2- (2-thienyl) -2-sulfo
Propyl and the like.

The substituent represented by R ₂ , R ₅ and R ₆ is preferably an aralkyl group, a sulfo group, a phosphate group or a carboxyl group substituted by the above-mentioned sulfo group, phosphate group or carboxyl group. An unsaturated hydrocarbon group, a sulfo group, a phosphate group, or an aryloxyalkyl group substituted with a carboxyl group, more preferably 2-sulfobenzyl, 4-sulfobenzyl, 4-sulfophenethyl, -Phenyl-3-sulfopropyl,
3-phenyl-2-sulfopropyl, 4,4-diphenyl-3-sulfobutyl, 2- (4′-sulfo-4
-Biphenyl) ethyl, 4-phosphobenzyl, 3-sulfo-2-propenyl, 2- (4-sulfophenoxy) ethyl and the like.

L ₁ , L ₂ , L ₃ , L ₄ , L ₅ , L ₆ , L
_{7, L 8, L 9,} L 10, L 11, L 12, L 13, L 14,
L ₁₅ , L ₁₆ , L ₁₇ and L ₁₈ each independently represent a methine group. The methine group represented by L _{1 to} L ₁₈ may have a substituent. Examples of the substituent include a substituted or unsubstituted C ₁ to C 15, preferably C ₁ to C 10, particularly preferably carbon An alkyl group of the formulas 1 to 5 (eg, methyl, ethyl, 2-carboxyethyl), a substituted or unsubstituted C 6 to C 20, preferably C 6 to C 15,
More preferably, an aryl group having 6 to 10 carbon atoms (for example, phenyl, o-carboxyphenyl), a substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 to 15 carbon atoms,
More preferably, a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-dimethylbarbituric acid group), a halogen atom,
(Eg, chlorine, bromine, iodine, fluorine), having 1 to 1 carbon atoms
5, preferably an alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methoxy, ethoxy), 0 to 15 carbon atoms, preferably 2 to 1 carbon atoms
0, more preferably an amino group having 4 to 10 carbon atoms (eg, methylamino, N, N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), 1 to 15 carbon atoms, preferably 1 carbon atom To 10, more preferably an alkylthio group having 1 to 5 carbon atoms (eg, methylthio, ethylthio), an arylthio group having 6 to 20, preferably 6 to 12, and more preferably 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. Further, a ring may be formed with another methine group, or an auxochrome ring may be formed.

P ₁ , p ₂ , p ₃ , p ₄ , p ₅ , and p ₆
Each independently represents 0, 1, 2, or 3. It is preferably 0, 1, or 2, and more preferably 0 or 1.
When p ₁ , p ₂ , p ₃ , p ₄ , p ₅ , and p ₆ are 2 or more, the methine group is repeated but need not be the same.

N ₁ and n ₂ each independently represent 0 or 1. Preferably it is 0.

M ₁ , M ₂ , M ₃ , and M ₄ are included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the molecule. .
Typical cations include hydrogen ions (H ⁺ ), alkali metal ions (sodium ions, potassium ions,
Inorganic ions such as lithium ions) and alkaline earth metal ions (eg, calcium ions); and organic ions such as ammonium ions (eg, ammonium ions, tetraalkylammonium ions, pyridinium ions, and ethylpyridinium ions). The anion may be an inorganic anion or an organic anion, and may be a halogen anion (eg, a fluorine ion, a chloride ion,
Bromide ion, iodine ion, substituted arylsulfonate ion (for example, p-toluenesulfonate ion, p-chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion,
1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion,
Picric acid ion, acetate ion, and trifluoromethanesulfonic acid ion. Further, an ionic polymer or a molecule having a charge opposite to that of the molecule may be used. m ₁ ,
m ₂ , m ₃ , and m ₄ represent the numbers required to balance the charges, and are 0 when forming a salt in the molecule.

The number of methine groups in Q ₁ or Q ₂ is preferably 0 to 7, more preferably 0 to 5, and particularly preferably 3. The methine group is preferably substituted by a substituent (heterocyclic group, aliphatic group, or aromatic group) necessary for forming a methine dye, and a preferable substituent is a heterocyclic group or an aromatic group. And particularly preferably a heterocyclic group. Examples of the heterocyclic group include Z ₄ and Z ₆ described above.
Are preferred as examples. As the aromatic group, a substituted or unsubstituted aromatic group (for example, a 4-dimethylaminophenyl group, a 4-methoxyphenyl group, a phenyl group,
-Dimethylaminonaphthyl group). As the aliphatic group, an alkoxycarbonyl group (for example, an ethoxycarbonyl group) and an acyl group (for example, an acetyl group) are preferable. Further, other examples include the substituents represented by the above-mentioned V. For example, a substituted or unsubstituted amino group (for example,
Preferred are an amino group, a dimethylamino group), a cyano group, an alkoxycarbonyl group (eg, ethoxycarbonyl), a substituted or unsubstituted alkylsulfonyl group (eg, a methylsulfonyl group), and a substituted or unsubstituted acyl group (eg, an acetyl group).

Specific examples of the compound represented by the general formula (I) of the present invention (including the general formula (IV) of the subordinate concept) are shown below, but the present invention is not limited thereto.

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Specific examples of the compound represented by the general formula (II) of the present invention (including the general formula (V) of the subordinate concept) are shown below, but the present invention is not limited thereto.

