CN100590931C - Dye-sensitized photoelectric conversion device - Google Patents
Dye-sensitized photoelectric conversion device Download PDFInfo
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- CN100590931C CN100590931C CN 200680021358 CN200680021358A CN100590931C CN 100590931 C CN100590931 C CN 100590931C CN 200680021358 CN200680021358 CN 200680021358 CN 200680021358 A CN200680021358 A CN 200680021358A CN 100590931 C CN100590931 C CN 100590931C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Abstract
Disclosed is a photoelectric conversion device wherein a thin film of oxide semiconductor particles formed on a substrate is loaded and sensitized with a methine dye represented by the following formula (1). (1) (In the formula, n represents an integer of 0-7; X and Y respectively represent a hydrogen atom, an optionally substituted aromatic residue, an optionally substituted aliphatic hydrocarbonresidue or the like, and X and Y may combine together to form an optionally substituted ring; A1, A2 and A3 independently represent an optionally substituted aromatic residue, an optionally substituted aliphatic hydrocarbon residue or the like, and when n is not 0, two or more of A1 and/or A2 and/or A3 may combine together to form an optionally substituted ring; and the benzene ring a may have ahalogen atom, an amide group, a hydroxyl group, a cyano group or the like as a substituent.) This photoelectric conversion device can be produced at low cost while having high conversion efficiency.
Description
Technical field
The present invention relates to a kind of components of photo-electric conversion and solar cell by organic pigment sensitizing, specifically, the solar cell that relates to a kind of components of photo-electric conversion and utilize these components of photo-electric conversion, the described components of photo-electric conversion, it is characterized in that, use the oxide semiconductor particulate that carries out sensitizing by methine class pigment with specific skeleton.
Background technology
Instead the energy of fossil fuel such as oil, coal utilizes the solar cell of sunlight to get most of the attention.At present, about silicon solar cell that uses crystallization or amorphous silicon (amorphous silicon) or the compound semiconductor solar cell that has used gallium, arsenic etc. etc., developmental researches such as its high efficiency are actively carried out.But they are difficult to widely used problem owing to make required energy and cost height so exist.In addition, known use is with the components of photo-electric conversion of dye-sensitized semiconductive particles or use the solar cell of this element, and discloses its manufactured materials, manufacturing technology (with reference to patent documentation 1, non-patent literature 1, non-patent literature 2).This components of photo-electric conversion use titanium oxide etc. compares cheap oxide semiconductor as made, with the solar cell that in the past used silicon etc. relatively, can obtain the more cheap components of photo-electric conversion of cost, in addition because to obtain colored solar cell etc. former thereby gazed at.But, in order to obtain the high element of conversion efficiency, used ruthenium class complex compound as sensitizing coloring matter, the cost height of pigment itself, and in its supply, also have problems.In addition, also attempt to use organic pigment as sensitizing coloring matter, have the present situation that does not reach practicability as yet but conversion efficiency, stability, durability are low etc., expectation further improves conversion efficiency (with reference to patent documentation 2).In addition, also can enumerate the example that uses methine class pigment to make the components of photo-electric conversion so far, especially the comparative studies example about Coumarins pigment (with reference to patent documentation 3) or merocyanine element (merocyanine) class pigment constantly increases (with reference to patent documentation 4,5,6,7), but expects the more raising of cost degradation, stability and conversion efficiency.
Patent documentation 1: No. 2664194 communique of Japan Patent
Patent documentation 2:WO2002011213 communique
Patent documentation 3: TOHKEMY 2002-164089 communique
Patent documentation 4: Japanese kokai publication hei 8-81222 communique
Patent documentation 5: Japanese kokai publication hei 11-214731 communique
Patent documentation 6: TOHKEMY 2001-52766 communique
Patent documentation 7: TOHKEMY 2003-59547 communique
Non-patent literature 1:B.O ' Regan and M.Graetzel, Nature, the 353rd volume, 737 pages (1991)
Non-patent literature 2:M.K.Nazeeruddin, A.Kay, I.Rodicio, R.Humphry-B aker, E.Muller, F.Liska, N.Vlachopoulos, M.Graetzel, J.Am.Chem.Soc., the 115th volume, 6382 pages (1993)
Non-patent literature 3:W.Kubo, K.Murakoshi, T.Kitamura, K.Hanabusa, H.Shirai, and S.Yanagida, Chem.Lett., 1241 pages (1998)
Summary of the invention
Use organic pigment to carry out in the semi-conductive components of photo-electric conversion of sensitizing, seeking to develop the organic pigment that uses cheapness, the stable and high high practicability components of photo-electric conversion of conversion efficiency.
The inventor etc. are for solving above-mentioned problem, through making great efforts research, found that by using specific methine class pigment to make semiconductive particles carry out sensitizing and make the components of photo-electric conversion, can obtain stable and the high components of photo-electric conversion of conversion efficiency, thereby finish the present invention.
Promptly the present invention relates to:
(1) a kind of components of photo-electric conversion, it uses the oxide semiconductor particulate that is carried out sensitizing by the methine class pigment of following formula (1) expression,
(in the formula (1), n represents 0 to 7 integer; X and Y represent hydrogen atom independently of one another, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, carboxyl, phosphate, sulfonic group, cyano group, the alkyl sulphonyl that can have substituent carbon number 1 to 5, acyl group, can substituted amide groups or alkoxy carbonyl, in addition, X and Y can have substituent ring in conjunction with forming (but Z does not comprise pyrazolone ring when representing the group of following formula (3)); A
1, A
2And A
3Represent hydrogen atom independently of one another, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, hydroxyl, phosphate, cyano group, halogen atom, carboxyl, formamido, can have substituent alkoxyl, aryloxy group, alkoxy carbonyl, aryl carbonyl or acyl group; In addition, n is more than 2 and A
2And A
3During a plurality of separately the existence, each A
2And A
3Can be identical or different mutually, in addition, n is beyond 0 the time, also can be by a plurality of A
1And/or A
2And/or A
3Formation can have substituent ring; Z represents the group of following formula (2) and (3) expression; )
(the phenyl ring a in the formula (2); except expression in the formula (2); also can have and be selected from by halogen atom, amide groups, hydroxyl, cyano group, nitro, can have substituent alkoxyl, acyl group, replacement or unsubstituted amino, can have substituent aliphatic hydrocarbon residue and can have 1 to 4 substituting group in the group that substituent aromatic residue constitutes; when a plurality of in addition substituting groups exist; these substituting groups can interosculate to form and can have substituent ring; in addition; this substituting group on the phenyl ring a, also can with described A
1And/or A
2And/or A
3Can have substituent ring in conjunction with forming;
Ring Cy in the formula (2) is 4 to 7 yuan of rings, constituting atom as ring can contain the hetero-atom in addition of the nitrogen-atoms shown in carbon atom and the formula (2), in addition, can have substituting group, when ring Cy has a plurality of substituting group, also can interosculate and further form ring by substituting group arbitrarily;
Phenyl ring b in the formula (3); except expression in the formula (3); also can have be selected from by halogen atom, can substituted amide groups, hydroxyl, cyano group, nitro, can have substituent alkoxyl, acyl group, replacement or unsubstituted amino, can have substituent aliphatic hydrocarbon residue and can have 1 to 3 substituting group in the group that substituent aromatic residue constitutes; when a plurality of in addition substituting groups exist; these substituting groups can interosculate to form and can have substituent ring; in addition; this substituting group on the phenyl ring b, can with described A
1, A
2And A
3In any one can have substituent ring in conjunction with forming; E in the formula (3) represents to have the saturated or unsaturated hydrocarbons residue of substituent carbon number 2 to 4, when E has a plurality of substituting group, can by wherein arbitrarily substituting group interosculate and form ring; R
1Expression can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or acyl group);
(2) a kind of components of photo-electric conversion, it uses the oxide semiconductor particulate that is carried out sensitizing by the methine class pigment of following formula (1a) expression,
(in the formula (1a), n represents 0 to 7 integer; R
1Expression can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or acyl group; E represents to comprise the substituent saturated or undersaturated alkyl of having of 2 to 4 of carbon numbers, when E has a plurality of substituting group, can by wherein arbitrarily substituting group interosculate and form ring; Y and X represent hydrogen atom independently of one another, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, carboxyl, phosphate, sulfonic group, cyano group, amide groups, can have the alkyl sulphonyl or the alkoxy carbonyl of substituent carbon number 1 to 5; A
1, A
2And A
3Expression independently of one another can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, hydroxyl, phosphate, cyano group, hydrogen atom, halogen atom, carboxyl, formamido, alkoxy carbonyl, aryl carbonyl or acyl group; In addition, n is more than 2 and A
2And A
3During a plurality of separately the existence, each A
2And each A
3Can be identical or different mutually, n is beyond 0 the time, also can be by a plurality of A
1And/or A
2And/or A
3Formation can have substituent ring, and they can further can have substituent ring with the common formation of phenyl ring a; Phenyl ring a can have and is selected from by halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or unsubstituted amino, can has substituent aliphatic hydrocarbon residue and can have 1 to 3 substituting group in the group that substituent aromatic residue constitutes; in addition; substituting group is a plurality of when existing, these substituting groups can be mutually or as previously mentioned with A
1And/or A
2And/or A
3In conjunction with and form and can have substituent ring, when E has substituting group in addition, can form by the substituting group of E and the substituting group on the phenyl ring a can have substituent ring);
(3) as (1) or (2) the described components of photo-electric conversion, wherein, the methine class pigment of formula (1a) expression described in above-mentioned (2) is the methine class pigment of following formula (2a) expression,
(in the formula (2a), n, R
1, Y, X, A
1, A
2, A
3And phenyl ring b respectively with formula (1a) in identical; R
2aTo R
7aRepresent hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or halogen atom, in addition, R
2aTo R
7aCan interosculate to form and to have substituent ring);
(4) as the components of photo-electric conversion in above-mentioned (3), wherein, the methine class pigment of the formula described in (3) (2a) expression is the methine class pigment of following formula (3a) expression,
(in the formula, n, R
1, Y, X, A
1, A
2, A
3And phenyl ring b respectively with formula (1a) in identical);
(5) as each the components of photo-electric conversion in above-mentioned (2) to (4), its X is a carboxyl;
(6) as each the components of photo-electric conversion in above-mentioned (1) to (5), its Y is cyano group, carboxyl or acyl group person;
(7) as each the components of photo-electric conversion in above-mentioned (1) to (6), its n is 0 to 6;
(8) as each the components of photo-electric conversion in above-mentioned (1) to (7), wherein, R
1For having substituent aliphatic hydrocarbon residue;
(9) as the components of photo-electric conversion of above-mentioned (8), wherein, can have substituent aliphatic hydrocarbon residue, for having the aliphatic hydrocarbon residue of substituent carbon number 5 to 36;
(10) as each the components of photo-electric conversion in above-mentioned (1) to (9), wherein, R
1For having substituent aromatic hydrocarbon residue;
(11) as the components of photo-electric conversion of above-mentioned (10), wherein, can have substituent aromatic hydrocarbon residue, for have can have substituent carbon number 1 to 36 aliphatic hydrocarbon residue as substituent aromatic hydrocarbon residue;
(12) a kind of components of photo-electric conversion, its use by the methine class pigment of more than one above-mentioned (2) described formulas (1a) expression, and metal complex and/or organic pigment with formula (1a) structure in addition carry out the oxide semiconductor particulate of sensitizing;
(13) as each the components of photo-electric conversion in above-mentioned (1) to (12), wherein, the oxide semiconductor particulate contains titanium dioxide, zinc oxide or tin oxide;
(14) as each the components of photo-electric conversion in above-mentioned (2) to (13), wherein, the oxide semiconductor particulate is the oxide semiconductor particulate that carries out sensitizing by the methine class pigment of the expression of the formula described in the load claim 2 (1a) in the presence of inclusion compound;
