CA1329622C - Ferrocene derivatives, surfactants containing them and process for producing organic thin film - Google Patents

Abstract

ABSTRACT

Provided are novel ferrocene derivatives represented by the general formula:

(wherein R1 and R2 are independently hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, m is an integer of 1 to 4, n is an integer of 1 to 5, r is an integer of 11 to 18, and s is a real number of 2.0 to 70.0) or the general formula:

Description

13~9622 FERROCENE DERIVATIVES AND PROCESS FOR PRODUCING
ORGANIC THIN FILMS

TECHNICAL FIELD
The present invention relates to ferrocene derivatives and a process for producing organic thin films, and more particularly to novel ferrocene derivatives, surfactants containing them, and a process for producing organic thin films using various ferrocene derivatives including said novel ferrocene derivatives.
BACKGROUND ART
In general, coloring matters such as phthalocyanine or its derivatives and the like are insoluble in water, and although they are soluble in organic solvents such as dimethylformamide (DMF), tetrahydrofuran (THF) and the like, their soluble amounts are small and the solubility is only several milligrams (mg).
Surfactants to make the phthalocyanine and the like soluble in water have heretofore been investigated, but no satisfactory surfactant has been developed. It is reported that functional group-substituted phthalocyanine derivatives can be dissolved in water to some extent by the use of sulfone-based surfactants. However, the solubility is not always sufficiently high and further unsubstituted phthalocyanine cannot be dissolved at all.
In connection with polymer insoluble in water, surfactants to make them soluble in water have been investigated in the same manner as described above. In fact, however, no satisfactory results have been obtained.
The present inventors have made extensive investigations to develop surfactants to make coloring matters such as phthalocyanine or its derivatives and the like, or water-insoluble polymers and the like, soluble in water.
In the course of the study, it has been found that ferrocene derivatives are promising as surfactants having the aforementioned performanc~. As a result of further investigations based on the above findings, the present inventors have discovered that new ferrocene derivatives derived by introducing a polyoxyethylene chain or a specified substituent containing pyridinium ion, in ferrocene or its derivatives can achieve the object. At the same time, they have discovered that a water-insoluble (hydrophobic) organic thin film can be efficiently produced from various ferrocene derivatives including the new ferrocene derivatives by electrochemical techniques.
An object of the present invention is to provide novel ferrocene derivatives. Another object of the present invention is to provide surfactants having superior performance, containing the novel ferrocene derivatives.
Another object of the present invention is to provide a process for efficiently producing thin films of hydrophobic organic substances.
DISCLOSURE OF INVENTION

1~29S22 That is, the present invention provides ferrocene derivatives represented by the general formula:

R ' ~ C n H 2 n_ ~ N~-- R
F e ... ( I

R 2~

(wherein R1 and R2 are each a hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, R3 is hydrogen, a methyl group, an ethyl group, a methoxy group, a carbomethoxy group, a hydroxyl group, a carboxyl group or a sulfonic acid group, and X is a halogen, and CnH2n is a straight chain or branched chain alkylene group having 4 to 16 carbon atoms), the general formula:

R ' ~~-( C H z) .--0--( C H 2 C H z O ) ~ H
F e R Z ~ ~ lI A ) 25 (wherein r is an integer of 11 to 18, s is a real number of 2.0 to 50.0, and Rl and R are the same as described above). or the general formula:

132~622 R ' ~~ ( C H 2) w--C --O--( ~ H ~ C H 2 0 ) S H
F e O .. t ~ B ) (wherein w is an integer of 2 to 20, and s, Rl and R2 are the same as described above).
The invention provide5 a ferrocene derivative represented by the general formula-:

R ~--C, H ' ~--X N~ R ' R~ (I) (wherein Rl and R are each independently a hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, R3 is a hydrogen, a ~ethyl group, an ethyl group, a methoxy group, a carbomethoxy group, a hydroxyl group, carboxyl group or a sulfonic acid group, X
is a halogen, and CnH2n is a straight or branched hydrocarbon group having 4 to 16 carbon atoms); or the general formula:

25(R '~( C H ~),~0~(C H t C H ~ O), H

(R 2~
~B 4 _, ...4A

1 (wherein ~ is an integer of 2 to 4, n is an integer of 2 to 5, r is an integer of 11 to 18, s is a real number of 2.0 to 70.0, and Rl and R2 are the same as described above), or the general formula: `

5 ~R ~ ( C H ~ C --O~( C H t C H ~ O ), ~{
F~ O
(R')~ ! (8) (wherein w is an integer of 2 to 18, and m, n, 9, R and R2 are the same as described above) The present invention further provides surfactants containing the ferrocene derivatives represented by the above general formula (I), (IIA) , (IIB), (A) or (~)~
The present invention further provides a process for producing organic thin films which comprises making hydrophobic organic substances soluble in an aqueous medium by the use of surfactants (micelle forming agents) comprising ferrocene derivatives, and electrolyzing the micelle solution thus obtained to form a thin film of the above hydrophobic organic substance.
The novel ferrocene derivatives of the present invention are the novel compounds represented by the general formula (I), (IIA) or (IIB). In accordance with the process 2~ of the present invention, using these novel ferrocen~

...4B
'~.

132~622 1 derivatives or other ferrocene derivatives as surfactants, thin films of hydrophobic organic substances can be formed efficiently and further in the desired thickness.
BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 is a view schematically illustrating the principle of the process of the present invention, wherein 1 indicates a ferrocene derivative; 2, a hydrophobic organic substance 3, micelle; 4, an oxidized ferrocene derivative;
5, an anode; 6, a cathode; Fc, ferrocene; and e , an electron.
Fig. 2 is a proton nuclear magnetic resonance (lHNMR) spectrum of the ferrocene derivative obtained in Example 1.
Fig. 3 is an infrared (IR) absorption spectrum of the ferrocene~derivative.
Fig. 4 is an ultraviolet-visible (UV-VIS) absorption spectrum of the ferrocene derivative.
Fig. 5 indicates W-VIS absorption spectra of the supernatants obtained in Example 2 and Comparative Example 1.
Fig. 6 is an electron micrograph showing the surface structure of the thin film formed in Example 3.
Fig. 7 indicates ultraviolet tUV) absorption spectra of the ethanol solutions of the thin films formed in Examples 3 and 4.
Fig. 8 is an electron micrograph showing the surface structure of the thin film formed in Example 4.
Fig. 9 is lH-NMR of the ferrocene derivative obtained in Example 5.

Fig. 10 is lH-MMR of the ferrocene derivative obtained in Example Ç.

Fig. 11 is H-NHR of the ferrocene derivative obtained in Example 7.
Fig. 12 indicates visible (VIS) absorption spectra of the supernatants obtained in Examples 8 to 12.
Fig. 13 indicates visible absorption spectra of the coloring matter thin films on IT~ as obtained in Examples 13 and 14.
Fig. 14 is an electron micrograph showing the surface structure of the thin film formed in Example 13.
Fig. 15 indicates UV absorption spectra of the ethanol solutions of the thin films formed in Examples 4, 15 and 16.
Fig. 16 is an electron micrograph showing the surface structure of the thin film formed in Example 17.
Fig. 17 is a UV absorption spectrum of the methanol solution of the thin film formed in Example 18.
Fig. 18 is an electron micrograph showing the surface structure of the thin film formed in Example 19.

Fig. l9(a) is an electron micrograph showing the surface structure of the thin film before post-treatment as formed in Example 20.
Fig. l9(b) is an electron micrograph showing the surface structure of the thin film after post-treatment as formed in Example 20.
Fig. 20 is a Fourier transformation infrared absorption spectrum of the thin film formed in Example 20.
Fig. 21 is a IR absorption spectrum using a KBr l pellet of the polymer used in Example 20.
Fig. 22 is a graph showing a relation between the film thickness of the thin film formed in Examples 20 and 21, and the amount of electricity having passed per unit area of ITO.
Fig. 23 is a UV absorption spectrum of the thin film formed in Example 21.
Fig. 24 is an electron micrograph showing the surface structure of the thin film formed in Example 21.
BEST MODE FOR CARRYING OUT THE INVENTION