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Next, the compound represented by formula (III) will be described in detail. In the general formula (III), D represents a sensitizing dye moiety having adsorptivity to semiconductor fine particles such as titanium dioxide. D dyes include cyanine dyes, merocyanine dyes, oxonol dyes, holopolar cyanine dyes,
Hemicyanine dye, styryl dye, hemioxonol dye, xanthene dye, triarylmethane dye, thiazine dye, acridine dye, oxazine dye, aminonaphthalene dye, phthalocyanine dye, porphyrin dye, other Metal chelate compounds are included. Preferable examples include a cyanine dye, a merocyanine dye, a rhodocyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, and a styryl dye. In this case, the cyanine dyes include those in which the substituent on the methine chain forming the dye forms a squarium ring or a croconium ring. For a detailed description of these dyes, see FM Harmer, Heterocyclic Compounds-Cyanine Soybeans and Related Compounds.
nds-Cyanine Dyes and Related Compounds), John Wiley & Sons
New York, London, 1964, DM
DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Compounds-Sp
ecial topics in heterocyclic chemistry), 18
Chapter 14, section 14, pages 482 to 515, and the like. The general formulas of cyanine dyes, merocyanine dyes and rhodacyanine dyes are described in US Pat. No. 5,340,694 No. 2
Those shown in (XI), (XII) and (XIII) on pages 1, 22 are preferred. Further, D preferably has a substituent having a high adsorptivity to semiconductor fine particles such as titanium dioxide.
It may be adsorbed by either physical adsorption or chemical adsorption. Representative examples of the adsorptive substituent include a carboxyl group, a phosphoric acid group, a sulfo group, a sulfinic acid group, a hydroxyl group, an amino group, and a mercapto group, and more preferably a carboxyl group and a phosphate group.

Representative examples of the luminescent dyes represented by A include cyanine dyes, merocyanine dyes, oxonol dyes, holopolar cyanine dyes, hemicyanine dyes,
Styryl dyes, hemioxonol dyes, xanthene dyes, triarylmethane dyes, thiazine dyes,
Examples include acridine dyes, oxazine dyes, aminonaphthalene dyes, phthalocyanine dyes, porphyrin dyes, and other metal chelate compounds. As the kind of these luminescent dyes, those having a skeleton structure of a dye used for a dye laser are preferable. These are, for example, Mitsuo Maeda, Laser Research, Vol. 8, p. 694,
803, 958 (1980) and 9:85 (1981), and by F. Sehaefer, "Dye Laser
s ", Springer (1973).
More preferred are a cyanine dye, a merocyanine dye, a rhodacyanine dye, a trinuclear merocyanine dye, an allopolar dye, a hemicyanine dye, a styryl dye, and the like.

L represents a divalent linking group or a single bond. The linking group preferably comprises an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Preferably an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene),
Arylene group (for example, phenylene, naphthylene), alkenylene group (for example), for example, ethenylene, propenylene), alkynylene group (for example, ethinylene, propynylene), amide group, ester group, sulfamide group, sulfonate group, ureido group, sulfonyl group , A sulfinyl group, a thioether group, an ether group, an arbonyl group, -N (Ra)-(Ra represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group),
One or more heterocyclic divalent groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2,4-diyl group, quinoxaline-2,3-diyl group) It represents a divalent linking group having 1 to 20 carbon atoms formed by combining the above. More preferably, an alkylene group having 4 or less carbon atoms (eg, methylene, ethylene, propylene, butylene), an arylene group having 6 to 10 carbon atoms (eg, phenylene, naphthylene), an alkenylene group having 4 or less carbon atoms (eg, eg, ethenylene) , Propenylene), an alkynylene group having 4 or less carbon atoms (e.g., ethynylene, propynylene), an amide group, an ester group, a sulfamide group, and a sulfonate group. It is a divalent linking group or a single bond.

N is an integer of 1 or more, and when it is 2 or more, a plurality of L and A contained therein may be different linking groups and luminescent dye portions, respectively.

In the general formulas (VI), (VII) and (VIII), Z ₇ , Z ₈ , Z ₉ , Z ₁₀ , Z ₁₁ , Z ₁₂ and Z ₁₃ form a nitrogen-containing heterocyclic ring. Represents the group of atoms required to perform Examples of the nitrogen-containing heterocycle formed by Z ₇ , Z ₈ , Z ₉ , Z ₁₁ and Z ₁₃ include a thiazoline nucleus, a thiazole nucleus,
Benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, Benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxalin nucleus, oxadiazole nucleus, Thiadiazole nucleus, tetrazole nucleus, pyrimidine nucleus and the like can be mentioned, preferably benzothiazole nucleus, benzoxazole nucleus,
3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3- It is an isoquinoline nucleus, more preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenin nucleus (for example, 3,3-dimethylindolenine), or a benzimidazole nucleus.

The same examples as in the above Z _{1 to} Z ₆ can be mentioned. Further, V may further substitute on these substituents. Preferred substituents are the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom and benzene ring condensation, more preferably methyl group, phenyl group, methoxy group chlorine atom, bromine atom, iodine atom, and benzene ring condensation. It is.

When the methine dye represented by formula (VI), (VII) or (VIII) represents the adsorptive sensitizing dye moiety represented by D in formula (I), Z ₇ , Z ₈ , Z ₉ , Z
Preferred substituents V on ₁₁ and Z ₁₃ include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a carboxyl group, a phosphate group, a hydroxyl group, an amino group, a sulfo group or a mercapto group, More preferably, an aryl group, a heterocyclic group, a carboxyl group, a phosphoric acid group, and especially a phenyl group, a naphthyl group, a biphenyl group, a thienyl group, and a furyl group are more preferable. , An amino group, a sulfo group or a mercapto group. More preferred are a carboxyl group, a phosphate group, a hydroxyl group, an amino group, a sulfo group and a mercapto group, and particularly preferred are a carboxyl group and a phosphate group.

