CN102471601B - Phthalocyanine compounds - Google Patents
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- CN102471601B CN102471601B CN2010800269183A CN201080026918A CN102471601B CN 102471601 B CN102471601 B CN 102471601B CN 2010800269183 A CN2010800269183 A CN 2010800269183A CN 201080026918 A CN201080026918 A CN 201080026918A CN 102471601 B CN102471601 B CN 102471601B
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- phthalocyanine
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- vanadium oxide
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/06—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide
- C09B47/067—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile
- C09B47/0675—Preparation from carboxylic acids or derivatives thereof, e.g. anhydrides, amides, mononitriles, phthalimide, o-cyanobenzamide from phthalodinitriles naphthalenedinitriles, aromatic dinitriles prepared in situ, hydrogenated phthalodinitrile having oxygen or sulfur linked directly to the skeleton
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Abstract
Disclosed are phthalocyanine compounds, which are to be subjected to film formation and then heating. When the temperature of the heating is raised from 60 DEG C to 80 DEG C, 150 DEG C or 200 DEG C, the light absorption bands of the phthalocyanine compounds are shifted to the near-infrared region. Therefore, the phthalocyanine compounds are suitable for use in fields wherein an absorption band in the near-infrared region is necessitated. Further, the phthalocyanine compounds exhibit excellent solubility in organic solvents and thus can be easily formed into films by spin coating or other simple methods.
Description
Technical field
The present invention relates to a kind of as useful phthalocyanine compounds of material such as photoelectric conversion element, optical recording medium and filter glass.
Background technology
Phthalocyanine compound is chemical stabilization and organic semiconductor with narrow band gap.Known the film that forms the phthalocyanine compound with this feature arranged, as organic photoelectric, press element or near-infrared-absorbing material (for example: patent documentation 1 and patent documentation 2).
Because phthalocyanine compound is generally insoluble to solvent, usually by vacuum vapour deposition etc., carry out filming, there is specific substituent phthalocyanine compound and demonstrate the deliquescent situation to solvent but disclose in patent documentation 2.
Patent documentation 1: the Unexamined Patent 5-152594 of Japan communique
Patent documentation 2: the JP 2000-63693 of Japan communique
Summary of the invention
The problem that invention will solve
By vacuum vapour deposition etc., phthalocyanine compound being carried out to the situation of filming, need relatively more large-scale device and complicated operation.Therefore, when the phthalocyanine compound film forming being manufactured to photoelectric conversion layer etc., can produce that cost increases, the problem of big area difficulty.
In addition, although use various phthalocyanine compounds according to various uses,, have the problem that has both the narrow range that phthalocyanine compound is less, material is selected of desired character according to the purposes difference.For example, although the phthalocyanine compound of a part demonstrates the solvability to solvent described above,, still fail to obtain being suitable as to dissolve in solvent, can absorb the phthalocyanine compound of the P type organic semiconductor material of near infrared light simultaneously.
Therefore, the purpose of this invention is to provide a kind of can film forming by simple operation, there is the phthalocyanine compound etc. of desired absorption region as the material of photoelectric conversion element etc. simultaneously.
For solving the method for problem
Phthalocyanine compound in the present invention is the phthalocyanine compound with following general formula (I) expression, and in formula, R1 to R8 means that carbonatoms is that straight chain halogenated alkoxy below 5 or carbonatoms are any of branched alkoxy below 5.These substituent R 1 to R8 separately can for identical can be also difference.
R1 to R8 in above-mentioned general formula (I) is preferably selected from the 1a to 1g shown in following chemical formula II.
Chemical formula (II)
1a：-OCH
2CF
3
1b：-OCH
2CH
2CF
3
1c：-OCH
2CCl
3
1d：-OCH
2CH
2CCl
3
1e：-OCH(CH
3)
2
1f：-OCH
2CH(CH
3)
2
1g：-OCH
2CH
2CH(CH
3)
2
Light absorbing material of the present invention is characterised in that and contains above-mentioned phthalocyanine compound.Light absorbing material is preferably formed membranaceous, in the temperature surpassed below 60 ℃ and 150 ℃, is heated.