(15) as each the components of photo-electric conversion in above-mentioned (1) to (14), wherein, the oxide semiconductor particulate is the oxide semiconductor particulate that carries out sensitizing by load methine class pigment on the film of oxide semiconductor particulate;
(16) solar cell of each described components of photo-electric conversion in the use (1) to (14);
(17) the methine class pigment of the expression of the formula (1a) described in above-mentioned (2);
(18) as the methine class pigment of above-mentioned (17), wherein, the methine class pigment of formula (1a) expression described in above-mentioned (2) is the methine class pigment of the formula described in (3) (2a) expression;
(19) as the methine class pigment of above-mentioned (18), wherein, the methine class pigment of representing as the formula (2a) of above-mentioned (3) is the methine class pigment of representing as the formula (3a) of above-mentioned (4);
(20) a kind of components of photo-electric conversion, wherein, on the semiconductive thin film of oxide semiconductor thin-film electrode load the methine class pigment of formula (1a) expression described in above-mentioned (2);
(21) as the components of photo-electric conversion of above-mentioned (1), wherein, the X in the formula (1) described in above-mentioned (1) is a carboxyl, and Y is cyano group, carboxyl or acyl group, and Z is the group of formula (3) expression, and the group of this formula (3) is N-R
1Tetrahydroquinoline-6-base or the N-R that replaces
1Carbazole-3-base (the R that replaces
1With identical in the formula (3));
(22) as the components of photo-electric conversion of above-mentioned (1), wherein, the X in the formula (1) described in above-mentioned (1) is a carboxyl, and Y is a cyano group, and Z is the group of formula (3) expression, and the group of this formula (3) is N-R
1Tetrahydroquinoline-6-base or the N-R that replaces
1Carbazole-3-base (the R that replaces
1With identical in the formula (3));
(23) as the components of photo-electric conversion of above-mentioned (22), wherein, Y is a cyano group, R
1For having the saturated and undersaturated straight or branched alkyl of substituent carbon number 1 to 18;
(24) by following formula HOOC (CN) C=CH-(CH=CH)
NaThe methine class pigment that-Za represents,
(in the formula, Za represents the tetrahydroquinoline-6-base of N-C1 to C18 alkyl replacement or carbazole-3-base that N-C1 to C18 alkyl replaces, and na represents 0 to 3 integer);
(25) a kind of components of photo-electric conversion, wherein, on the film that is arranged at the oxide semiconductor particulate on the substrate load methine class pigment of following formula (1b) expression,
(in the formula (1b), n represents 0 to 7 integer; X and Y represent hydrogen atom independently of one another, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, carboxyl, phosphate, sulfonic group, cyano group, acyl group, amide groups or alkoxy carbonyl, in addition, X also can have substituent ring in conjunction with forming with Y; A
1, A
2And A
3Independent separately, expression can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, hydroxyl, phosphate, cyano group, hydrogen atom, halogen atom, carboxyl, formamido, alkoxy carbonyl, aryl carbonyl or acyl group; In addition, n is more than 2 and A
2And A
3During a plurality of separately the existence, each A
2And each A
3Can be identical or different mutually, n is beyond 0 the time, also can be by a plurality of A
1And/or A
2And/or A
3Formation can have substituent ring, and they also can further can have substituent ring with the common formation of phenyl ring a; Phenyl ring a can have and is selected from by halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or unsubstituted amino, can has substituent aliphatic hydrocarbon residue and can have 1 to 4 substituting group in the group that substituent aromatic residue constitutes; In addition, substituting group is a plurality of when existing, these substituting groups can be mutually or as previously mentioned with A
1And/or A
2And/or A
3In conjunction with and form and can have substituent ring; Ring Cy is 4 to 7 yuan of rings, as the constituting atom of ring, can contain the hetero-atom beyond the nitrogen-atoms in carbon atom and the formula (1b), can have substituting group, when Cy contains a plurality of substituting group, can be interosculated by substituting group arbitrarily and form ring);
(26) a kind of components of photo-electric conversion, wherein, on the film that is arranged at the oxide semiconductor particulate on the substrate load methine class pigment of following formula (2b) expression,
(in the formula (2b), n, X, Y, A
1, A
2, A
3And phenyl ring a respectively with described formula (1b) in identical; R
1bTo R
8bRepresent hydrogen atom independently of one another, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic hydrocarbon residue, halogen atom or hydroxyl, R in addition
1bTo R
4bAnd R
5bTo R
8bCan interosculate separately to form and to have substituent ring; Q represents CR
9R
10, NR
11, oxygen atom, sulphur atom, selenium atom or SO
2R
9To R
11Represent hydrogen atom independently of one another, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic hydrocarbon residue);
(27) as the components of photo-electric conversion of above-mentioned (26), wherein, X is a carboxyl;
(28) as the components of photo-electric conversion of above-mentioned (27), the Y in its formula as above-mentioned (25) (1b) is cyano group, carboxyl or acyl group;
(29) as the components of photo-electric conversion of above-mentioned (25), wherein, X is a carboxyl, and Y is cyano group, carboxyl or acyl group, and n is 0 to 4;
(30) as the components of photo-electric conversion of above-mentioned (26), its X is a carboxyl, and Y is cyano group, carboxyl or acyl group, and n is 0 to 4, and Q is an oxygen atom;
(31) a kind of components of photo-electric conversion, wherein, go up methine class pigment, and the metal complex and/or the organic pigment of formula (1b) expression described in more than one above-mentioned (25) of load with formula (1b) structure in addition at the film (hereinafter referred to as oxide semiconductor thin-film) that is arranged at the oxide semiconductor particulate on the substrate;
(32) as each the components of photo-electric conversion in above-mentioned (25) to (31), wherein, oxide semiconductor thin-film contains titanium dioxide, zinc oxide or tin oxide;
(33) as each the components of photo-electric conversion in above-mentioned (25) to (31), wherein, carrying out oxide semiconductor particulate after the sensitizing by methine class pigment, is by at the methine class pigment of the expression of the formula (1b) described in the load above-mentioned (25) obtains on the oxide semiconductor particulate in the presence of the inclusion compound oxide semiconductor particulate;
(34) solar cell of each described components of photo-electric conversion in use as (25) to (33);
(35) as the components of photo-electric conversion of above-mentioned (1), wherein, X described in above-mentioned (1) is a carboxyl, Y is cyano group, carboxyl or acyl group, perhaps X combines with Y, and X (Y) C=is 2-phenyl-5-carboxyl-3-pyrazolone-4-base, and Z is the group of formula (2) expression, and the group of this formula (2) is the morpholino phenyl, and n is 0;
(36) the methine class pigment represented of following formula X (Y) C=CH-Zb,
(in the formula, X is a carboxyl, and Y is cyano group, carboxyl or acyl group, and perhaps X combines with Y, and X (Y) C=is 2-phenyl-5-carboxyl-3-pyrazolone-4-base, and Zb is the morpholino phenyl).
Therefore, by using specific methine class pigment, can provide conversion efficiency height and the high solar cell of stability.Use when carrying out the oxide semiconductor particulate of sensitizing further and with the pigment more than 2 kinds, the as seen lifting of conversion efficiency.
Embodiment
Below describe the present invention in detail.
The components of photo-electric conversion of the present invention use the oxide semiconductor particulate that is carried out sensitizing by the methine class pigment of aforementioned formula (1) expression.That is, the components of photo-electric conversion of the present invention are that the methine class pigment that the film (following also can only be called oxide semiconductor thin-film) of the oxide semiconductor particulate that is provided with on substrate is gone up the above-mentioned formula of load (1) expression forms.
In the above-mentioned formula (1), the methine class pigment during Z expression (3) is represented with following formula (1a).
In the formula, n represents 0 to 7 integer, is preferably 0 to 6, preferred especially 0 to 4.
R1 in the formula (1a) represents can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or acyl group, preferably can have substituent aromatic residue and maybe can have substituent aliphat family hydrocarbon residue.
Aromatic residue in above-mentioned " can have substituent aromatic residue ", be meant and from aromatic rings, remove 1 group that hydrogen atom forms, as aromatic rings, can enumerate for example benzene, naphthalene, anthracene, luxuriant and rich with fragrance, pyrene perylene, aromatic hydrocarbon rings such as terylene, indenes, Azulene, pyridine, pyrazine, pyrimidine, pyrazoles, pyrazolidine, thiazolidine oxazolidine, pyrans, chromene (chromene), the pyrroles, pyrrolidines, benzimidazole, imidazoline, imidazolidine, imidazoles, pyrazoles, triazole, triazine, diazole, indoline, thiophene, thienothiophene, furans oxazole oxadiazole, thiazine, thiazole, indoles, benzothiazole, diazosulfide, aphthothiazoles benzoxazole Nai Bing oxazole, indolenine, the benzo indolenine, quinoline, heterocyclic type aromatic rings such as quinazoline, fluorenes, carbazoles etc. condense type aromatic ring etc., preferably have the aromatic residue of the aromatic ring (aromatic ring and contain the condensed ring of aromatic ring) of carbon number 5 to 6.
Aliphatic hydrocarbon residue in above-mentioned " can have substituent aliphatic hydrocarbon residue ", can enumerate and to have substituent saturated and undersaturated straight chain, branched alkyl, cycloalkyl, saturated and undersaturated straight chain, the branched alkyl that preferably can have substituent carbon number 1 to 36 further preferably can have saturated and undersaturated straight chain, the branched alkyl of substituent carbon number 1 to 18.In addition, as having substituent cycloalkyl, can enumerate cycloalkyl of carbon number 3 to 8 for example etc.As their object lesson, as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, octyl group, octadecyl, isopropyl, cyclohexyl, vinyl, acrylic, pentenyl, cyclobutenyl, hexenyl, hexadienyl, isopropenyl, dissident's thiazolinyl, cyclohexenyl group, cyclopentadienyl group, acetenyl, propinyl, pentynyl, hexin base, dissident's alkynyl, hexamethylene alkynyl etc.
As above-mentioned acyl group, can enumerate the alkyl-carbonyl, aryl carbonyl of carbon number 1 to 10 for example etc., the alkyl-carbonyl of preferred carbon number 1 to 4.As object lesson, can enumerate acetyl group, trifluoromethyl carbonyl, pentafluoroethyl group carbonyl, propiono etc.
As the substituting group in the substituting group in " can have substituent aromatic residue " and " can have substituent aliphatic hydrocarbon residue "; there is no special qualification; can enumerate sulfonic group; sulfamoyl; cyano group; isocyano group; thiocyanogen; isothiocyano; nitro; nitrosyl radical; halogen atom; hydroxyl; phosphate; phosphate-based; replace or unsubstituted amino; can substituted sulfydryl; can substituted amide groups; can have substituent alkoxyl; can have substituent aryloxy group; carboxyl; carbamoyl; acyl group; aldehyde radical; substituted carbonyls such as alkoxy carbonyl can have substituent aromatic residue; can have substituent aliphatic hydrocarbon residue etc.
As halogen atom, can enumerate atoms such as fluorine, chlorine, bromine, iodine respectively at this; As phosphate-based, can enumerate phosphoric acid (C1 to C4) alkyl ester group etc., as replacing or unsubstituted amino, can enumerate amino, one or dimethylamino, one or diethylamino, one or the amino that replaces of alkyl such as dipropyl amino, one or diphenyl amino, one or the amino that replaces of aromatic series such as dinaphthyl amino, an alkyl one phenyl amino etc. by amino or benzyl amino or acetyl-amino, the phenyl acetyl amino etc. of each alkyl with the replacement of aromatic hydrocarbon residue; As can substituted sulfydryl, can enumerate sulfydryl, alkyl thiol, phenyl sulfydryl etc.; As can substituted amide groups, can enumerate amide groups, alkylamidoalkyl, aryl amido group etc.Be meant by between aforementioned aliphatic hydrocarbon residue and oxygen atom at this alkoxyl to combine the group that forms, can enumerate for example methoxyl group, ethyoxyl, butoxy, tert-butoxy etc.; As having substituent aryloxy group, can enumerate phenoxy group, naphthoxy etc. in addition; They also can have with " can have substituent aromatic residue " the item described in identical substituting group.In addition, as acyl group, can enumerate the alkyl-carbonyl, aryl carbonyl of carbon number 1 to 10 etc., the alkyl-carbonyl of preferred carbon number 1 to 4 specifically can be enumerated acetyl group, trifluoromethyl carbonyl, pentafluoroethyl group carbonyl, propiono etc.In addition as alkoxy carbonyl, can enumerate alkoxy carbonyl of carbon number 1 to 10 for example etc.
In addition, as the substituting group in " can have substituent aromatic residue ", except that aforementioned, also can enumerate and to have the example of substituent aliphatic hydrocarbon residue as preferred substituents.As having substituent aliphatic hydrocarbon residue, can enumerate can have substituent carbon number 1 to 36 aliphatic hydrocarbon residue as preferred example.As substituting group wherein, can enumerate aforementioned substituting group as the substituting group in " can have substituent aliphatic hydrocarbon residue ".