When the methine dye represented by formula (VI), (VII) or (VIII) represents a luminescent dye moiety represented by A in formula (I), Z ₇ , Z ₈ , Z ₉ , Z ₁₁ ,
And the substituent V on Z ₁₃ is preferably a halogen atom,
Examples thereof include an alkyl group, an aryl group, and a heterocyclic group, and more preferably an aryl group, a heterocyclic group, among which a phenyl group, a naphthyl group, a biphenyl group, a thienyl group, and a furyl group are more preferable, and particularly preferably chloro. , Bromo, methyl, ethyl, phenyl, thienyl, furyl.

Formula (VI), Formula (VII), and Formula
(VIII) R in₇, R₈, R₉, R ₁₁, And R₁₃Is replaced
Or unsubstituted alkyl group or substituted or unsubstituted
Represents an aryl group, and the substituent is described as a substituent V or the like.
And the like. As an alkyl group
For example, having 1 to 18 carbon atoms, preferably 1 to 7 carbon atoms, especially
Preferably 1 to 4 unsubstituted alkyl groups (for example, methyl
, Ethyl, propyl, isopropyl, butyl, isobu
Chill, hexyl, octyl, dodecyl, octadec
Aralkyl groups (eg, benzyl, 2-phenyl)
Ethyl, naphthylmethyl, 2- (4-biphenyl) ethyl
), Unsaturated hydrocarbon groups (eg, allyl,
), A hydroxyalkyl group (eg, 2-hydroxy
Ethyl, 3-hydroxypropyl), alkoxyalkyl
(E.g., 2-methoxyethyl, 2- (2-methoxy)
Ciethoxy) ethyl), aryloxyalkyl groups (eg
For example, 2-phenoxyethyl, 2- (1-naphthoxy) e
Chill, 2- (4-biphenyloxy) ethyl, 2- (o,
m, p-halophenoxy) ethyl, 2- (o, m, p-
Methoxyphenoxy) ethyl), alkoxycarbonyl
Alkyl group (for example, ethoxycarbonylethyl, 2-
Benzyloxycarbonylethyl), aryloxycarbo
Nylalkyl group (3-phenoxycarbonylpropyl,
2- (1-naphthoxycarbonyl) ethyl), acylo
Xyalkyl group (for example, 2-acetyloxyethyl
), An acylalkyl group (2-acetylethyl),
Bamoylalkyl group (for example, 2-morpholinocarboni
Ruethyl), a sulfamoylalkyl group (eg, N,
N-dimethylsulfamoylmethyl), heterocyclic-substituted alkyl
A kill group (for example, 2- (pyrrolidin-2-one-1-i)
Le) ethyl) and the like. R₁, R_Three, And R_Four
Aryl groups represented by phenyl, naphthyl, bi
Phenyl, furyl, thienyl and the like.

When the methine dye represented by formula (VI), (VII) or (VIII) represents the adsorptive sensitizing dye moiety represented by D in formula (I), R ₇ , R ₈ , R ₉ , R
₁₁ and R ₁₃ are preferably substituted alkyl groups (substituents such as carboxyl group, phosphate group,
A hydroxyl group, an amino group, a sulfo group or a mercapto group), an aralkyl group, an aryloxyalkyl group, a carboxyalkyl group, a sulfoalkyl group, and the like. , An amino group, a sulfo group or a mercapto group. More preferably, it is an alkyl group substituted by a carboxyl group or a phosphate group.

When the methine dye represented by formula (VI), (VII) or (VIII) represents the luminescent dye moiety represented by A in formula (I), R ₇ , R ₈ , R ₉ , R ₁₁ ,
And the substituent represented by R ₁₃ are preferably the above-mentioned unsubstituted alkyl group, aralkyl group, aryloxyalkyl group, carboxyalkyl group, sulfoalkyl group,
More preferred are an unsubstituted alkyl group, an aralkyl group and a sulfoalkyl group.

Z ₁₀ represents the group of atoms required to form an acidic nucleus, but can take the form of an acidic nucleus of any common merocyanine dye. The acidic nucleus referred to here is, for example, “Theory of the Photographic Process” edited by James (The Theory of th Photographic Process).
e Photographic Process) 4th Edition, Macmillan Publishing Company,
1977, p. 198. In particular,
U.S. Pat. Nos. 3,567,719 and 3,575,86
No. 9, No. 3,804,634, No. 3,837,862
No. 4,002,480, 4,925,777
And JP-A-3-167546. Acidic nuclei are preferred when forming a 5- or 6-membered nitrogen-containing heterocyclic compound consisting of carbon, nitrogen and chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms, the following nuclei being preferred: No. 2-pyrazolone-5-one, pyrazolidine-3,5-dione, imidazolin-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one,
-Oxazolin-5-one, 2-thiooxazoline-
2,4-dione, isoxazolin-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-
2,4-dithione, isorhodanine, indan-1,3
-Dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2-one, indoline-3-one, 2-oxoindazolium, 3-oxoindazolium, 5,7 -Dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinoline-
4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarnituric acid, coumarin-2,
4-dione, indazolin-2-one, pyrido [1,2
-A] pyrimidine-1,3-dione, pyrazolo [1,5
-B] quinazolone, pyrazolo [1,5-a] benzimidazole, pyrazolopyridone, 1,2,3,4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3
Nuclei of dihydrobenzo [d] thiophen-1,1-dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophen-1,1-dioxide;

[0125] Preferably hydantoin as Z _10, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thio-oxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine -
2,4-dithione, barbituric acid and 2-thiobarnituric acid, more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one,
Rhodanine, barbituric acid and 2-thiobarnituric acid. Particularly preferred are 4-thiohydantoin and 2-oxazolin-5-one.

The 5- or 6-membered nitrogen-containing heterocyclic ring formed by Z ₁₂ is obtained by removing an oxo group or a thiooxo group from the heterocyclic ring represented by Z ₁₀ . Preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazolin-5-one, 2-thiooxazoline-2,4
-Dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarnituric acid, except for the oxo group or the thiooxo group, more preferably hydantoin, 2 or It is obtained by removing an oxo group or a thiooxo group from 4-thiohydantoin, 2-oxazolin-5-one, rhodanine, barbituric acid, and 2-thiobarnituric acid. Particularly preferably, 4-thiohydantoin, 2
-Oxazoline-5-one, an oxo group from rhodanine,
Alternatively, the thiooxo group is excluded.