Photoelectric conversion element of the present invention is characterised in that: possess the photoelectric conversion layer that contains above-mentioned light absorbing material.
The invention effect
According to the present invention, can access as solvent soluble, can film forming by the simple operation such as coating method, there is the phthalocyanine compound etc. of desired absorption region as the material of photoelectric conversion element etc. simultaneously.
The accompanying drawing explanation
Fig. 1 is the figure of the molecular formula of expression phthalocyanine compound of the present invention.
Fig. 2 is the figure of the optical absorption spectra of expression phthalocyanine compound.
Fig. 3 is the figure of expression by the variation of the optical absorption spectra of the phthalocyanine compound of heat treated.
Fig. 4 is the figure of the reaction formula of the intermediate of expression generation phthalocyanine compound of the present invention.
Fig. 5 is for meaning to generate from intermediate the figure of the reaction formula of phthalocyanine compound.
Embodiment
Below, phthalocyanine compound of the present invention is described.Fig. 1 is the figure of the molecular formula of expression phthalocyanine compound of the present invention.
Carbonatoms is that a part that the straight chain halogenated alkoxy below 5 is methoxyl group, oxyethyl group, propoxy-, butoxy or pentyloxy is halogenated and forms.As the preferred fluorine of halogen (F) or chlorine (Cl).As the object lesson of phthalocyanine compound, can be listed below: Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (a fluorine methoxyl group) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (difluoro-methoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (trifluoromethoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (a chlorine methoxyl group) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (dichloro methoxyl group) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (trichlorine methoxyl group) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (2-mono-fluorine oxyethyl group) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (2,2-difluoroethoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (2,2,2-trifluoro ethoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (2-mono-chloroethoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (2,2-, bis-chloroethoxies) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (2,2,2-, tri-chloroethoxies) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (3-mono-fluorine propoxy-) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (3,3-difluoro propoxy-) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (3,3,3-trifluoro propoxy-) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (3-mono-chlorine propoxy-) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (3,3-dichloro propoxy-) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (3,3,3-trichlorine propoxy-) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (4-mono-fluorine butoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (4,4-difluoro butoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (4,4,4-trifluoro butoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (4-mono-chlorine butoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (4,4-dichloro butoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (4,4,4-trichlorine butoxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (5-mono-fluorine pentyloxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (5,5-difluoro pentyloxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (5,5,5-trifluoro pentyloxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (5-mono-chlorine pentyloxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (5,5-dichloro pentyloxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (5,5,5-trichlorine pentyloxy) phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-, eight-isopropoxy phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-, eight-isobutoxy phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-, eight-tert.-butoxy phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-, eight-isopentyloxy phthalocyanine vanadium oxide, Isosorbide-5-Nitrae, 5,8,9,12,13,16-, eight-neopentyl oxygen phthalocyanine vanadium oxide etc.
Here, substituent R 1 to R8 is preferably selected from the 1a to 1g shown in following chemical formula II.
Chemical formula (II)
1a：-OCH
2CF
3
1b：-OCH
2CH
2CF
3
1c：-OCH
2CCl
3
1d：-OCH
2CH
2CCl
3
1e：-OCH(CH
3)
2
1f：-OCH
2CH(CH
3)
2
1g：-OCH
2CH
2CH(CH
3)
2
The substituent R 1 to R8 that is selected from 1a to 1g separately can be identical, also can be different., substituent R 1 to R8 is not limited to be identical above-claimed cpd, for example: 1, 4, 5, 8, 9, 12, 13, 16-eight (2, 2, the 2-trifluoro ethoxy) phthalocyanine vanadium oxide, 1, 4, 5, 8, 9, 12, 13, 16-eight (2, 2, 2-tri-chloroethoxies) phthalocyanine vanadium oxide, 1, 4, 5, 8, 9, 12, 13, 16-eight (3, 3, 3-trifluoro propoxy-) phthalocyanine vanadium oxide, 1, 4, 5, 8, 9, 12, 13, 16-eight (3, 3, 3-trichlorine propoxy-) phthalocyanine vanadium oxide, 1, 4, 5, 8, 9, 12, 13, 16-eight-isopropoxy phthalocyanine vanadium oxide, 1, 4, 5, 8, 9, 12, 13, 16-eight-isobutoxy phthalocyanine vanadium oxide, 1, 4, 5, 8, 9, 12, 13, 16-eight-isopentyloxy phthalocyanine vanadium oxide etc.For example, to R8, also can make any repetition in above-mentioned 1a to 1g as the substituent R of 1,4,5,8,9,12,13,16 1.