E represents to comprise carbon number 2 to 4, can have substituent saturated or undersaturated alkyl.When E contains a plurality of substituting group, can form ring between this substituting group.As preferred E, preferably particularly including carbon number 2 to 3, can have substituent saturated or undersaturated alkyl, further to preferably include carbon number be 3, can have substituent saturated or undersaturated alkyl.With the ring that the substituting group on the E forms, preferred 5 to 10 yuan of rings, preferred especially person can enumerate pentamethylene, cyclohexane, benzene, naphthalene etc.Preferred person as in the group of the aforementioned formula (3) that contains E can enumerate N-R
1Tetrahydro pyridyl and this four hydrogen atom substituted N-R of replacing
1The tetrahydro pyridyl that replaces etc.Can a plurality ofly be substituted in these four hydrogen atoms, and this substituting group can form ring.Another preference can be enumerated N-R
1Carbazole-3-the base that replaces etc.This moment is as R
1, can enumerate aliphatic hydrocarbon residue, preferred alkyl or the phenyl (substituting group is C1 to a C36 aliphatic hydrocarbon residue, preferred alkyl) that is substituted of C1 to C36.This R
1In preferred C1 to the C18 alkyl of C1 to C36 aliphatic hydrocarbon residue.Be N-R
1During the tetrahydro pyridyl that replaces, further preferred R
1Be C5 to C18 alkyl.Through N-R
1R in the carbazole-3-base that replaces
1, preferred C1 to C18 alkyl, according to circumstances also preferably about C1 is to the alkyl of about C6.
Y represents hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, carboxyl, phosphate, sulfonic group, cyano group, can have substituent amide groups, can have the alkyl sulphonyl or the alkoxy carbonyl of substituent carbon number 1 to 5; wherein preferred carboxyl, phosphate, sulfonic group, cyano group, can have substituent amide groups, can have the alkyl sulphonyl or the alkoxy carbonyl of substituent carbon number 1 to 5, preferred especially cyano group.As the alkyl sulphonyl that can have substituent carbon number 1 to 5, preferred trifluoromethyl sulfonyl, pentafluoroethyl group sulfonyl etc.Can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, can have substituent amide groups and alkoxy carbonyl, can enumerate the substituent explanation that reaches in " can have substituent aliphatic hydrocarbon residue " with " can have substituent aromatic residue " respectively and represent identical.
X represents hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, carboxyl, phosphate, sulfonic group, cyano group, can have substituent amide groups, can have the alkyl sulphonyl or the alkoxy carbonyl of substituent carbon number 1 to 5; wherein preferred carboxyl, phosphate, sulfonic group, preferred especially carboxyl.Can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, can have the substituting group in substituent amide groups and the alkoxy carbonyl, each represents identical with the substituting group that " can have substituent aromatic residue " reaches in " can have substituent aliphatic hydrocarbon residue ".
A
1, A
2And A
3Independent separately; expression can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, hydroxyl, phosphate, cyano group, hydrogen atom, halogen atom, carboxyl, formamido, alkoxy carbonyl, aryl carbonyl or acyl group; preferred hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, cyano group or halogen atom, further preferred hydrogen atom.As having substituent aromatic residue, can having substituent aliphatic hydrocarbon residue, halogen atom, alkoxy carbonyl, aryl carbonyl and acyl group, represent identical with the substituting group that " can have substituent aromatic residue " reaches in " can have substituent aliphatic hydrocarbon residue " respectively.In addition, n is more than 2, and A
2And A
3During a plurality of the existence, each A
2And each A
3Can be identical or different.
In addition, n is beyond 0 the time, can be by a plurality of A
1And/or A
2And/or A
3Formation can have substituent ring, and these also can have substituent ring with the common formation of phenyl ring b in addition.As the example of the ring that can form, can enumerate unsaturated hydrocarbons ring or heterocycle.
More specifically, in the formula (1) of aforementioned (1) record, represent that when X represents carboxyl, Y cyano group, Z are the group of formula (3) expression, wherein the group of this formula (3) is N-R
1Tetrahydroquinoline-6-base or the N-R that replaces
1Carbazole-3-base (the R that replaces
1With identical in the formula (3)) time, A
1, A
2And A
3Be hydrogen atom, or A
1With A
3Between or adjacent A
2Between or A
3Between interosculate and form the binding group of carbon number 2 to 3 or comprise that carbon number is 2 the aliphatic chain and the binding group of oxygen atom, and form 15 to 6 yuan rings (this ring can have methyl as substituting group), remaining A
1, A
2And A
3Be hydrogen atom, or A
2With the A that crosses an interval
3In conjunction with, becoming 1 the heteroatomic binding group that comprises in the group that is selected from sulphur atom, nitrogen-atoms and oxygen atom formation, and form 5 yuan of rings, these 5 yuan rings form 1 to 3, preferably remaining A
1, A
2And A
3Be hydrogen atom.
At this, above-mentioned n is the unsaturated hydrocarbons ring that can form beyond 0 time or the example of heterocycle, can enumerate phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring, indenes ring, Azulene ring, fluorenes ring, cyclobutane ring, cyclohexene ring, cyclopentene ring, cyclohexadiene ring, cyclopentadiene ring etc., as the example of heterocycle, can enumerate pyridine ring, pyrazine ring, pyrrole piperazine ring, indole ring, furan nucleus, thiphene ring, pyranoid ring, oxazole ring, thiazole ring, thiadiazoles Huan, oxadiazole ring, indole ring, benzothiazole ring, benzoxazole ring, quinoline ring, carbazole ring, chromene ring etc.As preferred person wherein, can enumerate phenyl ring, cyclobutane ring, cyclopentene ring, cyclohexene ring, pyranoid ring, furan nucleus, thiphene ring etc.These rings also can form condensed ring jointly with phenyl ring b.These also can have substituting group as previously mentioned, and this substituting group is described identical with the substituting group that aforementioned " can have substituent aromatic residue " reaches in " can have substituent aliphatic hydrocarbon residue ".The ring that can form is heterocycle and they when having carbonyl, thiocarbonyl group etc., can form cyclic ketone or ring-type thioketones etc., and these rings can also have substituting group.Substituting group and aforementioned " can have substituent aromatic residue " of this moment reaches described in the substituent item in " can have substituent aliphatic hydrocarbon residue " identical.
Phenyl ring b can have and is selected from by halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or unsubstituted amino, can has substituent aliphatic hydrocarbon residue and can have 1 to 3 substituting group in the group that substituent aromatic yl residue constitutes.As halogen atom, amide groups, alkoxyl, acyl group, replace or the amino that is unsubstituted, can have substituent aliphatic hydrocarbon residue and can have substituent aromatic yl residue, the replacement ground term that reaches in " can have substituent aliphatic hydrocarbon residue " with " can have substituent aromatic residue " is described identical respectively.In addition, substituting group is a plurality of when existing, these substituting groups can be mutually between or as described above with A
1And/or A
2And/or A
3In conjunction with and form and can have substituent ring.At this, can have the substituting group that has in the substituent ring, can enumerate with " can have substituent aromatic residue " and reach the described identical substituting group of replacement ground term in " can have substituent aliphatic hydrocarbon residue ".
In the methine class pigment of aforementioned formula (1a) expression, the methine class pigment of preferred following formula (2a) expression.
About n, the R in the formula (2a)
1, Y, X, A
1, A
2, A
3And phenyl ring b, identical with expression in the formula (1a) respectively.In addition, R
2aTo R
7aRepresent hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or halogen atom, wherein preferred hydrogen atom maybe can have substituent aliphatic hydrocarbon residue.Preferred especially R
2aTo R
7aBe hydrogen atom or R
2aAnd R
3aFor having substituent aliphatic hydrocarbon residue and R
4aTo R
7aBe hydrogen atom.At this, can have substituent aromatic residue and can have substituent aliphatic hydrocarbon residue, to reach " can have substituent aliphatic hydrocarbon residue " identical with aforementioned " can have substituent aromatic residue " respectively.In addition, halogen atom can be enumerated atoms such as fluorine, chlorine, bromine, iodine.In addition, R
2aTo R
7aCan interosculate to form and to have substituent ring.As the substituting group that can have in the substituent ring, the replacement ground term that reaches in " can have substituent aliphatic hydrocarbon residue " with " can have substituent aromatic residue " is described identical.
In addition, the methine class pigment of formula (2a) expression, further the methine class pigment of preferred following formula (3a) expression.
N, R in the formula (3a)
1, Y, X, A
1, A
2, A
3And phenyl ring b is identical with expression in the formula (1a) respectively.
The methine class pigment of aforementioned formula (1) expression to the aforementioned formula (3a) is when having acidic-groups such as carboxyl, phosphate, hydroxyl, sulfonic group as substituting group, also can form various salt, example as salt, for example can enumerate the salt that forms with alkali metal such as lithium, sodium, potassium, magnesium, calcium or alkaline-earth metal etc., or with the organic base salt that forms such as quaternary ammoniums such as tetramethyl-ammonium, TBuA, pyridine, imidazoles, piperazine, piperidines for example.
Aforementioned formula (1) can obtain the constitutional isomer of cis body, trans body or its mixture, optical active matter (optical active substance), racemic modification etc. to the methine class pigment of the middle expression of aforementioned formula (3a), but there is no special qualification, any isomers all can use with pigment as the light sensitizing among the present invention well.
The methine class pigment of aforementioned formula (1a) expression can be made according to the reaction equation of for example following expression.Promptly, by in case of necessity at caustic soda, sodium methoxide, sodium acetate, diethylamine, triethylamine, piperidines, piperazine, base catalysts such as diazabicylo hendecene exist down, the carbonyls that the compound with active methylene of following formula (5a) expression and following formula (4a) are represented is at methyl alcohol, ethanol, isopropyl alcohol, alcohols or dimethyl formamides such as butanols, non-proton property polar solvent or toluene such as N-methyl pyrrolidone, acetic anhydride, in the acetonitrile equal solvent, 20 ℃ to 180 ℃ preferred 50 ℃ to 150 ℃ following condensations, can obtain the methine class pigment of formula (1a).The compound with active methylene suc as formula (5a) expression can be easy to buy from market, and X is the carbonyls suc as formula (4a) expression of trimethylene as an example; can be by 1,2,3; the 4-tetrahydroquinoline carries out known methods such as formylation and obtains after the N-alkylation.N, R in the formula (4a)
1, X, A
1, A
2, A
3And phenyl ring b respectively with formula (1a) in identical.In addition X in the formula (5a) and Y respectively with formula (1a) in identical.
Below enumerate the object lesson of the methine class pigment (compound) of aforementioned formula (1a) expression.
At first, in the methine class pigment of formula (1a) expression, the object lesson of the methine class pigment of following formula (6a) expression is shown in table 1 and table 2.In each table, Ph represents phenyl.
In the following formula (6a), preferred X
1Expression carboxyl, Y
1Expression cyano group, A
4To A
6Expression hydrogen atom, R
1Alkyl, the R of expression C1 to C18
9aTo R
13aThe expression hydrogen atom.