Examples of the alkyl group represented by R ₁₀ and R ₁₂ include the unsubstituted alkyl group and the substituted alkyl group mentioned as examples of R ₁ and the like, and similar ones are preferable. Further, it has 2 to 20 carbon atoms, preferably 6 carbon atoms.
To 10, more preferably an unsubstituted aryl group having 6 to 8 carbon atoms (eg, phenyl group, 1-naphthyl group), 2 to 20, preferably 6 to 10, more preferably 6 to 8 carbon atoms. A substituted aryl group (for example, Z
_And an aryl group substituted by V mentioned as a substituent such as ₁ . Specifically, a p-methoxyphenyl group, p
-Methylphenyl group, p-chlorophenyl group and the like. ), An unsubstituted heterocyclic group having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms (eg, 2-furyl group, 2-thienyl group 2-pyridyl group, 3-pyrazolyl group) , Isoxazolyl 3-isothiazolyl, 2-imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 5-tetrazolyl), carbon number 1 from 20, preferably from 3 to 10 carbon atoms, more preferably an aryl group V is substituted cited as substituents, such as Z ₁ substituted Hajime Tamaki (e.g., the aforementioned 8 from 4 carbon atoms. Specifically Is a 5-methyl-2-thienyl group, a 4-methoxy-2-pyridyl group, etc.). Preferred as R ₁₀ and R ₁₂ are methyl, ethyl, 2-sulfoethyl, 3-
Sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, carboxymethyl, phenyl, 2-pyridyl, 2-
Thiazolyl, and more preferably, ethyl, 2-sulfoethyl, carboxymethyl, phenyl, and 2-pyridyl.

L ₁₉ , L ₂₀ , L ₂₁ , L ₂₂ , L ₂₃ , L ₂₄ , L
_{25, L 26, L 27,} L 28, L 29, L 30, L 31, L 32,
_{L 33, L 34, L 35} , L 36, L 37 and L ₃₈ each independently represents a methine group. The methine group represented by L _{19 to} L ₃₈ may have a substituent, and examples of the substituent include a substituted or unsubstituted C 1 to C 15, preferably C 1 to C 10, particularly preferably carbon An alkyl group of the formulas 1 to 5 (eg, methyl, ethyl, 2-carboxyethyl), substituted or unsubstituted C 6 to C 20, preferably C 6
To 15, more preferably an aryl group having 6 to 10 carbon atoms (eg, phenyl, o-carboxyphenyl), substituted or unsubstituted 3 to 20 carbon atoms, preferably 4 carbon atoms.
To 15, more preferably a heterocyclic group having 6 to 10 carbon atoms (for example, N, N-dimethylbarbituric acid group), a halogen atom (for example, chlorine, bromine, iodine, fluorine), and having 1 to 15 carbon atoms, preferably An alkoxy group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methoxy,
Ethoxy), an amino group having 0 to 15 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms (eg, methylamino, N, N-dimethylamino, N-
Methyl-N-phenylamino, N-methylpiperazino), having 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably an alkylthio group having 1 to 5 carbon atoms (eg, methylthio, ethylthio);
An arylthio group having 0, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms (for example, phenylthio,
p-methylphenylthio) and the like. Further, a ring may be formed with another methine group, or an auxochrome ring may be formed.

Each of n ₃ , n ₄ , n ₅ and n ₆ independently represents 0, 1, 2 or 3. Preferably 0, 1,
2, more preferably 0 or 1. n ₃ , n ₄ ,
When n ₅ and n ₆ are 2 or more, the methine group is repeated but need not be the same.

P ₇ , p ₈ , p ₉ , p ₁₀ and p ₁₁ each independently represent 0 or 1. Preferably it is 0.

M ₅ , M ₆ , and M ₇ are included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the molecule. Typical cations include inorganic ions such as hydrogen ions (H ⁺ ), alkali metal ions (sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), and ammonium ions (eg, ammonium ions). , Tetraalkylammonium ions, pyridinium ions, and ethylpyridinium ions). The anion may be either an inorganic anion or an organic anion, and may be a halogen anion (eg, a fluorine ion, a chloride ion, a bromine ion, an iodine ion), a substituted arylsulfonate ion (eg, a p-toluenesulfonic acid ion, -Chlorobenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenedisulfonate ion, 1,
5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetic acid Ion and trifluoromethanesulfonic acid ion. Further, an ionic polymer or a molecule having a charge opposite to that of the molecule may be used. m _5, m
₆ and m ₇ represent the numbers required to balance the charges,
It is 0 when a salt is formed in the molecule.

Specific examples of the compounds represented by the general formula (III) of the present invention (including the general formulas (VI), (VII) and (VIII) as subordinate concepts) are shown below. It is not limited.

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The organic dyes of the present invention are described in FM Harmer, "Heterocyclic Compounds-Cyanine Dyes and Related Compounds".
Compounds), John Willie and Sons (Jo
hn Wiley & Sons)-New York, London, 196
Fourth year, DMSturmer, Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (Heter
ocyclic Compounds-Special topics in heterocyclic c
hemistry) ", Chapter 18, Section 14, 482-51
Section 5, John Wiley and Sands
& Sons)-New York, London, 1977,
`` Rodd's Chemistry of Carbon Compounds '' 2nd.Ed.v
ol. IV, partB, 1977, Chapter 15, Chapters 369-42
Section 2, Elsevier Science Publishing Company In
c.) New York, UK Patent No. 1,077,61
It can be synthesized based on the method described in No. 1 or the like.