The solvability of 10 pairs of organic solvents of phthalocyanine compound is good.The solvability of organic solvent is considered mainly by substituent R 1 to R8, to be caused.That is by there is carbonatoms as substituting group, be, that straight chain halogenated alkoxy below 5 or carbonatoms are the solvability that branched alkoxy below 5 has improved phthalocyanine compound 10.To improve deliquescent viewpoint, substituting group more preferably is selected from the 1a to 1g shown in chemical formula II, is particularly preferably the halogenated alkoxy of 2,2,2-trifluoro ethoxy (1a) etc.
In the situation that by phthalocyanine compound 10 as light absorbing material, be preferably formed membranaceous (below, the situation that is called filming is arranged).Although do not limit the formation method of film,, because the solvability of 10 pairs of organic solvents of phthalocyanine compound is good, therefore, can form by coating method.Coating method forms coating fluid for phthalocyanine compound 10 is dissolved in suitable solvent, coating fluid is coated to the method that forms film on substrate.As used solvent, can list: the alcohols such as methyl alcohol, ethanol; The ketone such as acetone, methylethylketone; The ester such as ethyl acetate, butylacetate class; The hydro carbons such as toluene, dimethylbenzene; The halohydrocarbon such as methylene dichloride, chloroform, chlorobenzene etc.Concentration in the solvent of phthalocyanine compound 10 is preferably 0.01 to 20 % by weight.
As substrate, can use such as sheet glass, plastics film etc.As plastics film, can list: the polyolefine such as polyethylene, polypropylene; The polyester such as polyethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate; Polyvinyl chloride; Polystyrene; The film that polyimide etc. form.The thickness of substrate is 10 μ m to 5mm left and right.In addition, also gas-insulated layer or conductive layer can be set on these substrates.As the gas-insulated layer, for example can list: the layer formed by silicon-dioxide or silicon nitride can list as conductive layer: the layer formed by Indium sesquioxide, stannic oxide, tin-doped indium oxide (ITO) or zinc oxide.
As coating fluid being coated to the method for substrate, can list: method of spin coating, scraping article coating method, intaglio plate coating method, spraying method etc.After adopting these methods that coating fluid is coated with, form as required the film of phthalocyanine compound by adding the heat extraction solvent.The thickness of the film formed is not particularly limited, and according to purposes and purpose, decides and get final product, still, is generally about 10nm to 10 μ m.In addition, the formation method as film, can adopt vacuum vapour deposition or sputtering method etc.
In addition, preferably the phthalocyanine compound of filming 10 is heated.By heating the maximum absorption wavelength displacement that can make phthalocyanine compound 10.Preferably Heating temperature is carried out below 60 ℃ and 150 ℃ surpassing.Heating means do not limit, and can adopt the method for hot-plate or baking oven (thermostatic bath) etc. to carry out.Be 1 minute to 1 hour heat-up time, preferably about 2 minutes to 30 minutes.The heating atmosphere can be in atmosphere, also can be under reduced pressure, under nitrogen or rare gas element fill.In addition, also can carry out drying and the thermal treatment of coated film simultaneously.
Herein, the optical absorption spectra of phthalocyanine compound 10 described.The optical absorption spectra that Fig. 2 is phthalocyanine compound 101a of the present invention (aftermentioned).As shown in Figure 2, the optical absorption spectra solution of phthalocyanine compound 101a is from membranaceous different.That is, shown in dotted line when being solution, there is maximum absorption wavelength near 740nm, when membranaceous, as shown in solid line, maximum absorption wavelength becomes about 836nm.In addition, membranaceous phthalocyanine compound 101a is for coating fluid being coated to filming on glass substrate, and heats and form in 150 ℃.