The novel ferrocene derivatives of the present invention are represented by the general formula (I), (IIA) or (IIB). In the general formula (I), R and R are each a hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, R3 is a hydrogen, a methyl group, an ethyl group, a methoxy group, a carbomethoxy group, a hydroxyl group, a carboxyl group or a sulfonic acid group, and X is a halogen, that is, chlorine, bromine, iodine, fluorine and the like. CnH2n indicates a straight or branched alkylene group having 4 to 16 carbon atoms (that is, n is an integer of 4 to 16 ). Specific examples are straight alkylene groups exemplified by polymethylene groups:
(CH2)n, such as a tetramethylene group, a pentamethylene group,an octamethylene group, an undecamethylene group, a dodecamethylene group, a hexadecamethylene group and the like~ or branched alkylene groups such as a 2-methylundecamethylene group, a 4-ethylundecamethylene 1 group and the like.
The ferrocene derivatives represented by the general formula (I) can be produced by various methods.
For example, they can be produced by adding pyridine-based compounds represented by the general formula:

R ~
~O) ( I -- b ) (wherein R3 is the same as described above) to halogen-containing ferrocene derivatives represented by the general formula:

D I
~~-- C n H Z n X
F ~ ( I - a ) R 2 ~

(wherein Rl, R2, X and CnH2n are the same as described above) and reacting them for about 1 to 5 hours in an atmosphere 25 of inert gas such as nitrogen gas and the like at a temperature of 20 to 70C while sufficiently stirring.
Thereafter, the product is washed with diethyl ether and 1 the like and dried, and then dissolved in a polar solvent such as acetone, methanol, ethanol, tetrahydrofuran and the like. The resulting solution is poured in diethyl ether and the like to precipitate. This operation is repeated several times, and upon filtration, the ferrocene derivatives of the general formula (I) can be obtained in a high purity.
On the other hand, in the ferrocene derivatives represented by the general formula (IIA), r is an integer of 11 to 18, and s is a real number of 2.0 to 50Ø Since r is an integer of 11 to 18 as described above, an alkylene group having 11 to 18 carbon atoms, such as an undecyl group, a dodecyl group and the like, is present between a ring-forming carbon atom and an oxygen atom (oxygen atom nearest the ferrocene structure). s means not only an integer between 2.0 to 50.0 but also a real number including them, and indicates an average repeating number of the oxyethylene group (-CH2CH2O-) constituting the ferrocene derivative.
The ferrocene derivatives of the general formula (IIA) can be produced by various methods. For example, they are produced as follows:

For example, the ferrocene derivatives represented by the general formula (IIA) are obtained by adding an alkali metal (metallic sodium, metallic potassium and the like) to polyethylene glycol represented by the general formula:
HO~CH2CH2O~sH ................... (II-a) (wherein s is the same as described above), stirring the resulting mixture for several minutes to several days at 1 a temperature of ordinary temperature to 200C, adding a halogencontaining ferrocene compound represented by the general formula:

R ' ~~( C H 2)~ X I
F e -- ( 11 -- b ) (wherein R1, R2 and r are the same as described abovel and xl is a halogen atom), reacting them with stirring, and then extracting and purifying.
On the other hand, the ferrocene derivatives 5 represented by the general formula (IIB) can be obtained by adding concentrated sulfuric acid to polyethylene glycol represented by the above general formula (I~-a), stirring the resulting mixture for several minutes to several days at a temperature of ordinary temperature to 200C, adding carboxyl group-containing ferrocene compounds represented by the general formula:

~~ ( C H z) w C O O H
F e ( ~ -- c ) R 2~

1 (wherein R1, R2 and w are the same as described above), reacting with stirring, and then extracting and purifying.
That is, in accordance with this method, the ferrocene derivatives represented by the general formula (IIB) are S obtained.