The following shows a synthesis example.

Synthesis Example 1 (Synthesis of Compound I-1) Compound (I-1) can be synthesized according to Scheme 1 shown below.

[0166]

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(A-1) 10 g and 26.4 g of phenethyl paratoluenesulfonate are heated at 160 ° C. for 5 hours. To the obtained brown candy substance, 25 ml of triethyl orthopropionate, 25 ml of pyridine and 10 ml of acetic acid are added, and the mixture is stirred at 150 ° C. for 1 hour. After cooling, ethyl acetate:
A hexane = 1: 3 solution is added, and the mixture is stirred at room temperature to separate a viscous oily substance. The solvent was removed by decantation, and the mixture was washed three times with hexane. The resulting brown candy substance was heated and dissolved in methanol, and a methanol solution of 3.0 g of sodium bromide was added. When the mixture was allowed to stand overnight, crystals precipitated. The crystals were separated by suction filtration and recrystallized from methanol to obtain 1.4 g of (I-1). (Λmax = 507 nm (ε = 1.62 × 10 ⁵ ) (in methanol))

Synthesis Example 2 (Synthesis of Compound I-17) Compound (I-17) can be synthesized according to Scheme 2 shown below.

[0169]

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(A-2) 10.8 g and 26.4 g of phenethyl paratoluenesulfonate are heated at 160 ° C. for 5 hours. 40 ml of triethylorthopropionate, 50 ml of pyridine, 25 ml of acetic acid were added to the obtained brown candy substance.
And stirred at 135 ° C. for 0.5 hour. After allowing to cool, a solution of ethyl acetate: hexane = 1: 4 is added, and the mixture is stirred at room temperature to separate viscous oily substances. The solvent was removed by decantation, and the mixture was washed three times with hexane. The resulting brown candy substance was heated and dissolved in methanol, and a methanol solution of 3.0 g of sodium bromide was added. When the mixture was allowed to stand overnight, crystals precipitated. The crystals were separated by suction filtration and recrystallized from methanol to obtain 1.30 g of (I-17). (Λmax = 565 nm (ε = 1.26 × 10 ⁵ ) (in methanol))

Synthesis Example 3 (Synthesis of Compound II-1) Compound (II-1) can be synthesized according to Scheme 3 shown below.

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(A-1) 10 g and 12.2 g of 1,2-benzopropanesultone are heated at 160 ° C. for 5 hours.
After cooling to 70 ° C., ethyl acetate was added, and the mixture was stirred at room temperature for 1 hour to obtain crystals. 20 ml of triethyl orthopropionate, 20 ml of pyridine and 8 ml of acetic acid are added thereto, and the mixture is stirred at 150 ° C. for 1.5 hours. After cooling, ethyl acetate is added and the mixture is stirred at room temperature to separate a viscous oily substance. The solvent was removed by decantation, and the obtained brown candy substance was heated and dissolved in methanol, triethylamine was added, and the mixture was allowed to stand for 1 hour to precipitate crystals. The crystals are separated by suction filtration, and methanol: chloroform =
The resultant was dissolved in a 1: 1 solvent by heating, concentrated by heating under normal pressure until the volume of the solution was reduced to half, and the precipitated crystals were taken out by standing overnight, and dried to obtain 5.8 g of (II-1). Obtained. (Λmax = 504 nm (ε = 1.46 × 10 ⁵ ) (in methanol))

Synthesis Example 4 (Synthesis of Compound III-54) Compound (III-54) can be synthesized according to schemes 4 to 6 shown below.

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Synthesis of compound (A): 5,6-dichloro-
20 g of 2-methylbenzimidazole and 25.4 g of N- (2-bromoethyl) phthalimide are dissolved in acetonitrile at room temperature. 4.4g of sodium hydroxide
Was added dropwise, and the mixture was stirred at room temperature for 2 days. After extraction with dichloromethane, drying and evaporation of the solvent under reduced pressure, 44 g of crystals were obtained. 8 g of ethyl tyl paratoluenesulfonate is added to 10 g of the obtained crystals, and the mixture is stirred at 150 ° C. for 5 hours.
After allowing to cool, acetone is added, and the mixture is stirred at room temperature to precipitate crystals. The crystals were separated by suction filtration and the compound (1)
A) (13.0 g, melting point: 289 ° C.) was obtained. Further, 30 g of 5-phenyl-2-methylbenzothiazole and 40 g of ethyltyl paratoluenesulfonate were mixed and stirred at 150 ° C. for 5 hours. After allowing to cool, crystallization was performed with acetone, and the crystals were collected by filtration and dried under reduced pressure to obtain 45 g of white crystals. This is 3.
8g, N, N'-diphenylformamidine 4g
Was dissolved in ethanol and heated to reflux at 100 ° C. for 1 hour. After allowing to cool, the precipitated crystals were collected by filtration and dried under reduced pressure to obtain 2.69 g of compound (2A). 2.5 g of acetic anhydride was added to 1 g of the compound (2A) obtained as described above.
and 4 ml of DMF were added, followed by stirring at 100 ° C. for 10 minutes. 1 g of the compound (1A) and 1.2 ml of triethylamine were sequentially added thereto, and the mixture was further stirred at 100 ° C. for 30 minutes. After the reaction, water was added, the obtained Harz was taken out by decantation, and recrystallized with a methanol-chloroform solvent to obtain compound (3A). The resulting compound (3
A) To 7.0 g, 230 ml of a 31% aqueous solution of hydrobromic acid, 100 ml of a 49% aqueous solution of hydrobromic acid and 70 ml of trifluoroacetic acid were added, and the mixture was refluxed at 130 ° C. for 3 days. After the reaction solution was concentrated under reduced pressure, acetone was added, and the crystals were collected by filtration and dried to obtain 4.9 g of the compound (A) crystals (λmax = 5).
28 nm (ε = 5.68 × 10 ⁴ ) (in methanol) was obtained.