Moreover, although the phthalocyanine compound 101a of film like has the optical absorption spectra as shown in the solid line of Fig. 2, by the heating optical absorption spectra, change.In addition, the solution of Fig. 2 is for being used chlorobenzene as solvent.And, owing to not finding that for chlorobenzene absorption is arranged near 740nm, therefore, the variation of the maximum absorption wavelength in Fig. 2 results from phthalocyanine compound 101a.
Fig. 3 means to change the variation of the optical absorption spectra in the situation of Heating temperature of the filming phthalocyanine compound 101a shown in Fig. 2.As shown in Figure 3, in the situation of 60 ℃ of heating, there is the optical absorption spectra (dotted line) that approaches the solution shape.Then, when Heating temperature is made as 80 ℃, absorption peak is to the near infrared region displacement.Moreover, in the situation that Heating temperature is made as 150 ℃, 200 ℃, maximum absorption wavelength is to the near infrared region displacement and show the value roughly the same with the situation of 80 ℃, known is the phthalocyanine compound with stable absorption peak.Therefore, phthalocyanine compound 101a can be suitable for needing in the field of absorption band of near infrared region.In addition, as shown in the figure, when when being heated for 200 ℃, can find the decline of absorption intensity as shown in the figure.Therefore, preferably in surpassing the temperature range below 60 ℃ and 150 ℃, heat phthalocyanine compound 101a.
In addition, during the film of the phthalocyanine compound 101a after heating with microscopic examination, can be observed the zone of the birefringence that shows high crystalline.Thus, can consider that phthalocyanine compound 101a passes through heating and crystallization, and, when thering is crystal structure, there is absorption band near infrared region.
As shown in the reaction formula (1) of Fig. 4, by the reaction of dicyano quinhydrones and 2,2,2-trifluoroethyl tosylate, synthetic Isosorbide-5-Nitrae-bis-(2,2,2-trifluoro ethoxy) phthalonitrile (compound 12).Should be synthetic dicyano quinhydrones and 2,2,2-trifluoroethyl tosylate be added in the solvent of DMF (DMF) etc., in 80 to 130 ℃ of stir abouts carry out in 1 to 60 hour.In addition, 2,2,2-trifluoroethyl tosylate can be by for example: the method for putting down in writing in 0360 paragraph of JP 2005-84584 communique obtains.In addition, resulting compound 12 can be separated by known method, washing and purifying.
Then, as shown in Figure 5, by resulting compound 12, vanadic salts and urea (Urea) are added in benzonitrile, dichlorobenzene equal solvent, in 100 to 170 ℃ of stir abouts 10 to 120 minutes, thus the compound 101a of one of above-mentioned phthalocyanine compound 10 (with reference to Fig. 1) can be synthesized, that is: 1,4,5,8,9,12,13,16-eight (2,2,2-trifluoro ethoxy) phthalocyanine vanadium oxide.Can use vanadous chloride, vanadium trichloride, vanadium pentoxide etc. as vanadic salts.Resulting Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (2,2,2-trifluoro ethoxy) phthalocyanine vanadium oxide can be separated by known method, washing and purifying.
At this, to having as substituent-OCH
2CF
3Phthalocyanine compound be illustrated, still, if by compound 12-OCH
2CF
3Replace with other the straight chain halogenated alkoxy of carbonatoms below 5, or the branched alkoxy of carbonatoms below 5, just can access and there is these substituent phthalocyanine compounds 10.
Next, photoelectric conversion element of the present invention is described.Photoelectric conversion layer of the present invention possesses the light absorbing material that contains phthalocyanine compound 10.The photoelectric conversion element generally has two electrodes, i.e. anode and negative electrode, and there is the structure that possesses photoelectric conversion layer between anode and negative electrode.In anode or negative electrode, at least one is necessary to see through light, still, and usually using anode as the photopermeability electrode.