[table 1]
Compound n X
1Y
1A
4A
5A
6R
8aR
9aR
10aR
11aR
12aR
13a
1a 0 H H H - - H H H H H H
2a 0 COOH CN H - - CH
3 H H H H H
3a 0 COOH CN H - - C
2H
5 H H H H H
4a 0 COOH CN H - - n-C
4H
9 H H H H H
5a 0 COOH CN H - - n-C
8H
17 H H H H H
6a 0 COOH CN H - - n-C
18H
37 H H H H H
7a 0 COOH CN H - - Ph H H H H H
8a 0 COOH COOH H - - n-C
8H
17 H H H H H
9a 0 COOH COCH
3 H - - n-C
8H
17 H H H H H
10a 0 COOH COCF
3 H - - n-C
8H
17 H H H H H
11a 0 PO(OH)
2 CN H - - n-C
8H
17 H H H H H
12a 0 SO
3H CN H - - n-C
8H
17 H H H H H
13a 0 COOCH
3 CN H - - n-C
8H
17 H H H H H
14a 0 COOLi CN H - - n-C
8H
17 H H H H H
15a 0 COONa CN H - - n-C
8H
17 H H H H H
16a 0 COOK CN H - - n-C
8H
17 H H H H H
17a 0 COOH PO(OH)
2 H - - n-C
8H
17 H H H H H
18a 0 PO(OH)
2 PO(OH)
2 H - - n-C
8H
17 H H H H H
19a 0 COOH NO
2 H - - n-C
8H
17 H H H H H
20a 0 COOH Cl H - - n-C
8H
17 H H H H H
21a 0 COOH CN H - - n-C
8H
17 CH
3 CH
3 H H H
22a 0 COOH CN H - - n-C8H
17 H H H OH H
23a 0 COOH CN H - - n-C
8H
17 H H CH
3 CH
3 CH
3
24a 0 COOH CN H - - n-C
8H
17 H H H H OCH
3
25a 0 COOH CN H - - n-C
8H
17 H H H Cl H
26a 0 COOH COPh H - - n-C
8H
17 H H H H H
27a 0 COOH COC(CH
3)
3 H - - n-C
8H
17 H H H H H
28a 0 COOH SO
2CF
3 H - - n-C
8H
17 H H H H H
29a 0 COONa COONa H - - n-C
8H
17 H H H H H
30a 0 COOH CN CH
3 - - n-C
8H
17 H H H H H
31a 0 COOH CN Ph - - n-C
8H
17 H H H H H
32a 1 COOH CN H H H n-C
8H
17 H H H H H
33a 1 COOH CN H H H n-C
8H
17 CH
3 CH
3 H H H
34a 1 COOH CN H CH
3 CH
3 n-C
8H
17 H H H H H
35a 1 COOH CN H H CH
3 n-C
8H
17 H H H H H
36a 1 COOH CN H CH
3 H n-C
8H
17 H H H H H
37a 1 COOH CN CH
3 CH
3 CH
3 n-C
8H
17 H H H H H
38a 1 COOH CN H H Ph n-C
8H
17 H H H H H
39a 1 COOH CN H H H Ph H H H H H
40a 1 COOH CN H H H CH(CH
3)
2 H H H H H
41a 1 COOH CN H H H C(CH
3)
3 H H H H H
42a 1 COOH Ph H H H n-C
8H
17 H H H H H
43a 1 COOH CH
2CH
3 H H H n-C
8H
17 H H H H H
44a 1 PO(ONa)
2 CN H H H n-C
8H
17 H H H H H
45a 1 COOH CN H H H C
2H
4Cl H H H H H
46a 1 COOH CN H H H C2H
4OH H H H H H
47a 1 COOH CN H H H C
2H
4OCH
3 H H H H H
48a 1 COOH CN H H H C
2H
4CN H H H H H
[table 2]
Compound n X
1Y
1A
4A
6A
8R
KaR
9aR
10aR
11aR
12aR
13a
49a 1 COOH CN H H H C
4H
8OCH
3 H H H H H
50a 1 COOH CN H H H C
2H
4OPh H H H H H
51a 1 COOH CN H H H n-C
8H
17 H H C
2H
6 H H
52a 1 COOH CN H H H n-C
8H
17 H H H NO
2 H
53a 1 COOH CN H H H n-C
8H
17 H H H OCH
3 H
54a 1 COOH CN H H H n-C
8H
17 H H H H Cl
55a 1 COOH CN H H H n-C
8H
17 H H H CN H
56a 1 COOH CN CN H H n-C
8H
17 H H H H H
57a 1 COOH CN H H H n-C
8H
17 Ph H H H H
58a 1 COOH CN H H H n-C
8H
17 H H H NHCOCH
3 H
59a 1 COOH CN H H H n-C
8H
17 H H H N
HCOCF
3 H
60a 1 COOH CN H H H n-C
8H
17 H H H CF
3 H
61a 1 COOH CF
3 H H H n-C
8H
17 H H H H H
62a 1 COOH F H H H n-C
8H
17 H H H H H
63a 1 COOH CN H H H CF
3 H H H H H
64a 1 COOH CN H H H C
2F
6 H H H H H
65a 1 COOH CN H H H C
4F
9 H H H H H
66a 1 COOH CN H H H C
8F
17 H H H H H
67a 1 COOH CN H H H CH
2CF
3 H H H H H
68a 1 COOH CN H H H n-C
8H
17 CF
3 CF
3 H H H
69a 1 COOH CN H H H n-C
8H
17 H H H NH
2 H
70a 1 COOH CN H H H n-C
8H
17 H H H NHCH
3 H
71a 1 COOH CN H H H n-C
8H
17 H H H NHPh H
72a 1 COOH CN H H H n-C
8H
17 H H H N(CH
3)
2 H
73a 1 COOH CN H H H n-C
8H
17 H H H COCH
3 H
74a 1 COOH CN H H H n-C
8H
17 H H H COCF
3 H
75a 1 COOH CN H H H CH
2Ph H H H H H
76a 1 COOH CN H H H C
2H
4Ph H H H H H
77a 1 COOH CN H H H n-C
8H
17 H H H OH H
78a 1 COOH CN H H H n-C
8H
17 H H H ONa H
79a 1 COONa CN H H H n-C
8H
17 H H HO Na H
80a 1 COOH CN H H H n-C
8H
17 H H H OC
4H
3 H
81a 1 COOH CN H H H n-C
8H
17 H H H O(n-C
3H
17) H
82a 1 COOH CN H H H n-C
8H
17 H H H H CH
3
83a 1 COOH CN H H H C
3H
8Cl H H H H H
84a 1 COOH CN H H H C
3H
6Br H H H H H
85a 1 COOH CN H H H CH
2COOH H H H H H
86a 1 CN CN H H H CH
2COOH H H H H H
87a 2 COOH CN H H H n-C
8H
17 H H H H H
88a 2 COOH CN CH
3 H H n-C
8H
17 H H H H H
89a 2 COOH CN CH
3 CH
3 CH
3 n-C
8H
17 H H H H H
90a 2 COOH CN H H CH
3 n-C
8H
17 H H H H H
91a 2 COOH CN H H H n-C
8H
17 CH
3 CH
3 H H H
92a 3 COOH CN H H H n-C
8H
17 H H H H H
93a 4 COOH CN H H H n-C
8H
17 H H H H H
94a 5 COOH CN H H H n-C
8H
17 H H H H H
95a 6 COOH CN H H H n-C
8H
17 H H H H H
96a 7 COOH CN H H H n-C
8H
17 H H H H H
Secondly, in the methine class pigment of formula (1a) expression, the object lesson of the methine class pigment of following formula (7a) expression is shown in table 3 and table 4.In each table, Ph represents phenyl.
In the following formula (7a), preferred X
2Expression carboxyl, Y
2Expression cyano group, A
7To A
9Expression hydrogen atom, R
14aTo R
17aExpression hydrogen atom, R
18aAlkyl, the R of expression C1 to C18
19aTo R
23aThe expression hydrogen atom.
[table 3]
Compound n X
2Y
2A
7A
8A
9R
14aR
15aR
16aR
17aR
18aR
19aR
20aR
21aR
22aR
23a
97a 0 H H H - - H H H H H H H H H H
98a 0 COOH CN H - - H H H H H H H H H H
99a 0 COOH CN H - - H H H H CH
3 H H H H H
100a 0 COOH CN H - - H H H H C
2H
5 H H H H H
101a 0 COOH CN H - - H H H H n-C
4H
9 H H H H H
102a 0 COOH CN H - - H H H H n-C
8H
17 H H H H H
103a 0 COOH CN H - - H H H H n-C
18H
37 H H H H H
104a 0 COOH COOH H - - H H H CH
3 H CH
3 H H H H
105a 0 COOH COCH
3 H - - H H H H CH
3 H H H H H
106a 0 COOH COCF
3 H - - H H H H CH
3 H H H H H
107a 0 PO(OH)
2 CN H - - H H H H n-C
8H
17 H H H H H
108a 0 SO
3H CN H - - H H H H n-C
8H
17 H H H H H
109a 0 COOCH
3 CN H - - H H H H n-C
8H
17 H H H H H
110a 0 COOLi CN H - - H H H H n-C
8H
17 H H H H H
111a 0 COONa CN H - - H H H H n-C
8H
17 H H H H H
112a 0 COOK CN H - - H H H H n-C
8H
17 H H H H H
113a 0 COOH PO(OH)
2 H - - H H H H n-C
8H
17 H H H H H
114a 0 PO(OH)
2 PO(OH)
2 H - - H H H H n-C
8H
17 H H H H H
115a 0 COOH NO
2 H - - H H H H CH
3 H H H H H
116a 0 COOH Cl H - - H H H H CH
3 H H H H H
117a 0 COOH CN H - - CH
3 CH
3 H H CH
3 H H H H H
118a 0 COOH CN H - - H H H OH CH
3 H H H H H
119a 0 COOH CN H - - H H H H OCH
3 H H H H H
120a 0 COOH CN H - - H H H OCH
3 H H H H H H
121a 0 COOH CN H - - H H H Cl H Cl H H H H
122a 0 COOH COPh H - - H H CH
3 H H H CH
3 H H H
123a 0 COOH COC(CH
3)
3 H - - H H CH
3 H CH
3 H H H H H
124a 0 COOH SO
2CF
3 H - - H H H H H H H H H H
125a 0 COONa COONa H - - H H H H H H H H H H
126a 0 COOH CN CH
3 - - H H H H H H H H H H
127a 0 COOH CN Ph - - H H H H H H H H H H
128a 1 COOH CN H H H H H H H Ph H H H H H
129a 1 COOH CN H H H CH
3 CH
3 H H Ph H H H H H
130a 1 COOH CN H CH
3 CH
3 H H H H CH
3 H H H H H
131a 1 COOH CN H H CH
3 H H H H CH
3 H H H H H
132a 1 COOH CN H CH
3 H H H H H CH
3 H H H H H
133a 1 COOH CN CH
3 CH
3 CH
3 H H H H CH
3 H H H H H
134a 1 COOH CN H H Ph H H H H CH
3 H H H H H
135a 1 COOH CN H H H H H H n-C
4H
9 H n-C
4H
9 H H H H
136a 1 COOH CN H H H H H H H NO
2 H H H H H
137a 1 COOH CN H H H H H H H NH
2 H H H H H
138a 1 COOH Ph H H H H H H H O(n-C
4H
9)H H H H H
139a 1 COOH C
2H
5 H H H H H H H H H H H H H
140a 1 PO(ONa)
2 CN H H H H H H H n-C
4H
9 H H H H H
141a 1 COOH CN H H H H H H H n-C
6H
13 H H H H H
142a 1 COOH CN H H H H H H H n-C
4H
9 H H Cl H H
143a 1 COOH CN H H H H H H H n-C
4H
9 H H H Cl H
144a 1 COOH CN H H H H H H H n-C
4H
9 H H H H Cl
[table 4]
Compound n X
2Y
2A
7A
8A
9R
14aR
15aR
16aR
17aR
18aR
19aR
20aR
21aR
22aR
23a
145a 1 COOH CN H H H H H H H Cl H H H H H
146a 1 COOH CN H H H H H H H Br H H H H H
147a 1 COOH CN H H H H H H H CH
3 H H H H H
148a 1 COOH CN H H H H H H H C
2H
5 H H H H H
149a 1 COOH CN H H H H H H H n-C
4H
9 H H H H H
150a 1 COOH CN H H H H H H H n-C
8H
17 H H H H H
151a 1 COOH CN H H H H H H H n-C
18H
37 H H H H H
152a 1 COOH CN H H H H H H CH
3 H CH
3 H H H H
153a 1 COOH CN H H H H H H H OH H H H H H
154a 1 COOH CN n-C
8H
17 H H H H H H CH
3 H H H H H
155a 1 COOH CN H H H H H H H n-C
8H
17 H H H H H
156a 1 COOH CN H H H H H Cl H Cl H H H H H
157a 1 COOH CF
3 H H H H H H H n-C
8H
17 H H H H H
158a 1 COOH F H H H H H H H n-C
8H
17 H H H H H
159a 1 COOH C
2H
5 H H H H H H H n-C
8H
17 H H H H H
160a 1 COOH CN H H H H H H H n-C
8H
17 H H H H H
161a 1 COOH CN H H H H H n-C
8H
17 H n-C
8H
17 H H H H H
162a 1 COOH CN H H H H H H H n-C
18H
37 H H H H H
163a 1 COOH CN H H H H H H H CH
3 H H H H H
164a 1 COOH CN H H H H H H H CH
3 H H H H H
165a 1 COOH CN H H H CH
3 CH
3 H H CH
3 H H H H H
166a 1 COOH CN H H H H H H OH CH
3 H H H H H
167a 1 COOH CN H H H H H H H OCH
3 H H H H H
168a 1 COOH CN H H H H H H OCH
3 H H H H H H
169a 1 COOH CN H H H H H H Cl H Cl H H H H
170a 1 COOH CN H H H H H CH
3 H H H CH
3 H H H
171a 1 COOH CN H H H H H CH
3 H CH
3 H H H H H
172a 1 COOH CN H H H H H H H H H H H H H
173a 1 COOH CN H H H H H H H SCN H H H H H
174a 1 COOH CN CH
3 H H H H H H H H H H H H
175a 1 COONa CN Ph H H H H H H H H H H H H
176a 1 COOH CN H H H H H H H Ph H H H H H
177a 1 COOH CN H H H CH
3 CH
3 H H Ph H H H H H
178a 1 COOH CN H CH
3 CH
3 H H H H CH
3 H H H H H
179a 1 COOH CN H H CH
3 H H H H CH
3 H H H H H
180a 1 COOH CN H CH
3 H H H H H CH
3 H H H H H
181a 1 COOH CN CH
3 CH
3 CH
3 H H H H CH
3 H H H H H
182a 1 CN CN H H Ph H H H H CH
3 H H H H H
183a 2 COOH CN H H H H H H n-C
4H
9 H C
4H
9 H H H H
184a 2 COOH CN H H H H H H H CH
3 H H H H H
185a 2 COOH CN H H H H H H H H H H H H H
186a 2 COOH CN H H H H H H H n-C
8H
17 H H H H H
187a 2 COOH CN H H H H H H CH
3 H CH
3 H H H H
188a 3 COOH CN H H H H H H H n-C
8H
17 H H H H H
189a 4 COOH CN H H H H H H H n-C
8H
17 H H H H H
190a 5 COOH CN H H H H H H H n-C
8H
17 H H Cl H H
191a 6 COOH CN H H H H H H H n-C
8H
17 H H H Cl H
192a 7 COOH CN H H H H H H H n-C
8H
17 H H H H Cl
In addition, other object lesson of the methine class pigment of formula (1a) expression is as follows.