[0177]

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Synthesis of compound (B): 20 g of 5-chloro-N-ethyl-2-methylbenzimidazole and 11 g of 2-bromopropionamide were mixed and stirred at 160 ° C. for 6 hours. Crystallized with ethyl acetate, the crystals were collected by filtration, and 100 ml of a 49% aqueous solution of hydrobromic acid and 100 ml of water were added thereto.
The mixture was heated at 140 ° C. for 8 hours. After the reaction solution was concentrated under reduced pressure, acetone was added, and the crystals were collected by filtration and dried to obtain 12 g of compound (1B) crystals. Also, 5-chloro-
20 g of N-ethyl-2-methylbenzimidazole and 15 g of butanesultone were mixed and stirred at 160 ° C. for 6 hours. Crystallized with acetone, the crystals were collected by filtration, dried, and N,
20 g of N'-diphenylformamidine was added, acetic anhydride was added, and the mixture was refluxed under heating at 150 ° C. for 6 hours. After cooling, the precipitated crystals were collected by filtration and dried under reduced pressure to give Compound (2).
7.3 g of B) were obtained. 2.2 g of the compound (1B) and 3 g of the compound (2B) were dissolved in dimethyl sulfoxide at room temperature, and 3.1 ml of 1,8-diazabicyclo [5,4,0] -7-undecene was added, followed by stirring at room temperature for 1 hour. When ethyl acetate was added, crystals precipitated, which were taken out and recrystallized from methanol to obtain 0.9 g of compound (B) (λma
x = 507 nm (ε = 6.97 × 10 ⁴ ) (in methanol))
I got

[0179]

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Synthesis of compound (III-54): 100 mg of compound (A) and 115 mg of compound (B) were dissolved in 5 ml of dimethyl sulfoxide at room temperature, and 30 mg of dimethylaminopyridine and 2-chloro-1-methylpyridinium iodide were added thereto. 100 mg was added, and the mixture was stirred at room temperature for 20 minutes. To this, triethylamine (0.08 ml) was added, and the mixture was further stirred at room temperature for 7 hours. Ethyl acetate was added to precipitate crystals, and the obtained crystals were purified by silica gel column chromatography to give 20 mg of compound (I-54) (λ
max = 507.7 nm (ε = 1.39 × 10 ⁵ ) (in methanol).

Next, a dye-sensitized photoelectric conversion element to which the polymethine dye of the present invention is applied and a photochemical cell will be described in detail. In the present invention, the dye-sensitized photoelectric conversion element is an electrode comprising a conductive support and a layer (photosensitive layer) of semiconductor fine particles having a polymethine dye adsorbed thereon, which is coated on the conductive support. The photosensitive layer is designed according to the purpose and may have a single-layer structure or a multilayer structure. The dye in one photosensitive layer may be one kind or a mixture of many kinds. Light incident on the photosensitive layer excites the dye. The excited dye has high-energy electrons, which are transferred from the dye to the conduction band of the semiconductor fine particles and reach the conductive support by diffusion. At this time, the dye molecules are oxidized, but it is the photochemical cell that the electrons on the electrodes return to the oxidized dye while working in the external circuit, and the dye-sensitized photoelectric conversion element acts as the negative electrode of this battery .

Hereinafter, the conductive support and the photosensitive layer will be described in detail. The conductive support is a support such as a metal, which has conductivity, or a glass or plastic support having a conductive agent layer on the surface. In the latter case, a preferred conductive agent is a metal (eg, platinum,
Gold, silver, copper, aluminum, rhodium, indium, etc., carbon, or a conductive metal oxide (indium-tin composite oxide, tin oxide doped with fluorine, or the like). The lower the surface resistance of the conductive support, the better. The preferable range of the surface resistance is 50 Ω / cm ² or less, more preferably 10 Ω / cm ² or less. Preferably, the conductive support is substantially transparent. Substantially transparent means that the light transmittance is 10% or more, preferably 50% or more, and particularly preferably 80% or more. As the transparent conductive support, glass or plastic coated with a conductive metal oxide is preferable. When a transparent conductive support is used, it is preferable that light is incident from the support side.

The semiconductor fine particles are fine particles of metal chalcogenide (eg, oxide, sulfide, selenide, etc.) or perovskite. The metal chalcogenide preferably includes titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium, or tantalum oxide, cadmium sulfide, cadmium selenide, and the like. As the perovskite, strontium titanate, calcium titanate and the like are preferably mentioned. Among these, titanium oxide, zinc oxide, tin oxide and tungsten oxide are particularly preferred.

Examples of the method of coating semiconductor fine particles on a conductive support include a method of coating a dispersion or a colloid solution of semiconductor fine particles on a conductive support, and a method of coating a precursor of semiconductor fine particles on a conductive support. A method of coating and hydrolyzing with water in the air to obtain a semiconductor fine particle film, and the like can be given. Examples of a method for preparing a dispersion of semiconductor fine particles include a method of grinding in a mortar, a method of dispersing while grinding using a mill, and a method of precipitating and using fine particles in a solvent when synthesizing a semiconductor. . Examples of the dispersion medium include water and various organic solvents (eg, methanol, ethanol, dichloromethane, acetone, acetonitrile, ethyl acetate, etc.). At the time of dispersion, a polymer, a surfactant, an acid, a chelating agent, or the like may be used as a dispersing aid, if necessary.