As the electro-conductive material that forms anode, can list: Indium sesquioxide, stannic oxide, tin-doped indium oxide (ITO), iridium oxide, zinc oxide, gallium-doped zinc oxide etc., but, from electroconductibility and the transparency for well, preferred tin-doped indium oxide (ITO), gallium-doped zinc oxide.In addition, as the electro-conductive material that forms negative electrode, can list: the metals such as platinum, gold, aluminium, iridium, chromium; Carbon nanotube etc.
Anode and negative electrode be by, such as the method for utilizing the PVD (physical vapor evaporation) such as vacuum evaporation, sputter, ion plating, form the layer formed by electro-conductive material and obtain on substrate or photoelectric conversion layer.As substrate preferred glass plate or plastics film.As plastics film, can list: the polyolefine such as polyethylene, polypropylene; The polyester such as polyethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate; Polyvinyl chloride; Polystyrene; The film that polyimide etc. form.The thickness of substrate is 10 μ m to 5mm left and right.The thickness of anode and negative electrode preferably is respectively 10 to 500nm.
Photoelectric conversion layer is the layer that has absorb light and light energy conversion is become to the function of electric energy, can list: for example p-type semiconductor layer and N-shaped semiconductor multilayer are formed.Phthalocyanine compound is the p-type semi-conductor, and phthalocyanine compound 10 of the present invention plays a role as the p-type semiconductor layer in such photoelectric conversion layer.
In addition, the N-shaped semi-conductor can be inorganic semiconductor, can be also organic semiconductor.The silicone of arsenic doped or phosphorus can be listed as inorganic semiconductor, as organic semiconductor, soccerballene, [6,6]-phenyl-C can be listed
61The derivative of the soccerballenes such as-methyl-butyrate (PCBM).
In photoelectric conversion layer, also proper semiconductor (i N-type semiconductorN) layer can be arranged between p-type semiconductor layer and N-shaped semiconductor layer.Can improve transformation efficiency by making photoelectric conversion layer form such formation.
Each layer that forms photoelectric conversion layer can be by such as the coating methods such as the PVD such as vacuum evaporation, sputter, ion plating (physical vapor evaporation), method of spin coating, scraping article coating method, intaglio plate coating method, spraying method formation.The thickness of photoelectric conversion layer is preferably 10nm to 3 μ m.
In addition, also buffer layer can be set on the photoelectric conversion element.Can list the layer of the bathocuproine (Bathocuproine) (2,9-dimethyl-4,7-phenylbenzene-1,10-phenanthroline) contained as the electron hole blocking material as buffer layer.This buffer layer (electron hole blocking material) is arranged between N-shaped semiconductor layer and negative electrode usually.As the photoelectric conversion element, can list such as solar cell or optical sensor etc.
Embodiment
Below, enumerate embodiment the present invention is described more specifically.But the present invention is not limited to following examples.
In addition, the structure of compound is determined, solvability, light absorption and crystalline mensuration/evaluation are carried out as follows.
The structural confirmation of compound
By
1H NMR measures and IR mensuration is determined.
1H NMR measures and uses nuclear magnetic resonance device (NMR) (Bruker company system, " Avance500 "), IR measures and uses Fourier transform infrared photoabsorption (FT-IR) determinator (PERKIN ELMER company system, " SPECTRUM ONE "), by Potassium Bromide (KBr) pressed disc method, is measured.
Dissolubility test
For the concentration that makes phthalocyanine compound is 10 % by weight, phthalocyanine compound is added in each solvent and stirred, by the solvability of visual observation phthalocyanine compound, according to having or not solute to observe solvability.Use methylene dichloride, chloroform, chlorobenzene, tetrahydrofuran (THF), acetone, ethyl acetate, toluene as solvent.
Light absorption
Use spectrophotometer (Shimadzu Scisakusho Ltd's system, " UV-3101PC ") to be measured.
Crystalline definite
Use polarizing microscope (Olympus Co., Ltd's system, " BX51 ") to be observed with 10 times of ratio of enlargement.