In the aforementioned formula (1a), the methine class pigment when Z is formula (2) is represented with following formula (1b).
(in the formula, n represents 0 to 7 integer.X and Y are independent separately, represent hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, carboxyl, phosphate, sulfonic group, cyano group, acyl group, amide groups or alkoxy carbonyl.In addition, X can have substituent ring in conjunction with forming with Y.A
1, A
2And A
3Independent separately, expression can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, hydroxyl, phosphate, cyano group, hydrogen atom, halogen atom, carboxyl, formamido, alkoxy carbonyl, aryl carbonyl or acyl group.N is more than 2 and A
2And A
3During a plurality of separately the existence, each A
2And each A
3Can be identical or different mutually.N is beyond 0 the time, also can be by a plurality of A
1And/or A
2And/or A
3Formation can have substituent ring, and they can also can have substituent ring with the common formation of phenyl ring a.Phenyl ring a can have and is selected from by halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or unsubstituted amino, can has substituent aliphatic hydrocarbon residue and can have 1 to 4 substituting group in the group that substituent aromatic residue constitutes.In addition, substituting group exists when a plurality of, these substituting groups can be mutually or as previously mentioned with A
1And/or A
2And/or A
3In conjunction with and form and can have substituent ring.
Ring Cy is 4 to 7 yuan of rings, as ring atom, except the nitrogen-atoms of expression in the carbon atom, formula (1b), also can contain hetero-atom, also can have substituting group in addition, when Cy has a plurality of substituting group, can form ring mutually by substituting group arbitrarily.) ring Cy group one of preferred, can enumerate the morpholino base.
In the above-mentioned formula (1b), n represents 0 to 7 integer, preferred 0 to 6, preferred especially 0 to 4.
X and Y are as describing about descriptive item in the aforementioned formula (1) to (3a).
That is, preferred X is a carboxyl, and Y is cyano group, carbonyl or acyl group, more preferably Y is a cyano group, and this moment, n was 0 to be one of preferred combination.
When X combines situation that formation has substituent ring and replenishes with Y, as the ring that forms, can enumerate pyrazolone ring, rhodanine ring, double wrap tannin ring, barbital ring, pyridone ring etc., preferred pyrazolone ring, rhodanine ring, double wrap tannin ring, preferred especially pyrazolone ring.This moment, preferred n was 0.
A
1, A
2And A
3Independent separately; expression can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, hydroxyl, phosphate, cyano group, hydrogen atom, halogen atom, carboxyl, formamido, alkoxy carbonyl, aryl carbonyl or acyl group; preferred hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, cyano group or halogen atom, further preferred hydrogen atom.Can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, halogen atom, carboxyl, alkoxy carbonyl, aryl carbonyl and acyl group, the substituting group that reaches in " can have substituent aliphatic hydrocarbon residue " with " can have substituent aromatic residue " is described identical respectively.In addition, n is more than 2, and A
2And A
3During a plurality of the existence, each A
2And each A
3Can be identical or different each other.
N is beyond 0 the time, can be by a plurality of A
1And/or A
2And/or A
3Formation can have substituent ring, and they can also can have substituent ring with the common formation of phenyl ring a.As the example of the ring that can form, can enumerate unsaturated hydrocarbons ring or heterocycle.
Wherein as the example of unsaturated hydrocarbons ring, as phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, pyrene ring, indenes ring, Azulene ring, fluorenes ring, cyclobutane ring, cyclohexene ring, cyclopentene ring, cyclohexadiene ring, cyclopentadiene ring etc.; As the example of heterocycle, can enumerate pyridine ring, pyrazine ring, pyrrole piperazine ring, indole ring, furan nucleus, thiphene ring, pyranoid ring, oxazole ring, thiazole ring, thiadiazoles Huan, oxadiazole ring, indole ring, benzothiazole ring, benzoxazole ring, quinoline ring, carbazole ring, chromene ring etc.The wherein preferred person of conduct can enumerate phenyl ring, cyclobutane ring, cyclopentene ring, cyclohexene ring, pyranoid ring, furan nucleus, thiphene ring etc. in addition.They can have substituting group as described above, and this substituting group can be described identical with the replacement ground term that aforementioned " can have substituent aromatic residue " reaches in " can have substituent aliphatic hydrocarbon residue ".The ring that can form is a heterocycle and when having carbonyl, thiocarbonyl group etc., can form cyclic ketone or ring-type thioketones etc., and these rings also can have substituting group.This moment can be described identical with the replacement ground term that aforementioned " can have substituent aromatic residue " reaches in " can have substituent aliphatic hydrocarbon residue " as substituting group.
Phenyl ring a also can have to be selected from and comprises halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or unsubstituted amino, can have substituent aliphatic hydrocarbon residue and can have 1 to 4 substituting group in the group of substituent aromatic residue.Halogen atom, amide groups, alkoxyl, acyl group, replacement or unsubstituted amino, can have substituent aliphatic hydrocarbon residue and can have substituent aromatic residue, the replacement ground term that reaches in " can have substituent aliphatic hydrocarbon residue " with " can have substituent aromatic residue " is described identical respectively.In addition, when a plurality of substituting groups exist, these substituting groups can be mutually or as previously mentioned with A
1And/or A
2And/or A
3In conjunction with and form and can have substituent ring.Wherein can have the substituting group in the substituent ring, the replacement ground term that reaches in " can have substituent aliphatic hydrocarbon residue " with " can have substituent aromatic residue " is described identical.
Ring Cy in the formula (1b) is 4 to 7 yuan of rings, as the constituting atom of ring, the nitrogen-atoms of record, also can have hetero-atom in carbon atom, formula (1b).In addition, can have when having a plurality of substituting group among substituting group and the Cy, can form ring mutually by substituting group arbitrarily.As the object lesson of ring Cy, can enumerate the ring of following expression, they also can further have substituting group.As this substituting group, can enumerate with " can have substituent aromatic residue " and reach the described substituting group of replacement ground term in " can have substituent aliphatic hydrocarbon residue ".
In the methine class pigment of formula (1b) expression, the methine class pigment of preferred following formula (2b) expression.
N, X, Y, A in the formula (2b)
1, A
2, A
3And phenyl ring a respectively with formula (1b) in identical.Identical in the preferred object lesson of n, X and Y and the aforementioned formula (1b).
For example, X and Y combination one of preferred, X is that carboxyl, Y are cyano group, carboxyl or acyl group, more preferably Y is a cyano group.In addition, as other preferred compositions, for X combines the situation that forms ring with Y, the ring of this formation is that the methine that pyrazolone ring, X (Y) C=represent is the situation of 2-phenyl-5-carboxyl-3-pyrazolone-4-base.
When preferably making up for these, n is preferably 0.In the group of aforementioned formula (2b) expression, 6 yuan of rings that contain oxygen atom or sulphur atom except nitrogen-atoms of expression in the ring Cy preferred formula (2b) more preferably encircle the Cy base and are the morpholino base.In this preferred compound, A
1Can be identical with the situation of formula (1b), hydrogen atom more preferably.
R
1bTo R
8bIndependent separately, to represent hydrogen atom respectively, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic hydrocarbon residue, halogen atom or hydroxyl, preferred hydrogen atom maybe can have substituent aliphatic hydrocarbon residue.Can have substituent aliphatic hydrocarbon residue, can have substituent aromatic hydrocarbon residue, can be with identical described in " can have substituent aliphatic hydrocarbon residue ", " can have substituent aromatic residue " item.Halogen atom can be described identical with the replacement ground term that " can have substituent aromatic residue " reaches in " can have substituent aliphatic hydrocarbon residue ".In addition, R
1bTo R
4bAnd R
5bTo R
8bCan interosculate to form and to have substituent ring.Can have the substituting group in the substituent ring, can be described identical with the replacement ground term that " can have substituent aromatic residue " reaches in " can have substituent aliphatic hydrocarbon residue ".R
1bTo R
8bIndependent separately, preferred hydrogen atom, comprise the alkyl of carbon number 1 to 4, preferred especially R
1b, R
2b, R
7bAnd R
8bMethyl, R respectively do for oneself
3b, R
4b, R
5bAnd R
6bThe hydrogen atom of respectively doing for oneself.
Q in the formula (2b) represents CR respectively
9R
10, NR
11, oxygen atom, sulphur atom, selenium atom or SO
2, wherein preferred CR
9R
10, oxygen atom, SO
2, preferred especially CR
9R
10Or oxygen atom.R
9And R
10Independent separately, expression hydrogen atom or substituting group when be substituting group, can be enumerated and " can have substituent aromatic residue " reaches the described substituting group of replacement ground term in " can have substituent aliphatic hydrocarbon residue ".R
11Represent hydrogen atom, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic hydrocarbon residue, acyl group etc.; preferred hydrogen atom, can have substituent aliphatic hydrocarbon residue, can have substituent aromatic hydrocarbon residue, especially preferably can have substituent aliphatic hydrocarbon residue.Can have substituent aliphatic hydrocarbon residue, can have substituent aromatic hydrocarbon residue, can reach described in " can have substituent aromatic residue " item identical with " can have substituent aliphatic hydrocarbon residue ".As acyl group, can be described identical with X and the Y item in the formula (1b).As R
9And R
10, preferred respectively hydrogen atom, comprise the alkyl of carbon number 1 to 4, preferred especially hydrogen atom or methyl.As R
11, preferred hydrogen atom, comprise the alkyl or phenyl of carbon number 1 to 4, preferred especially hydrogen atom, methyl, phenyl.
In addition, when aforementioned formula (1), (1a), (1b) or aforementioned formula represented methine class pigments such as (2b) have acidic-groups such as carboxyl, phosphate, hydroxyl and sulfonic group as substituting group, can form salt respectively, as this salt, for example can enumerate the salt that forms with alkali metal such as lithium, sodium, potassium, magnesium, calcium or alkaline-earth metal etc., or organic base such salt of quaternary ammonium salt such as tetramethyl-ammonium, TBuA, pyridine, imidazoles, piperazine, piperidines for example.
The compound of aforementioned formula (1b) or aforementioned formula (2b) expression, can obtain constitutional isomers such as cis body, trans body, racemic modification, but there is no special qualification, any isomers and composition thereof all can use with pigment as light sensitizing among the present invention well.
The methine class pigment of aforementioned formula (1b) expression for example can be made according to the reaction equation of following expression.By in case of necessity at caustic soda, sodium methoxide, sodium acetate, diethylamine, triethylamine, piperidines, piperazine, base catalysts such as diazabicylo hendecene exist down, the carbonyls that the compound that contains active methylene of formula (22) expression and formula (21) are represented is at methyl alcohol, ethanol, isopropyl alcohol, alcohols or dimethyl formamides such as butanols, non-proton property polar solvent or toluene such as N-methyl pyrrolidone, acetic anhydride, in the acetonitrile equal solvent, the known method of carrying out condensation under 20 ℃ to 180 ℃ preferred 50 ℃ to 150 ℃ obtains the methine class pigment that formula of the present invention (1b) is represented.