In producing the ferrocene derivatives represented by the general formulas (IIA) and (IIB), similar polyethers can be used in place of the polyethyene glycol of the general formula (II-a). It suffices that the extraction treatment after the reaction is carried out using alcohol, THF and the like, and the purification is carried out by chromatographic purification and the like.
The ferrocene derivatives of the present invention as represented by the general formula (I), (IIA) or (IIB) which are obtained by the methods as described above are effective as surfactants and can be used particularly as surfactants (micelle forming agents) to make hydrophobic organic substances soluble in water or an aqueous medium.

In this case, ferrocene derivatives of the general formula (IIA) wherein r is 11 to 15 and specifically ll to 13 are suitably used as surfactants. In the general formula (IIB~, ferrocene derivatives in which w is 7 to 15 are particularly suitably used as surfactants.

The surfactants of the present invention contain the ferrocene derivatives of the general formula (I), (IIA) or (IIB) as the major component, and other various additives can be added thereto, if necessary. When the surfactants 1 of the present invention are used, various hydrophobic organic substances can be made soluble in water or in an aqueous medium.
A process for production of organic thin films of the present invention will hereinafter be explained.
In the process of the present invention, the ferrocene derivatives are used as surfactants (micelle forming agents).
As the ferrocene derivatives, not only the ferrocene derivatives of the above general formula (I), (IIA) or (IIB), but also various ferrocene derivatives can be used.
Examples of such ferrocene derivatives include, as well as those represented by the general formula (I), (IIA) or (IIB), ferrocene derivatives of the general formula (IIA) wherein r is 2 to 10, and ferrocene derivatives in which a ferrocene compound (ferrocene or ferrocene having a suitable substitutent (an alkyl group, an acetyl group and the like)) is bonded to a cationic surfactant of the ammonium type (preferably the quaternary ammonium type) having a main chain having 4 to 16 carbon atoms (preferably 2~ 8 to 14). If the number of carbon atoms in the main chain is too small, no micelle is formed, and if it is too large, the resulting ferrocene derivatives are not soluble in water.
The ferrocene compound is bonded to the surfactant in various embodiments. Main embodiments are an embodiment in which the ferrocene compound is bonded to the terminal of the main chain of the surfactant, an embodiment in which the ferrocene compound is bonded to an intermediate point of 1 the main chain, directly or through an alkyl group, and an embodiment in which the ferrocene compound is incorporated in the main chain. Ferrocene derivatives of this type are represented by the general formula:

R ' R 5 M
~ ( C H 2 ) u ( C H z) ~ H F e o ~T

~wherein R4 and R5 are each a hydrogen or an alkyl group having 1 to 4 carbon atoms (but not exceeding t as described hereinafter), M and T are each a hydrogen or a substituent, X is a halogen, and t and u are integers satisfying the requirements: t ~ O, u ~ O, and 4 _ t + u s 16), the general formula:

R R S
N ~ X ~
~ t C H 2 ) j C H ( C H 2 ) 11--H
( C H 2) h H
( C H 2) D

F e ~ T

13~9622 1 (wherein R4, R5, X, M and T are the same as described above (provided that the number of carbon atoms of R4 and R5 does not exceed h as described hereinafter), and h, j and k are integers satisfying the requirements: h > O, i 2 O, k , 1 and 3 < h + j + k < 15), the general formula:

N X ~ ) ~ ~ C H 2 ) ~ H
( C H z)x H F e lo ~T

(wherein R4, R5, X, M and T are the same as described above (provided that the number of carbon atoms of R4 and R5 does not exceed x as described hereinafter), and x, y and z are integers satisfying the requirements: x > O, Y ~ , Z 2 1, and 4 s x + y + z < 16), or the general formula:

R 4 R ' ~ M
N X~ ~
( C H 2~ ~C H ~ ( C H 2) :~ H

(wherein R4, R5, M, T, x, y and z are the same as described above).

In the process of the present invention, as 13~9622 1 ferrocene derivatives to be used as the micelle forming agent, those derived by replacing a part of the alkyl chain of the general surfactant (surface active agent) with ferrocene can be used.
Representative examples of ferrocene compounds as the micelle forming agent (surfactant) are shown below.