Embodiment 1
As shown in the reaction formula (1) of Fig. 4, from the synthetic Isosorbide-5-Nitrae of dicyano quinhydrones (Tokyo changes into Co., Ltd.'s system)-bis-(2,2,2-trifluoro ethoxy) phthalonitrile (compound 12).That is, under nitrogen atmosphere, in room temperature, the solution that sodium Metal 99.5 2.3g is dissolved in to methyl alcohol (solvent) 80ml adds in dicyano quinhydrones 8.0g, in stirring at room 30 minutes, removes unreacted methyl alcohol under decompression.By 2,2,2-trifluoroethyl tosylate 40.0g and as the N of solvent, N-dimethyl formyl (DMF) adds wherein, is warming up to 120 ℃ and stirs 48 hours.After this reaction mixture is cooled to room temperature, add frozen water, after the solid filtering generated is collected, use methanol wash.By the solid recrystallization from ethanol/hexane (mixed solution) obtained like this, in 50 ℃ of drying under reduced pressure 6 hours.Like this, obtain the Isosorbide-5-Nitrae of 11.7g-bis-(2,2,2-trifluoro ethoxy) phthalonitrile (compound 12) (yield 70%).
Isosorbide-5-Nitrae-bis-(2,2,2-trifluoro ethoxy) phthalonitrile (compound 12) 5.0g is mixed with urea 40.0g and vanadium trichloride 1.6g.This reaction mixture is stirred, simultaneously in 160 ℃ of heating approximately 90 minutes.Then, 1N hydrochloric acid 100ml is added to place be cooled in the reaction solution of room temperature, be heated to 100 ℃.Place cooling after, the green solid filter generated reclaims, and after fully washing with pure water, by ethyl acetate, is extracted.The organic layer extracted is concentrated, and with column chromatography (silica gel, acetone: hexane=1: 1) purifying.And then, carry out recrystallization (ethanol/hexane), obtain the compound (yield 40%, fusing point: 290 ℃ (decomposition)) of 2.0g.By the gained compound
1The result that H NMR measures and IR measures is expressed as follows.
1H NMR measures (in deuterated acetone)
8.99ppm(phH，8H)、5.78ppm(-OCH
2CF，16H)
Visible in not importing the phthalocyanine of metal---do not observe near chemical shift 1.0ppm.
IR measures
Observe the 1002cm of the vibration peak that belongs to vanadium oxide (VO)
-1.
From these results, can determine, resulting compound is Isosorbide-5-Nitrae, 5,8,9,12,13,16-eight (2,2,2-trifluoro ethoxy) phthalocyanine vanadium oxide (phthalocyanine compound 101a).The evaluation result of this phthalocyanine compound 101a is expressed as follows.
<dissolubility test >
Can determine in all solvents that use and not find not solute, show good solubility.
<light absorption >
10mg phthalocyanine compound 101a is dissolved in chlorobenzene 0.75ml, and drops on the surface of glass substrate.Then, by making substrate rotation, carry out the spin-coating film of phthalocyanine compound 101a, in 60 ℃ of dryings 10 minutes and filming phthalocyanine compound 101a.Dried film thickness is 40nm.The film obtained in use carries out in the mensuration of light absorption, and maximum absorption wavelength is 740nm.Film is to 836nm in the maximum absorption wavelength of 80 ℃, 150 ℃, 200 ℃ heating after 10 minutes, has shown good near infrared ray absorbing.
<crystalline definite
The film that method that will be same with dissolubility test is made respectively at 80 ℃, 150 ℃, 200 ℃ heating after, in the use polarizing microscope is observed, can be observed the zone of the birefringence that shows high crystalline, and can determine the excellent in crystallinity of phthalocyanine compound 101a.In addition, do not observe the zone that shows crystalline birefringence in the phthalocyanine compound 101a of 60 ℃ of dryings.
From above result, can consider, phthalocyanine compound 101a is crystallization by heating, and has absorption band when having crystal structure near infrared region.