The object lesson of the methine class pigment of following enumerative (1b) expression.At first, the object lesson of the methine class pigment of following formula (23) expression is shown in table 5 and table 6.Ph in each table represents phenyl.In addition, enumerate table 5 and table 6 examples of compounds in addition according to structural formula more thereafter.
[table 5]
Compound n X
1Y
1A
4A
5A
6R
1R
2R
3R
4R
6R
6R
7R
8Q
1
1 0 H H H - - H H H H H H H H CH
2
2 0 COOH CN H - - H H H H H H H H CH
2
3 0 COOH CN H - - CH
3 CH
3 CH
3 CH
3 H H H H CH
2
4 0 COOH CN H - - H H H H H H H H C(CH
3)
2
5 0 COOH CN H - - H H H H H H H H C(Ph)
2
6 0 COOH CN H - - H H H H H H H H O
7 0 COOH CN H - - H H H H H H H H SO
2
8 0 COOH COOH H - - H H H H H H H H O
9 0 COOH COCH
3 H - - H H H H H H H H S
10 0 COOH COCF
3 H - - H H H H H H H H O
11 0 PO(OH)
2 CN H - - H H H H H H H H SO
2
12 0 SO
3H CN H - - H H H H H H H H O
13 0 COOCH
3 CN H - - H H H H H H H H O
14 0 COOLi CN H - - H H H H H H H H O
15 0 COONa CN H - - H H H H H H H H O
16 0 COOK CN H - - H H H H H H H H O
17 0 COOH PO(OH)
2 H - - H H H H H H H H NH
18 0 PO(OH)
2 PO(OH)
2 H - - H H H H H H H H NCH
3
19 0 COOH NO
2 H - - H H H H H H H H O
20 0 COOH Cl H - - H H H H H H H H O
21 0 COOH CN H - - H H H H H CH
3 H H O
22 0 COOH CN H - - H H H H H CH
3 H CH
3 O
23 0 COOH CN H - - H H H H H OCH
3 H CH
3 O
24 0 COOH CN H - - H H H H Cl H H H O
25 0 COOH CN H - - H H H H H NHCOCH
3 H OCH
3 O
26 0 COOH COPh H - - H H H H H H H H O
27 0 COOH COC(CH
3)
3 H - - H H H H H H H H O
28 0 COOH SO
2CF
3 H - - H H H H H H H H O
29 0 COONa COONa H - - H H H H H H H H O
30 0 COOH CN CH
3 - - H H H H H H H H O
31 0 COOH CN Ph - - H H H H H H H H O
32 1 COOH COOH H H H H H H H H H H H O
33 1 COOH CN H H H H H H H H H H H SO
2
34 1 COOH CN H CH
3 CH
3 H H H H H H H H O
35 1 COOH CN H H CH
3 H H H H H H H H O
36 1 COOH CN H CH
3 H H H H H H H H H O
37 1 COOH CN CH
3 CH
3 CH
3 H H H H H H H H O
38 1 COOH CN H H Ph H H H H H H H H O
39 1 COOH CN H H H H H H H H CH
3 H H O
40 1 COOH CN H H H H H H H H CH
3 H H SO
2
41 1 COOH CN H H H H H H H H H H H NCH
3
42 1 COOH Ph H H H H H H H H H H H O
43 1 COOH CH
2CH
3 H H H H H H H H H H H O
44 1 PO(ONa)
2 CN H H H H H H H H n-C
4H
9 H H O
45 1 COOH CN H H H Cl Cl Cl Cl H H H H O
46 1 COOH CN H H H CH
3 CH
3 CH
3 CH
3 H H H H S
47 1 COOH CN H H H CH
3 CH
3 CH
3 CH
3 H H H H O
48 1 COOH CN H H H CH
3 CH
3 CH
3 CH
3 H H H H SO
2
[table 6]
Compound n X
1Y
1A
4A
5A
6R
1R
2R
3R
4R
5R
6R
7R
8Q
1
49 1 COOH CN H H H H H H H CH
3 CH
3 CH
3 CH
3 O
50 1 COOH CN H H H H H H H CH
3 CH
3 CH
3 CH
3 O
51 1 COOH CN H H H H H H H F F F F O
52 1 COOH CN H H H H H H H Cl Cl Cl Cl O
53 1 COOH CN CH
3 CH
3 CH
3 H H H H CH
3 CH
3 CH
3 CH
3 O
54 1 COOH CN CH
3 CH
3 CH
3 CH
3 CH
3 CH
3 CH
3 CH
3 CH
3 CH
3 CH
3 NCH
3
55 1 COOH CN Cl Cl Cl H H H H H H H H O
56 1 COOH CN H H H H H H H NH
2 H H H O
57 1 COOH CN H H H H H H H H NHPh H H O
58 2 COOH CN H H H H H H H H H H H O
59 2 COOH CN H H H H H H H H H H H S
60 2 COOH CN H H H H H H H H H H H NH
61 2 COOH CN H H H H H H H H H H H SO
2
62 2 COOH CN H H H H H H H H H H H C(CH
3)
2
63 2 COOH COCF
3 H H H H H H H H H H H O
64 2 COOH COCH
3 H H H H H H H H H H H O
65 2 COOH CF
3 H H H H H H H H H H H O
66 2 COOH NO
2 H H H H H H H H H H H O
67 2 COOH SO
2Ph H H H H H H H H H H H O
68 3 COOH CN H H H H H H H H H H H O
69 3 COOH CN H H H H H H H H H H H S
70 3 COOH CN H H H H H H H H H H H NH
71 3 COOH CN H H H H H H H H H H H SO
2
72 3 COOH CN H H H H H H H H H H H C(CH
3)
2
73 3 COOH COCF
3 H H H H H H H H H H H O
74 3 COOH COCH
3 H H H H H H H H H H H O
75 3 COOH CF
3 H H H H H H H H H H H O
76 3 COOH NO
2 H H H H H H H H H H H O
77 3 COOH SO
2Ph H H H H H H H H H H H O
78 4 COOH CN H H H H H H H H H H H O
79 4 COOH CN H H H H H H H H H H H S
80 4 COOH CN H H H H H H H H H H H NH
81 4 COOH CN H H H H H H H H H H H SO
2
82 4 COOH CN H H H H H H H H H H H C(CH
3)
2
83 4 COOH COCF
3 H H H H H H H H H H H O
84 4 COOH COCH
3 H H H H H H H H H H H O
85 4 COOH CF
3 H H H H H H H H H H H O
86 4 COOH NO
2 H H H H H H H H H H H O
87 4 COOH SO
2Ph H H H H H H H H H H H O
88 5 COOH CN H H H H H H H H H H H O
89 5 COOH CN H H H H H H H H H H H SO
2
90 5 COOH CN H H H H H H H H H H H C(CH
3)
2
91 6 COOH CN H H H H H H H H H H H O
92 6 COOH CN H H H H H H H H H H H SO
2
93 6 COOH CN H H H H H H H H H H H C(CH
3)
2
94 7 COOH CN H H H H H H H H H H H O
95 7 COOH CN H H H H H H H H H H H SO
2
96 7 COOH CN H H H H H H H H H H H C(CH
3)
2
Dye-sensitized photoelectric conversion element of the present invention for example, is to use the oxide semiconductor particulate at the film that the oxide semiconductor particulate is set on the substrate, the methine class pigment of the aforementioned formula of load (1) and the components of photo-electric conversion that obtain on this film then.
Among the present invention, as the substrate of the film that the oxide semiconductor particulate is set, preferably its surface is a conductivity, and such substrate can be easy to obtain from the market.For example, can use at glass or polyethylene terephthalate, polyether sulfone etc. to have on the surface of macromolecular material etc. of the transparency, the substrate that the film of metals such as the metal oxide of conductivity such as tin oxide of mixed indium, fluorine, antimony etc. or copper, silver, gold forms is set.As long as its conductivity generally is that 1000 Ω are following, below preferred especially 100 Ω.
In addition, the object lesson of the metal oxide of using as the film of oxide semiconductor particulate can be enumerated the oxide of titanium, tin, zinc, tungsten, zirconium, gallium, indium, yttrium, niobium, tantalum, vanadium etc.Wherein, the oxide of preferred titanium, tin, zinc, niobium, indium etc., preferred especially titanium oxide, zinc oxide, tin oxide.These oxide semiconductors can be used alone, but also also mix together.In addition, the particle diameter of oxide semiconductor particulate is generally 1 to 500nm with regard to average grain diameter, be preferably 1 to 100nm.This oxide semiconductor particulate can mix big particle diameter particulate and small particle diameter particulate in addition, or forms multilayer and use.
The oxide semiconductor particle film can be by following method manufacturing, and described method is by methods such as atomisation direct film forming method on substrates such as aforementioned macromolecular material with the aforesaid oxides semiconductive particles; Separate out the method for semiconductive particles film as electrolysis with substrate; The precursor that will contain semiconductive particles such as slurries by making semiconductive particles or semiconductor alkoxide is hydrolyzed after the paste of the particulate that obtains is coated on the substrate, carries out drying, curing or calcining etc.From the aspect of performance of oxide semiconductor electrode, preferably wherein use the method for slurries.In the method, in the slurries that use, the oxide semiconductor particulate by making 2 aggegations becomes 1 to 200nm mode according to well-established law with average 1 particle diameter and is dispersed in the dispersant and makes.
As the dispersant that disperses these slurries; as long as can disperse semiconductive particles can use any one; for example can make hydrocarbon such as ketone such as alcohol, acetone, pentanediones such as water, ethanol or hexane; these also can mix use; in addition, with regard to reducing slurry viscosity variation aspect, preferably make water.In addition, the dispersity with the oxide semiconductor particulate stabilize to purpose aspect, can use dispersion stabilizer.As the example of spendable dispersion stabilizer, for example can enumerate acid such as acetate, hydrochloric acid, nitric acid or pentanedione, acrylic acid, polyethylene glycol, polyvinyl alcohol etc.
The substrate of painting slurry can be calcined, and its calcining heat is generally more than 100 ℃, and is preferred more than 200 ℃, and the upper limit is roughly below the melting point (softening point) of base material, is limited to 900 ℃ on general, preferred below 600 ℃.In addition, calcination time there is no special qualification, preferably roughly in 4 hours.Film thickness on the substrate is generally 1 to 200 μ m, preferred 1 to 50 μ m.
Can implement 2 times to the oxide semiconductor particle film handles.For example, with the solution of the alkoxide of metal-oxide semiconductor (MOS) same metal, chloride, itrated compound, sulfide etc. in direct impregnation be provided with the entire substrate of film, by dry or calcining again, also can improve the performance of semiconductive thin film.As the example of operable metal alkoxide, can enumerate for example titanium ethanolate, isopropyl titanate, tert-butyl alcohol titanium, positive dibutyl diacetyl tin etc., can use their alcoholic solution.In addition,, for example titanium tetrachloride, butter of tin, zinc chloride etc. can be enumerated, their aqueous solution can be used as chloride.Even on the oxide semiconductor thin-film that obtains like this, also can keep the graininess of oxide semiconductor through handling for 2 times.
Below, describe about the method for the methine class of the present invention of load on oxide semiconductor thin-film pigment.
The method of the methine class pigment that uses among the present invention as the expressions such as (1) of the aforementioned formula of load, for example can enumerate: this pigment of dissolving in the solvent of methine class pigment that can dissolution type (1) etc. and solution or make during low methine class pigment for dissolubility in the dispersion liquid that its dispersion obtains, dipping is provided with the method for the substrate of above-mentioned oxide semiconductor thin-film.The concentration of pigment in solution or the dispersion liquid can be according to the kind of the methine class pigment of formula (1) and suitably decision.Pigment solution during dipping or the temperature of dispersion liquid are roughly normal temperature to the boiling point that dissolves the employed solvent of pigment, and dip time is about 1 minute to about 48 hours in addition.As the object lesson of the spendable solvent of methine class pigment of dissolution type (1) etc., can enumerate for example methyl alcohol, ethanol, acetonitrile, dimethyl sulfoxide (DMSO), dimethyl formamide, acetone, the tert-butyl alcohol etc.Pigment concentration in the solution is generally 1 * 10
-6M to 1M, preferred 1 * 10
-5M to 1 * 10
-1M.Can obtain having the components of photo-electric conversion of the present invention that carry out the oxide semiconductor particle film of sensitizing with the methine class pigment of formula (1) etc. like this.