C H
C H ~ 7 N ~-- C,, H
lo C H 3 F e C H
\ B r~
C H 7 N ' C H z C 1 2 H Z5 F e \ B r~

C I b H ~ F e -- i5 --1 In the process of the present invention, a surfactant (micelle forming agent) comprising the aforementioned ferrocene derivative, a supporting salt and a hydrophobic organic substance are introduced in an aqueous medium and thoroughly dispersed by the use of supersonic waves, a homogenizer, or a stirrer and the like to form a micelle and then, if necessary, an excess of the hydrophobic organic substance is removed and the micelle solution thus obtained is subjected to electrolytic treatment using the aforementioned electrode while allowing it to stand or somewhat stirring it. During the electric treatment, the hydrophobic organic substance may be supplementarily added to the micelle solution, or there may be provided a recycle circuit in which the micelle solution in the vicinity of the anode is withdrawn out of the system, the hydrophobic organic substance is added to the withdrawn micelle solution and thoroughly stirred, and then the resulting solution is returned to the vicinity of the cathode. Electrolytic conditions are determined appropriately depending on various circumstances. Usually the liquid temperature is 0 to 70C and preferably 20 to 30C, the voltage is 0.03 to l.S V and preferably 0.1 to 0.5 V, and the current density is not more than 10 mA/cm2 and preferably 50 to 300 ~A/cm2.
On performing this electrolytic treatment, the reaction as illustrated in Fig. 1 proceeds. Explaining in connection with the behavior of Fe ion of the ferrocene 1 derivative, Fe2 is converted into Fe3 on the anode, leading to break-down of the micelle, and particles (about 600 to 900 A) of the hydrophobic organic substance are deposited on the anode. On the other hand, on the cathode, Fe3 S oxidized on the anode is reduced to Fe2 , recovering the original micelle and, therefore, a film forming operation can be carried out repeatedly using the same solution.
By the electrolytic treatment as described above, a thin film made from particles about 600 to 900 A in size of the desired hydrophobic organic substance is formed on the anode.
The supporting salt (supporting electrolyte) to be used in the process of the present invention is added, if necessary, in order to control the electrical conductance of the aqueous medium. The amount of the supporting salt added is usual~y about 10 to 300 times and preferably about 50 to 200 times that of the above surfactant (micelle forming agent~. The type of the supporting salt is not critical as long as it is able to control the electric conductance of the aqueous medium without inhibiting the formation of the micelle and the deposition of the above hydrophobic organic substance.
More specifically, sulfuric acid salts (salts of lithium, potassium, sodium, rubidium, aluminum and the like) and acetic acid salts (salts of lithium, potassium, sodium, rubidium, magnesium, calcium, strontium, barium, aluminum ahd the like) are suitable.

~32~22 1 The electrode to be used in the process of the present invention may be a metal more noble than the oxidation potential (against +0.15 V saturated calomel electrode) of ferrocene, or an electrically conductive substance. More specifically, IT0 (mixed oxide of indium oxide and tin oxide), platinum, gold, silver, glassy carbon, an electrically conductive metal oxide, an electrically conductive organic polymer and the like can be used.
Various hydrophobic organic substances can be used in the production of organic thin films according to the process of the present invention. As well as coloring matters for optical memory and organic coloring matters, such as phthalocyanine, metal complexes thereof, and derivatives thereof, naphthalocyanine, metal complexes thereof and derivatives thereof, porphyrin and its metal complexes, and the like, electrochromic materials such as 1,1,-diheptyl-4,4'-bipyridinium dibromide, 1,l'didodecyl-4,4'-bipyridinium dibromide and the like, lightsensitive materials (photochromic materials) and light sensor materials, such as 6-nitro-1,3,3-trimethylspiro-(2'H-l'benzopyran-2,2'-indoline) (commonly called spiropyran) and the like, liquid crystal display coloring matters such as p-azoxyanisole and the like, electrically conductive organic materials and gas sensor materials, such as the 1:1 complex of 7,7,8,8-tetracyanoquinonedimethane (TCNQ) and tetrathiafulvalene ( TTF ), light curing paints such as 1 pentaerythritol diacrylate and the like, insulating materials such as stearic acid and the like, diazo-type light-sensitive materials and paints such as 1-phenylazo-2-naphthol and the like, and the like can be used. In addition, water-insoluble polymers, for example, general purpose polymers such as polycarbonate, polystyrene, polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (PP0), polyacrylonitrile (PAN) and the like, polyphenylene, polypyrrole, polyaniline, polythiophene, acetyl cellulose, polyvinyl acetate, polyvinyl butyral, and various polymers (polyvinyl pyridine and the like) and copolymers (a copolymer of methyl methacrylate and methacrylic acid) can be used.