Then, use resulting phthalocyanine compound 101a to make the photoelectric conversion element, and estimated.At first, wash and UV (ultraviolet ray)-ozonize, ITO film (anode) at clean ito glass (forming transparent conductivity glass, the resistance value 14 Ω/sq of tin-doped indium oxide (ITO) film on glass substrate) is upper, at pressure 3.3 * 10
-4Pa, stackeding speed
Under the condition of second, that resulting phthalocyanine compound 101a is stacked to form thickness 50nm.Then, on phthalocyanine compound 101a layer, at pressure 1.1 * 10
-4Pa, stackeding speed
Will be stacked to form thickness 50nm as N-shaped organic semi-conductor soccerballene (Nano-C company system) under the condition of second.Again, on Fullerene layer, at pressure 8.5 * 10
-5Pa, stackeding speed
To be laminated into thickness 10nm as the bathocuproine (HJEC of Co., Ltd. O system) of hole blocking agent under the condition of second.On the bathocuproine layer, at pressure 8.2 * 10
-5Pa, stackeding speed
Second condition under, will be laminated into 50nm as the silver of negative electrode (Japanese high-purity chemical Co., Ltd. system), thereby make the photoelectric conversion element.Current value while using tengsten lamp (100W) to irradiate light from ito glass side direction photoelectricity conversion elements, measuring short circuit, can obtain the current value of 27.4 μ A, and can obtain showing the photoelectric conversion element of superperformance.
Comparative example
At the phthalocyanine compound with substituent R identical with phthalocyanine compound 101a, and, in the central metal comparative example 1 that is copper and the central metal compound comparative example 2 that is tindichloride, can determine and not there is absorption band near infrared region.In addition, in substituent R 1 to R8 (with reference to Fig. 1 etc.), be all in the comparative example 3 of vanadium oxide phthalocyanine of hydrogen, to the solvability of each solvent of using in above-mentioned dissolubility test lower than phthalocyanine compound 101a.
According to the present invention as above, phthalocyanine compound 10 can be become membranization by the coating method than simpler method of spin coating such as existing vapour deposition method etc.In addition, phthalocyanine compound 10 of the present invention is owing to having absorbing properties, therefore, can be suitable for photovoltage element, optical recording medium of organic thin film solar cell or optical sensor etc. etc.
Moreover, phthalocyanine compound 10 by heat treated can be easily by absorption band to the near infrared region displacement.Therefore, phthalocyanine compound 10 meets the performance of special requirement in field of P type organic semiconductor material etc., also can be described as in this respect useful.
Claims (6)
1. the phthalocyanine compound meaned with following logical formula I:
（Ⅰ）
Wherein, in formula, R1 to R8 means that carbonatoms is the straight chain halogenated alkoxy below 5.
2. phthalocyanine compound according to claim 1, it is characterized in that: the R1 to R8 in described logical formula I is selected from the 1a to 1d shown in following chemical formula II:
Chemical formula (II)
1a：-OCH
2CF
3
1b：-OCH
2CH
2CF
3
1c：-OCH
2CCl
3
1d：-OCH
2CH
2CCl
3。
3. a light absorbing material, is characterized in that: contain phthalocyanine compound claimed in claim 1.
4. light absorbing material according to claim 3 is characterized in that: described light absorbing material is formed membranaceous, heated in the temperature surpassed below 60 ℃ and 150 ℃.
5. a photoelectric conversion element is characterized in that: possess the light absorbing material that contains the phthalocyanine compound that following logical formula I means:
（Ⅰ）
Wherein, in formula, R1 to R8 means that carbonatoms is that straight chain halogenated alkoxy below 5 or carbonatoms are any of branched alkoxy below 5.
6. a photoelectric conversion element, it is characterized in that possessing light absorbing material, it is membranaceous that described light absorbing material is that the light absorbing material that will contain the phthalocyanine compound that following logical formula I means forms, and in the temperature surpassed below 60 ℃ and 150 ℃, heated and obtain:
（Ⅰ）
Wherein, in formula, R1 to R8 means that carbonatoms is that straight chain halogenated alkoxy below 5 or carbonatoms are any of branched alkoxy below 5.