The methine class pigment that carries out the aforementioned formula (1) etc. of load can be a kind, also can multiplely mix.In addition, also can mix methine class pigment and other metal complex dye or the organic pigment that uses the formula (1) used among the present invention etc.Especially use the different pigment of absorbing wavelength by mixing, can utilize the absorbing wavelength of wide cut, obtain the high solar cell of light-to-current inversion efficient.Example as the metal complex dye that can mix, there is no special qualification, can enumerate ruthenium complex as shown in non-patent literature 2 or its quaternary salt, phthalocyanine, porphyrin etc., in addition, as the example of the organic pigment that can mix, can enumerate methine class pigments such as phthalocyanine, porphyrin or cyanine, merocyanine, Oxonol, the triphenylmethane pigment of no metal, the acrylic compounds pigment shown in the patent documentation 2 or oxa anthracenes pigment, azo class pigment, anthraquinone pigments, perylene class pigment etc.As preferred person, can enumerate ruthenium complex or methine class pigments such as merocyanine class pigment, acrylic compounds pigment.When using more than 2 kinds pigment, element of all kinds is adsorbed on the semiconductive thin film in turn, also can uses the mixed solution etc. of pigment to adsorb simultaneously.
The ratio of the pigment that mixes there is no special qualification, can suitably determine according to various pigments, and generally to wait mole to mix, preferred every kind of pigment uses about more than 10% mole.Use is with mixed dissolution or disperse the solution of 2 kinds of pigments, and during the load pigment, the total concentration of the pigment in the solution can be identical with the situation of the aforementioned a kind of pigment of a load on the oxide semiconductor particle film.Solvent when using as hybrid pigment can use foregoing solvent, and the solvent that each pigment of use is used can be identical or different.
During the load pigment, in order to prevent the combination between the pigment, the load pigment is very effective in the presence of inclusion compound on the film of oxide semiconductor particulate.At this as inclusion compound, can enumerate for example steroid compound, crown ether, cyclodextrin, calixarenes (Calixarene), poly(ethylene oxide) etc. such as cholic acid, cholic acid classes such as preferred deoxycholic aicd, dehyrodesoxycholic acid, chenodeoxycholic acid, Methyl cholate, sodium taurocholate, poly(ethylene oxide) etc.In addition, behind the load pigment, also can handle the semiconductive thin film surface with amines such as 4-tert .-butylpyridine.Processing method can adopt the substrate that for example will be provided with the semiconductive particles film behind the load pigment to impregnated in method in the ethanolic solution of amines etc.
Solar cell of the present invention, be that the methine class pigment etc. with aforementioned formula of load (1) on above-mentioned oxide semiconductor thin-film etc. and the components of photo-electric conversion that obtain are as electrode, by electrode, redox electrolytes matter, hole transporting material, p N-type semiconductor N etc. are constituted.As the form of redox electrolytes matter, hole transporting material, p N-type semiconductor N etc., can enumerate liquid, solidifying body (gel or gel), solid etc.As aqueous material, can enumerate redox electrolytes matter, fuse salt, hole transporting material, p N-type semiconductor N etc. are dissolved in the aqueous material that forms in the solvent or normal temperature fuse salt etc. respectively, during for solidifying body (gel or gel), can enumerate making them be included in material that forms in polymer substrate or the low molecular gel agent etc. etc.As solid matter, the fuse salt of fusion, hole transporting material, p N-type semiconductor N etc. in the time of can directly using redox electrolytes matter, heating.As hole transporting material, can enumerate material that for example uses discotic mesogenic phases such as electroconductive polymer, benzophenanthrene compounds such as amine derivative or polyacetylene, polyaniline, polythiophene etc.In addition, as the p N-type semiconductor N, can enumerate for example CuI, CuSCN etc.As to electrode, preferably has conductivity person, play the material of catalytic action in the reduction reaction with redox electrolytes matter, can use the material that for example evaporation platinum, carbon, rhodium, ruthenium etc. form on glass, polymeric membrane, with material of coated electrically conductive microparticle etc.
Example as the redox electrolytes matter that can be used for solar cell of the present invention, can enumerate and comprise with halide ion as to the halogen redox class electrolyte of the halogen compounds of ion and halogenic molecule, ferrocyanic acid salt-ferricyanate or the two luxuriant burning reduction class electrolyte that close metal complexs such as iron-ferricyanic acid ion (ferricinium ion), cobalt complex etc., organic oxidations such as alkyl hydrosulfide-alkyl disulfide, purple protochrome (Viologen dye), quinhydrones-quinone reduction class electrolyte etc., preferred halogen redox class electrolyte.Halogenic molecule in comprising the halogen redox electrolytes matter of halogen compounds and halogenic molecule can be enumerated for example iodine molecule or molecular bromine etc., preferred iodine molecule.In addition, as halogen compounds, can enumerate for example LiBr, NaBr, KBr, LiI, NaI, KI, CsI, CaI with halide ion to ion
2, MgI
2, halogen such as metal halide salt such as CuI or tetra-allkylammonium iodide, imidazoles iodide, pyridine iodide organic quaternary ammonium salt etc., preferably with iodide ion as salt to ion.In addition, except that above-mentioned iodide ion, preferably use with acid imide ions such as two (trifluoromethane sulfonyl group) acid imide ion, dicyano acid imide ions as electrolyte to ion.
In addition, when redox electrolytes matter constitutes with the form of the solution that contains it, can use that electrochemical properties is the material of inertia in this solvent.Can enumerate for example acetonitrile, propene carbonate, ethylene carbonate, the 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, gamma-butyrolacton, dimethoxy-ethane, ether, diethyl carbonate, dimethyl carbonate, 1, the 2-dimethoxy-ethane, dimethyl formamide, dimethyl sulfoxide (DMSO), 1, the 3-dioxolane, methyl formate, the 2-methyltetrahydrofuran, 3-methyl-mute piperazine-2-ketone, sulfolane (Sulfolane), oxolane, water etc., wherein, preferred especially acetonitrile, propene carbonate, ethylene carbonate, the 3-methoxypropionitrile, methoxyacetonitrile, ethylene glycol, 3-methyl-mute piperazine-2-ketone, gamma-butyrolacton etc.These can be used singly or two or more kinds in combination.As gel-like electrolyte, can be set forth in and contain the material of electrolyte or electrolyte solution in the matrix such as oligomer, polymer or contain same electrolyte in low molecular gel agent contained in the non-patent literature 3 etc. or the material of electrolyte solution etc.The concentration of redox electrolytes matter is generally 0.01 to 99 weight %, preferred 0.1 to 90 weight %.
Solar cell of the present invention, be on the oxide semiconductor thin-film on substrate load in the electrode of the components of photo-electric conversion of pigment, dispose electrode in the mode of clamping electrode, obtain by filling the solution that contains redox electrolytes matter betwixt.
Embodiment
Following according to embodiment, be described in more detail the present invention, but the present invention is not limited to these embodiment.Among the embodiment, do not specify if having, part is then represented mass parts.In addition, compound number is the compound number in the aforementioned concrete example.Maximum absorption wavelength is measured respectively by ジ エ ミ ニ 300 (バ リ ア Application corporate system) by UV-3150 spectrophotometer (Shimadzu Seisakusho Ltd.'s system), nulcear magnetic resonance (NMR) in addition.
Embodiment 1
(318) 2 parts of 1 part of methyl cyanoacetate and following compounds are dissolved in 20 parts the ethanol.The piperidines that in this solution, adds 0.01 part, reflux 2 hours.With this solution cooling, the crystallization so that the column chromatography separation and purification is separated out by with ethyl alcohol recrystallization, obtains 2.1 parts orange crystallization after the reaction.This orange crystallization in the presence of 1 part potassium hydroxide in 20 parts ethanol back flow reaction 2 hours.The water that adds 50 parts in this reaction solution again with the hydrochloric acid neutralization, filters the orange crystallization of separating out, wash, and further uses ethyl alcohol recrystallization, promptly obtains the tenne crystallization of 1.2 parts compound number (32a).
Maximum absorption wavelength and the measured value in the nuclear magnetic resonance device about this compound are as follows.
Maximum absorption wavelength: λ max=448nm (water: acetonitrile=7: 3)
The measured value of nulcear magnetic resonance (NMR):
1H-NMR(PPM：d6-DMSO)：0.85(m.3H)，1.27(m.10H)，1.53(m.2H)，1.84(m.2H)，2.73(m.2H)，3.35(m.4H)，6.60(d.1H)，6.81(m.1H)，7.25(m.3H)，7.82(d.1H)
Embodiment 2
Except 2 parts above-claimed cpd (318) being changed to 2 parts following compound (319), other and embodiment 1 handle equally, obtain the tenne crystallization of 1.4 parts compound number (278) thus.
Maximum absorption wavelength and the measured value in the nuclear magnetic resonance device about this compound are as follows.
Maximum absorption wavelength: λ max=395nm (water: acetonitrile=7: 3)
The measured value of nulcear magnetic resonance (NMR):
1H-NMR(PPM：d6-DMSO)：1.34(t.3H)，4.50(m.2H)，7.28(m.2H)，7.52(m.1H)，7.69(t.2H)，7.84(m.2H)，8.14(d.1H)，8.31(d.1H)，8.62(d.1H)
Embodiment 3 to 9
The methine class pigment of the compound number of expression in the table 7 is dissolved in the ethanol (EtOH), makes it become 3.2 * 10
-4M.By under the room temperature (20 ℃) porous substrate (semiconductor electrode film that sintered porous titanium oxide 30 minutes forms on the transparent conductivity glass electrode under 450 ℃) being impregnated in this solution 12 hours, make each pigment load, clean, make its drying with solvent (ethanol) again, obtain comprising the components of photo-electric conversion of the present invention through dye-sensitized semiconductive thin film.For embodiment 8 and embodiment 9, use 2 kinds of pigments (respectively and with methine class pigment of the present invention, with as the following formula (320) of the light sensitizing metal complex dye described in the non-patent literature 2 or as the compound of the formula (321) of the light sensitizing organic pigment described in the patent documentation 2) allocate and make 1.6 * 10
-4The EtOH solution of M similarly obtains the components of photo-electric conversion by 2 kinds of pigments of load.In addition, among the embodiment 4 to embodiment 9, at thin film of titanium oxide part (about 0.25cm of semiconductor electrode film
2) in splash into the titanium tetrachloride aqueous solution of the 0.2M of about 1cc, leave standstill 24 hours under the room temperature after, washing once more 450 ℃ of following sintering 30 minutes, is used the semiconductor electrode film of making of handling through titanium tetrachloride, similarly the load pigment.In addition,, during the load pigment, add cholic acid (Tokyo changes into industry (strain) system), be 3 * 10 as following formula (322) expression of inclusion compound about embodiment 5 and embodiment 7
-2M, pigment solution is made in allotment, and it is carried on the semiconductive thin film, obtains the dye-sensitized semiconductive thin film of handling through cholic acid.To on substrate, be provided with the semiconductive thin film of the dye-sensitized semiconductive thin film that obtains like this, the sputter face of the conductive glass that obtains with the platinum sputter is relative, the space that 20 μ m are set is also fixed, and injects to contain electrolytical solution in this space, is full of this space.Can use as electrolyte and to be dissolved with iodine/lithium iodide/1,2 dimethyl-3-n-pro-pyl imidazoles iodide/tert .-butylpyridine in the 3-methoxypropionitrile and to make it be respectively the solution of 0.1M/0.1M/0.6M/1M.
The size of the battery of measuring makes actual effect partly be 0.25cm
2Light source uses the xenon lamp of 500W, becomes 100mW/cm by AM (atmospheric thermodynamics passes through air capacity) 1.5 filters
2Short circuit current, open circuit voltage, conversion efficiency are used ソ one ラ シ ユ ミ レ one タ WXS-155S-10, and AM1.5G (initiative of (strain) ワ コ system electricity) measures.
[table 7]
| Embodiment | Compound number | Short circuit current (mA/cm 2) | Open circuit voltage (V) | Conversion efficiency (%) | The TiCl of film 4Handle | Having or not of cholic acid |
| 3 | 32a | 10.7 | 0.72 | 5.4 | Be untreated | Do not have |
| 4 | 32a | 12.8 | 0.71 | 6.3 | Handle | Do not have |
| 5 | 32a | 12.6 | 0.73 | 6.4 | Handle | Have |
| 6 | 278 | 12.1 | 0.69 | 5.8 | Handle | Do not have |
| 7 | 278 | 15.2 | 0.62 | 6.6 | Handle | Have |
| 8 | 32a+320 | 17.2 | 0.61 | 7.2 | Handle | Do not have |
| 9 | 32a+321 | 15.9 | 0.61 | 6.8 | Handle | Do not have |
As shown in Table 7, by using the components of photo-electric conversion that carry out sensitizing with the methine class pigment of the present invention of formula (1) expression, the conversion visible light is effectively.In addition, as can be known by be used in combination as the sensitizing coloring matter compound known, can further improve conversion efficiency.