The semiconductor fine particles preferably have a large surface area so that many dyes can be adsorbed. For example, in a state where semiconductor fine particles are coated on a support, the surface area thereof is preferably 10 times or more as large as the projected area.
More preferably, it is 0 times or more. In general, as the thickness of the layer of semiconductor fine particles increases, the amount of dye that can be carried per unit area increases, so that the light absorption efficiency increases. However, the diffusion distance of generated electrons increases, and the loss due to charge recombination also increases. The preferred thickness of the semiconductor fine particle layer varies depending on the application of the device, but typically ranges from 0.1 μm to 1 μm.
00 microns. 1 when used as a photochemical battery
It is preferably from 50 to 50 microns, more preferably from 3 to 30 microns. After applying the semiconductor fine particles to the support, the semiconductor fine particles may be baked in order to bring the particles into close contact with each other.

For adsorbing the dye on the semiconductor fine particles, a method of immersing well-dried semiconductor fine particles in a dye solution for a long time is general. The dye solution may be heated to 50 ° C to 100 ° C as needed. The dye may be adsorbed before or after the application of the semiconductor fine particles. Also,
The semiconductor fine particles and the dye may be simultaneously applied and adsorbed. Unadsorbed dye is removed by washing. When baking the coating film, it is preferable that the dye is adsorbed after baking. It is particularly preferable that the dye is quickly adsorbed after the firing and before the water is adsorbed on the coating film surface. The dye to be adsorbed may be one kind or a mixture of several kinds. When mixing, the polymethine dyes of the present invention may be mixed with each other,
U.S. Pat. Nos. 4,927,721, 4,684,537 and 508
4365, 5350644, 5463057, 5
The complex dyes described in JP-A-525440 and JP-A-7-249790 may be mixed with the dye of the present invention.
When the application is a photochemical battery, a dye to be mixed is selected so as to widen the wavelength range of photoelectric conversion as much as possible. Also,
A colorless compound may be co-adsorbed for the purpose of reducing the interaction between dyes such as association. Examples of the hydrophobic compound to be co-adsorbed include steroid compounds having a carboxyl group (for example, cholic acid).

In the present invention, the amount of the dye adsorbed on the semiconductor fine particle layer is 0.01% per square meter of the coating film as the total amount of the dye.
To 100 mmol, more preferably 0.1 to 50 mmol per square meter, and still more preferably 0.5 to 0.5 mmol per square meter.
20 mmol.

After the dye is adsorbed, the surface of the semiconductor fine particles may be treated with amines. Preferred amines include pyridine, 4-tert-butylpyridine, polyvinylpyridine and the like. When these are liquid, they may be used as they are, or may be used by dissolving them in an organic solvent.

The dye-sensitized photoelectric conversion element thus produced can be applied to various sensors and photochemical cells. When applied to a photochemical cell, a charge transfer layer and a counter electrode are required. Hereinafter, the charge transfer layer and the counter electrode will be described in detail. The charge transfer layer is a layer having a function of replenishing the oxidized dye with electrons. Representative examples include a liquid in which a redox couple is dissolved in an organic solvent, a so-called gel electrolyte in which a liquid in which a redox couple is dissolved in an organic solvent is impregnated in a polymer matrix, and a molten salt containing a redox couple. Examples of the redox couple include a combination of iodine and iodide (eg, lithium iodide, tetrabutylammonium iodide, tetrapropylammonium iodide, etc.), an alkyl viologen (eg, methyl viologen chloride, hexyl viologen bromide, benzyl viologen tetrafluoroborate) And its reduced form combination. Combinations of polyhydroxybenzenes (eg, hydroquinone, naphthohydroquinone, etc.) and oxidized forms thereof. A combination of divalent and trivalent iron complexes (for example, red blood salt and yellow blood salt) and the like can be mentioned. Of these, a combination of iodine and iodide is preferred. As an organic solvent for dissolving these, aprotic polar solvents (for example, acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide,
Dimethylsulfoxide, sulfolane, 1,3-dimethylimidazolinone, 3-methyloxazolidinone, etc.) are preferred. Examples of the polymer used for the matrix of the gel electrolyte include polyacrylonitrile and polyvinylidene fluoride. Examples of the molten salt include those obtained by mixing polyethylene iodide with lithium iodide and at least one other lithium salt (eg, lithium acetate, lithium perchlorate, etc.) to give fluidity at room temperature. . Since the redox couple becomes a carrier of electrons, a certain concentration is required. The preferred concentration is 0.01 mol / L or more in total, more preferably 0.1 mol / L, and particularly preferably 0.3 mol / L or more.

The counter electrode serves as the positive electrode of the photochemical cell. The counter electrode is usually synonymous with the above-mentioned conductive support, but the support is not necessarily required in a configuration in which the strength is sufficiently maintained. However, having a support is advantageous in terms of hermeticity. In order for light to reach the photosensitive layer,
At least one of the conductive support and the counter electrode described above must be substantially transparent. In the photochemical cell of the present invention, it is preferable that the conductive support is transparent and sunlight is incident from the support side. In this case, it is more preferable that the counter electrode has a property of reflecting light. As the counter electrode of the photochemical cell, glass or plastic on which metal or a conductive oxide is deposited is preferable, and glass on which platinum is deposited is particularly preferable.

In the case of a photochemical battery, it is preferable to seal the side surface of the battery with a polymer, an adhesive or the like in order to prevent the components from evaporating.

[0192]

EXAMPLES Hereinafter, the method for producing the dye-sensitized photoelectric conversion element and the photochemical cell of the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

Example 1 Preparation of Titanium Dioxide Dispersion In a 200 ml stainless steel vessel coated with Teflon, 15 g of titanium dioxide (Degussa P-25, Nippon Aerosil Co., Ltd.), 45 g of water, and a dispersant (Triton X, manufactured by Aldrich) -100) 1
g, 30 g of zirconia beads (manufactured by Nikkato) having a diameter of 0.5 mm were dispersed in a sand grinder mill (manufactured by Imex) at 1500 rpm for 2 hours. The zirconia beads were removed by filtration from the dispersion.