The present invention will hereinafter be explained in more detail with reference to Examples and Comparative Examples.

0.5 g of 1-ferrocenyl-12-bromoundecane and 0.1 ml of pyridine were mixed and reacted for 120 hours in a nitrogen atmosphere while heating at 60C on a water bath.

In 4 hours from the start of the reaction, at least 95%
of the reaction was completed. This reaction mixture solidified with an advance of the reaction and finally solidified. This solid powder was well washed by adding 2S 10 ml of dimethyl ether. After washing, the powder was separated by filtration. After the powder was fully dried, 10 ml of acetone was added thereto to dissolve it therein.

1~29622 1 Upon addition of 10 ml of dimethyl ether to the solution, a precipitate was obtained. This operation was repeated three times, and after drying, 0.22 g of a purified product was obtained (yield, 38%).
The elemental analytical values of the substance were as shown below. The results of measurement of proton nuclear magnetic resonance ( H-NMR) spectrum (CDC13, TMS
standard) are as shown in Fig. 2, the results of measurement of infrared (IR) absorption spectrum (KBr tablet method, 25C) are as shown in Fig. 3, and the results of measurement of ultraviolet-visbiel (UV-VIS) absorption spectrum are as shown in Fig. 4.
Elemental Analytical Values (%) Carbon Hydrogen Nitrogen Calculated 62.67 7.28 2.81 Found 62.08 7.65 2.73 The above results confirmed that the above substance was a ferrocene derivative represented by the formula:

,~ ( C H 2 ) I I B r -F e To 100 ml of water, 99.6 mg of the ferrocene -- O

13~22 1 derivative obtained in Example ] as a surfactant (micelle forming agent) and 2.56 y of lithium sulfate as a supporting salt were added, and 10 mg of 1-phenylazo-2-naphthol was added and dispersed and dissolved by application of supersonic waves for 10 minutes. The resulting mixture was further stirred for two days and nights with a stirrer, and then the micelle solution thus obtained was subjected to centrifugal separation at 2,000 rpm for one hour. A

UV-VIS absorption spectrum of the supernatant is shown in Fig. 5 (indicated by (1)). This confirmed that 1-phenylazo-2-naphthol was made soluble in the micelle solution. The solubility was 59 M/2mM micelle forming agent solution. For comparison, a solution of only the surfactant without addition of lphenylazo-2-naphthcl was prepared, and its UV-VIS absorption spectrum is shown in Fig. 5 (indicated by (3)).

To 100 ml of water, 95.6 mg of a ferrocene derivative having the formula:

C H 3 \/ N ~-- C,, H 2 2 C H 3 F e ~

as a surfactant (micelle forming agent) and 2.56 g of lithium l sulfate as a supporting salt were added, and lO mg of 1-phenylazo-2-naphthol was added and dispersed and dissolved application of supersonic waves for 10 minutes. The resulting mixture was further stirred for two days and nights by the use of a stirrer, and the micelle solution thus obtained was subjected to centrifugal separation at 2,000 rpm for one hour. A UV-VIS absorption spectrum of the supernatnat is shown in Fig. 5 (indicated by (2)). The solùbility of the l-phenylazo-2~naphthol was 38 ~M/2mM
micelle forming agent solution.
From the above results, it can seen that when the micelle forming agent of Example 1 is used, l-phenylazo -2-naphthol is dissolved in an amount of about 1.5 times that when the micelle forming agent of Comparative Example l is used.