According to the embodiment of the compound of formula (1b), be described in more detail the present invention, but the present invention is not limited to these embodiment below.
Embodiment 1A
(171) 1.6 parts of 1 part of methyl cyanoacetates, following compound are dissolved in 20 parts the ethanol.The piperidines that in this solution, adds 0.01 part, reflux 2 hours.With this solution cooling, the crystallization so that column chromatographic isolation and purification is separated out by using ethyl alcohol recrystallization, obtains 2.1 parts yellow crystal after the reaction.This yellow crystal in the presence of 1 part potassium hydroxide in 20 parts ethanol back flow reaction 2 hours.The water that adds 50 parts in this reaction solution, and, after the yellow crystal of separating out filters, washes,, obtain the yellow crystal of 1.2 parts compound (6) further through ethyl alcohol recrystallization with the hydrochloric acid neutralization.
Maximum absorption wavelength and the measured value in the nuclear magnetic resonance device about this compound (6) are as follows.
Maximum absorption wavelength: λ max=354nm (in the ethanol)
The measured value of nulcear magnetic resonance (NMR):
1H-NMR(PPM：d6-DMSO)：3.40(t.4H)，3.75(t.4H)，7.08(d.2H)，7.97(d.2H)，8.12(s.1H)
Embodiment 2A
1 part above-claimed cpd (171) and 1 part following compound (172) added in 20 parts the ethanol, reflux 2 hours, after the cooling with the crystallization of gained through ethyl alcohol recrystallization, obtain the vermilion crystallization of 1.2 parts compound (128).
Maximum absorption wavelength and the measured value in the nuclear magnetic resonance device about this compound (128) are as follows.
Maximum absorption wavelength: λ max=473nm (water: acetonitrile=7: 3)
The measured value of nulcear magnetic resonance (NMR):
1H-NMR(PPM：d6-DMSO)：3.57(t.4H)，3.77(t.4H)，7.10(s.2H)，7.28(t.1H)，7.48(t.2H)，7.93(d.2H)，8.52(s.1H)，8.63(d.2H)
Embodiment 3A
Except 1 part above-claimed cpd (172) being changed to 0.6 part following compound (173), other and embodiment 2A handle equally, obtain the purple crystal of 1.1 parts compound (135).
Maximum absorption wavelength and the measured value in the nuclear magnetic resonance device about this compound (135) are as follows.
Maximum absorption wavelength: λ max=552nm (in the ethanol)
The measured value of nulcear magnetic resonance (NMR):
1H-NMR(PPM：d6-DMSO)：1.80(s.6H)，3.55(t.4H)，3.75(t.4H)，4.00(s.3H)，7.14(d.2H)，7.36(d.1H)，7.82(d.1H)，8.14(m.3H)，8.34(s.1H)，8.42(d.1H)
Embodiment 4A
Except 1 part above-claimed cpd (172) being changed to 0.6 part following compound (174), other is handled similarly to Example 2, obtains the vermilion crystallization of 1.1 parts compound (134).
Measured value about the maximum absorption wavelength of this compound (134) is as follows.
Maximum absorption wavelength: λ max=440nm (in the ethanol)
Embodiment 5A
The methine class pigment of the present invention of compound number 128 is dissolved in the ethanol (EtOH), makes it become 3.2 * 10
-4M.Under the room temperature (20 ℃) with the porous substrate (under 450 ℃ on the transparent conductivity glass electrode sintered porous titanium oxide 30 minutes and semi-conductive film portion (about 0.25cm of forming
2) in, splash into the titanium tetrachloride aqueous solution of the 0.2M of about 1cc, after leaving standstill 24 hours under the room temperature (20 ℃), through washing, the semiconductor electrode film of handling through titanium tetrachloride that obtains 450 ℃ of following sintering 30 minutes once more) impregnated in this solution 12 hours, make each pigment load, clean, make its drying with solvent (ethanol) again, obtain comprising the components of photo-electric conversion of the present invention through dye-sensitized semiconductive particles film.To on substrate, be provided with the semiconductive thin film of the dye-sensitized semiconductive particles film that obtains like this, the sputter face of the conductive glass that obtains with the platinum sputter is relative, the space that 20 μ m are set is also fixed, and injects to contain electrolytical solution (electrolyte) in this space, is full of this space.Can use as electrolyte and to be dissolved with iodine/lithium iodide/1,2 dimethyl-3-n-pro-pyl imidazoles iodide/tert .-butylpyridine in the 3-methoxypropionitrile and to make it be respectively the solution of 0.1M/0.1M/0.6M/1M.
The size of the battery of measuring makes actual effect partly be 0.25cm
2Light source uses the xenon lamp of 500W, by becoming 100mW/cm behind AM (atmospheric thermodynamics passes through air capacity) 1.5 filters
2Short circuit current, open circuit voltage, conversion efficiency are used ソ one ラ シ ユ ミ レ one タ WXS-155S-10, and AM1.5G (initiative of (strain) ワ コ system electricity) measures.
Its as a result short circuit current be 12.1mA/cm
2, open circuit voltage is 0.67V, conversion efficiency is 5.5%.
As can be known from the above results, use the components of photo-electric conversion that carry out sensitizing with the methine class pigment of the present invention of formula (1) expression, the conversion visible light is effectively.In addition, methine pigment of the present invention as can be known mixes with other pigment when using, and can further improve conversion efficiency.
Utilizability on the industry
According to the present invention, can the high dye-sensitized photoelectric conversion element of low cost fabrication light-to-current inversion efficient, therefore can make cheapness, solar cell that light-to-current inversion efficient is high, extremely useful in industry.
Claims (22)
1. components of photo-electric conversion, it has used the oxide semiconductor particulate that is carried out sensitizing by the methine class pigment of following formula (1a) expression,
In the formula (1a), n represents 0 to 7 integer; R
1Expression can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or acyl group; E represents that carbon number is 2 to 4 the substituent saturated or undersaturated alkyl that has, when E has a plurality of substituting group, can by wherein arbitrarily substituting group interosculate and form ring; X represents carboxyl, and Y represents cyano group, carboxyl or acyl group; A
1, A
2And A
3Expression independently of one another can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue, cyano group, hydrogen atom or halogen atom; In addition, n is more than 2 and A
2And A
3During a plurality of separately the existence, each A
2And each A
3Can be identical or different mutually; N is beyond 0 the time in addition, can be by a plurality of A
1And/or A
2And/or A
3Formation can have substituent ring, and they can further can have substituent ring with the common formation of phenyl ring b; Phenyl ring b can have and is selected from by halogen atom, amide groups, hydroxyl, cyano group, nitro, alkoxyl, acyl group, replacement or unsubstituted amino, can has substituent aliphatic hydrocarbon residue and can have 1 to 3 substituting group in the group that substituent aromatic residue constitutes; In addition, substituting group is a plurality of when existing, these substituting groups can be mutually or as previously mentioned with
A1And/or A
2And/or A
3In conjunction with and form and can have substituent ring, when E had substituting group in addition, the substituting group on the substituting group of E and the phenyl ring b can form can have substituent ring.
2. the components of photo-electric conversion as claimed in claim 1, wherein, the methine class pigment of the formula described in the claim 1 (1a) expression is the methine class pigment of following formula (2a) expression,
In the formula (2a), n, R
1, Y, X, A
1, A
2, A
3And phenyl ring b respectively with formula (1a) in identical; R
2aTo R
7aRepresent hydrogen atom, can have substituent aromatic residue, can have substituent aliphatic hydrocarbon residue or halogen atom, in addition, R
2aTo R
7aCan interosculate to form and to have substituent ring.
3. the components of photo-electric conversion as claimed in claim 2, wherein, the methine class pigment of the formula described in the claim 2 (2a) expression is the methine class pigment of following formula (3a) expression,
In the formula, n, R
1, Y, X, A
1, A
2, A
3And phenyl ring b respectively with formula (1a) in identical.
4. as each described components of photo-electric conversion in the claim 1 to 3, wherein, n is 0 to 6.
5. as each described components of photo-electric conversion in the claim 1 to 3, wherein, R
1For having substituent aliphatic hydrocarbon residue.
6. the components of photo-electric conversion as claimed in claim 5 wherein, can have substituent aliphatic hydrocarbon residue, for having the aliphatic hydrocarbon residue of substituent carbon number 5 to 36.
7. as each described components of photo-electric conversion in the claim 1 to 3, wherein, R
1For having substituent aromatic hydrocarbon residue.
8. the components of photo-electric conversion as claimed in claim 7 wherein, can have substituent aromatic hydrocarbon residue, for have can have substituent carbon number 1 to 36 aliphatic hydrocarbon residue as substituent aromatic hydrocarbon residue.
9. components of photo-electric conversion, its use by the methine class pigment of the formula described in the claim 1 (1a) expression more than one, and metal complex and/or organic pigment with formula (1a) structure in addition carry out the oxide semiconductor particulate of sensitizing.
10. as each described components of photo-electric conversion in the claim 1 to 3, wherein, the oxide semiconductor particulate contains titanium dioxide, zinc oxide or tin oxide.
11. the components of photo-electric conversion as claimed in claim 1, wherein, the oxide semiconductor particulate is the oxide semiconductor particulate that carries out sensitizing by the methine class pigment of the expression of the formula described in the load claim 1 (1a) in the presence of inclusion compound.
12. the components of photo-electric conversion as claimed in claim 2, wherein, the oxide semiconductor particulate is the oxide semiconductor particulate that carries out sensitizing by the methine class pigment of the expression of the formula described in the load claim 2 (2a) in the presence of inclusion compound.
13. the components of photo-electric conversion as claimed in claim 3, wherein, the oxide semiconductor particulate is the oxide semiconductor particulate that carries out sensitizing by the methine class pigment of the expression of the formula described in the load claim 3 (3a) in the presence of inclusion compound.
14. as each described components of photo-electric conversion in the claim 1 to 3, wherein, the oxide semiconductor particulate is the oxide semiconductor particulate that carries out sensitizing by load methine class pigment on the film of oxide semiconductor particulate.
15. use the solar cell of each described components of photo-electric conversion in the claim 1 to 3.
16. the methine class pigment of the formula described in the claim 1 (1a) expression.
17. methine class pigment as claimed in claim 16, wherein, the methine class pigment of the formula described in the claim 1 (1a) expression is the methine class pigment of the formula described in the claim 2 (2a) expression.
18. methine class pigment as claimed in claim 17, wherein, the methine class pigment of the formula described in the claim 2 (2a) expression is the methine class pigment of the formula described in the claim 3 (3a) expression.
19. components of photo-electric conversion, wherein, on the semiconductive thin film of oxide semiconductor thin-film electrode load the methine class pigment of formula (1a) expression described in the claim 1.
20. the components of photo-electric conversion as claimed in claim 1, wherein, the X in the formula described in the claim 1 (1a) is a carboxyl, and Y is cyano group, carboxyl or acyl group, by phenyl ring b, N-R
1And the group that substituting group E forms is N-R
1Tetrahydroquinoline-6-base or the N-R that replaces
1Carbazole-3-base, the wherein R that replaces
1With identical in the formula (1a).
21. the components of photo-electric conversion as claimed in claim 20, wherein, Y is a cyano group, R
1For having the saturated or undersaturated straight or branched alkyl of substituent carbon number 1 to 18.
22. by following formula HOOC (CN) C=CH-(CH=CH)
NaThe methine class pigment that-Za represents, in the formula, Za represents the tetrahydroquinoline-6-base of N-C1 to C18 alkyl replacement or carbazole-3-base that N-C1 to C18 alkyl replaces, na represents 0 to 3 integer.
Applications Claiming Priority (3)
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|---|---|---|---|
| JP173429/2005 | 2005-06-14 | ||
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| JP177087/2005 | 2005-06-17 |
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| EP3168847B1 (en) * | 2014-07-07 | 2018-05-16 | Fujifilm Corporation | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, and terpyridine compound or esterification product thereof |
| CN105777628B (en) * | 2016-03-30 | 2018-06-26 | 阜阳欣奕华材料科技有限公司 | A kind of compound, organic electroluminescence device and display device |
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