Preparation of Photoelectric Conversion Element Conductive glass coated with fluorine-doped tin oxide (TCO glass manufactured by Asahi Glass, 20 mm × 20 mm
The above dispersion was applied using a glass rod to the conductive surface side of the substrate (which had been cut to the size of). At this time, an adhesive tape was stretched on a part (3 mm from the end) on the conductive surface side to form a spacer, and glass was lined up so that the adhesive tape came to both ends and applied eight sheets at a time. After application, air dry at room temperature for one day,
The adhesive tape was peeled off. (The part with the adhesive tape is used to make electrical contact with the measuring instrument during the photoelectric conversion measurement.) Then, this glass is placed in an electric furnace (Yamato Scientific muffle furnace FP-32). And baked at 450 ° C. for 30 minutes. After the glass was taken out and cooled, an ethanol solution of the dye of the present invention shown in Table 1 ｛6 × 10 ⁻⁴ mol / liter [3 × 10 ⁻⁴ each of the dyes represented by the general formulas (I) and (II)] Mol / l]} for 3 hours. The dyed glass was treated with 4-tert-butylpyridine 10
After immersion in a 30% ethanol solution for 30 minutes, it was washed with ethanol and dried naturally.

Preparation of Photochemical Battery The above-mentioned photoelectric conversion element was superimposed on a platinum-deposited glass of the same size (the uncoated portion of the photoelectric conversion element was shifted so as not to come into contact with the platinum-deposited glass). next,
An electrolytic solution (acetonitrile and a mixture of N-methyl-2-oxazolidinone in a volume ratio of 90:10, 0.05 mol / liter and 0.5 mol of lithium iodide using a mixture of 90 to 10 volumes by means of capillary action in the gap between both glasses) Per liter of solution).

Measurement of Photoelectric Conversion Efficiency The light of a 500 W xenon lamp (Ushio) was applied to AM1.
5G filter (made by Oriel) and sharp cut
Purple by passing through the filter (Kenko L-42)
Simulated sunlight without outside lines was generated. The intensity of this light
Is 50mW / cm ^TwoMet. The photoelectric conversion element of the present invention
Of light, and the generated electricity is measured by a current-voltage measurement
Sley 238). It was determined by this
Open-circuit voltage, short-circuit current, form factor, and
The conversion efficiency is summarized in Table 1.

[0197]

[Table 1]

Example 2 Example 1 was different from Example 1 in that an ethanol solution (3 × 10 ⁻⁴ mol / l) of the dye of the present invention shown in Table 2 below was used instead of the dye in Table 1 when the photoelectric conversion element was prepared. Table 2 summarizes the open-circuit voltage, short-circuit current, shape factor, and conversion efficiency of a photoelectric conversion element and a photochemical cell manufactured by a method different from the above-described method in the same manner as in Example 1.

[0199]

[Table 2]

As shown in Examples 1 and 2, any of the dyes of the present invention has higher photoelectric conversion characteristics than conventional dyes.

[0201]

It has been clarified that the present invention provides a dye-sensitized photoelectric conversion element using an organic dye having high photoelectric conversion characteristics.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tetsuya Watanabe 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. (72) Inventor Takashi Kato 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (6)

[Claims] 1. A photoelectric conversion element using semiconductor fine particles sensitized by an organic dye, wherein the organic dye is adsorbed such that a plurality of dye chromophores exist in a direction perpendicular to the surface of the semiconductor fine particles. Characteristic photoelectric conversion element. However, the polynuclear metal complex is one chromophore. However, the polynuclear metal complex is one chromophore. 2. The photoelectric conversion element according to claim 1, wherein semiconductor fine particles sensitized by simultaneously using at least one kind of cationic dye and at least one kind of anionic dye are used. 3. A semiconductor fine particle sensitized by simultaneously using at least one methine dye represented by the following general formula (I) and at least one methine dye represented by the following general formula (II): The photoelectric conversion device according to claim 1, wherein the photoelectric conversion device is used. General formula (I) In the formula, Z ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. R ₁ is an alkyl group or an aryl group. Q ₁
Represents a methine group or a polymethine group necessary for the compound represented by the general formula (I) to form a methine dye. L ₁ and L ₂ represent a methine group. p ₁ represents 0 or 1. However, Z ₁ , R ₁ and Q ₁ have a substituent in which the methine dye represented by the general formula (I) becomes a cationic dye as a whole. M ₁ represents an anion for charge balancing;
m ₁ represents a number of 0 or more and 10 or less necessary for neutralizing the electric charge of the molecule. General formula (II) In the formula, Z ₂ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. R ₂ is an alkyl group or an aryl group. Q ₂
Represents a methine group or a polymethine group necessary for the compound represented by the general formula (II) to form a methine dye. L ₃ and L ₄ represent a methine group. p ₂ represents 0 or 1. However, Z ₂ , R ₂ and Q ₂ have a substituent in which the methine dye represented by the general formula (II) becomes an anion dye as a whole. M ₂ represents a cation for charge balancing,
m ₂ represents a number from 0 to 10 required to neutralize the charge of the molecule. 4. The photoelectric conversion device according to claim 1, wherein semiconductor fine particles sensitized by at least one compound having two or more dye moieties linked by a covalent bond via a divalent linking group are used. . 5. The photoelectric conversion device according to claim 1, wherein semiconductor fine particles sensitized by at least one compound represented by the following general formula (III) are used. General formula (III) In the formula, D represents a sensitizing dye moiety adsorbed on the semiconductor fine particles. L represents a divalent linking group or a single bond. A represents a luminescent dye moiety linked to D by a linking group L. n is 1
In the case where the number is 2 or more, a plurality of L and A included in the group may be different linking groups and luminescent dye portions. 6. A photochemical cell using the photoelectric conversion element according to claim 1, 2, 3, 4, or 5.