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|---|---|---|---|
| JP2009-160965 | 2009-07-07 | ||
| JP2009160965 | 2009-07-07 | ||
| PCT/JP2010/060334 WO2011004688A1 (en) | 2009-07-07 | 2010-06-18 | Phthalocyanine compounds |
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| JP (1) | JP4967074B2 (en) |
| KR (1) | KR20120112345A (en) |
| CN (1) | CN102471601B (en) |
| TW (1) | TWI476250B (en) |
| WO (1) | WO2011004688A1 (en) |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000063693A (en) * | 1998-08-24 | 2000-02-29 | Nippon Shokubai Co Ltd | Preparation of phthalocyanine compound |
| JP2002114790A (en) * | 2000-10-04 | 2002-04-16 | Nippon Shokubai Co Ltd | Method for purifying phthalocyanine compound and naphthalocyanine compound |
| JP2004240043A (en) * | 2003-02-04 | 2004-08-26 | Fuji Photo Film Co Ltd | Original plate for lithographic printing plate |
| CN101255163A (en) * | 2008-03-14 | 2008-09-03 | 中国科学院长春应用化学研究所 | Soluble tetraalkyl phthalocyanine compound and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295283A (en) * | 1991-06-19 | 1993-11-09 | Mitsui Toatsu Chem Inc | Colorant for filter and color filter containing the colorant |
| JPH1059974A (en) * | 1996-08-21 | 1998-03-03 | Yamamoto Chem Inc | Production of phthalocyanine compound |
| JPH11106386A (en) * | 1997-10-02 | 1999-04-20 | Ricoh Co Ltd | Production of metallophthalocyanines |
| JP4079234B2 (en) * | 1998-01-23 | 2008-04-23 | 株式会社リコー | Method for producing metal phthalocyanines |
| JP4238822B2 (en) * | 2004-12-03 | 2009-03-18 | セイコーエプソン株式会社 | Pattern-formed substrate, electro-optical device, pattern-formed substrate manufacturing method, and electro-optical device manufacturing method |
-
2010
- 2010-06-18 CN CN2010800269183A patent/CN102471601B/en active Active
- 2010-06-18 KR KR1020127000334A patent/KR20120112345A/en not_active Application Discontinuation
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- 2010-06-18 WO PCT/JP2010/060334 patent/WO2011004688A1/en active Application Filing
- 2010-06-30 TW TW099121413A patent/TWI476250B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000063693A (en) * | 1998-08-24 | 2000-02-29 | Nippon Shokubai Co Ltd | Preparation of phthalocyanine compound |
| JP2002114790A (en) * | 2000-10-04 | 2002-04-16 | Nippon Shokubai Co Ltd | Method for purifying phthalocyanine compound and naphthalocyanine compound |
| JP2004240043A (en) * | 2003-02-04 | 2004-08-26 | Fuji Photo Film Co Ltd | Original plate for lithographic printing plate |
| CN101255163A (en) * | 2008-03-14 | 2008-09-03 | 中国科学院长春应用化学研究所 | Soluble tetraalkyl phthalocyanine compound and preparation method thereof |
Non-Patent Citations (4)
| Title |
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| 《可溶性镍酞菁的光谱特性研究》;魏少华 等;《感光科学与光化学》;20021130;第20卷(第6期);411-416 * |
| 《烷氧基取代金属酞菁固态薄膜光谱及结构的研究》;刘恺;《感光科学与光化学》;19960531;第14卷(第2期);121-124 * |
| 刘恺.《烷氧基取代金属酞菁固态薄膜光谱及结构的研究》.《感光科学与光化学》.1996,第14卷(第2期), |
| 魏少华 等.《可溶性镍酞菁的光谱特性研究》.《感光科学与光化学》.2002,第20卷(第6期),411-416. |
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| WO2011004688A1 (en) | 2011-01-13 |
| TW201107427A (en) | 2011-03-01 |
| KR20120112345A (en) | 2012-10-11 |
| JP4967074B2 (en) | 2012-07-04 |
| CN102471601A (en) | 2012-05-23 |
| TWI476250B (en) | 2015-03-11 |
| JPWO2011004688A1 (en) | 2012-12-20 |
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