In lO0 ml of water, 0.02 mol of lithium sulfate as a supporting salt was dissolved, and as a micelle forming agent, 0.2 m mol of the ferrocene derivative obtained in Example 1 was added and dispersed by application of supersonic waves to form a micelle. Then, 0.2 m mol of a coloring matter (1-phenylazo-2-naphthol, which was a hydrophobic organic substance, was added and incorporated in the micelle by application of supersonic waves. After the mixture was stirred for two days and nights, an excess of the coloring matter was removed by cnetrifugal separation to obtain a micelle solution. Using the micelle solution 1 as an electrolyte, IT0 as the anode, platinum as the cathode, and a saturated calomel electrode as a reference electrode, electrolytic treatment was performed under the conditions of temperature 25C, applied voltage 0.3 V, current density 36 ~A/cm2. After 60 minutes, coloring matter thin film having primary particles having an average particle size of 700 to 1,000 A was obtained on the IT0.
A scanning type electron microscope (SEM) photograph (magnification, 35,000 using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the coloring matter thin film formed is shown in Fig. 6. A W absorption spectrum of the thin film dissolved in ethanol is shown in Fig. 7 ~Curve (3)). A UV absorption spectrum of the above coloring matter in eth~nol is shown in Fig. 7 (Curve (1)). Since the absorption peaks of Curves (3) and (1) are in agreement with each other, it can be seen that the thin film on the IT0 is made of the above coloring matter.
The deposited amount of the thin film was 18 nano mol/cm2 .

In 100 ml of water was dissolved 0.02 mol of lithium sulfate as a supporting salt, and as a micelle forming agent, 0~2 m mol of the same ferrocene derivative as used in Comparative Example 1 was added and dispersed by application of supersonic waves to form a micelle. Then, 0.2 m mol of a coloring matter (1-phenylazo-2-naphthol) which was a hydrophobic organic substance was added to the 1 micelle solution and then incorporated in the micelle by application of supersonic waves. After the resulting mixture was stirred for two days and nights, an excess of the coloring matter was removed by centrifugal separation to obtain a micelle solution. Using this micelle solution as an electrolyte, ITO as the anode, platinum as the cathode, and a saturated calomel electrode as a reference electrode, electrolytic treatment was performed under the conditions of temperature 25C, applied voltage 0.3 V, current density 35 ~A/cm2. After 60 minutes, a coloring matter thin film having primary particles having an average particle size of 700 A was obtained on the ITO.
A scanning type electron microscope (SEM) photograph (magnification, 35,000, using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the coloring matter thin film formed is shown in Fig. 8. A UV absorption spectrum of the thin film dissolved in ethanol is shown in Fig. 7 (Curve (2)). A UV absorption spectrum of the above coloring matter dissolved in ethanol is shown in Fig. 7 (Curve (1)).
Since the absorption peaks of Curves (2) and (1) are in agreement with each other, it can be seen that the thin film on the ITO is made of the above coloring matter.
The deposited amount of the thin film was 12 nano mol/cm .

0.064 g of metallic sodium was added to 6.5 g of polyethylene glycol (average molecular weight, 600), 1329$22 1 and stirred at 70C for one day and night. Then, 1.1 g of 1-ferrocenyl-12-bromoundecane was added and reacted at 110C for 10 hours. This reaction solution was extracted with a 1:1 mixture of water and n-butanol. The extract was washed with water and then was subjected to chromatographic purification by developing on a silica gel column with a mixture of benzene and ethanol (benzene :
ethanol = 5:1) as a solvent. After drying, a purified product was obtained, and the yield was 41% and the amount was 0.96 g. The elemental analytical values of the purified product were carbon 60.21%, hydrogen 9.46%, nitrogen 0.00%.
The results of measurement of the proton nuclear magnetic spectrum (lHNMR) are as shown in Fig. 9.

From the above results, it can be seen that the above purified product is a ferrocene derivative having the following structure:

~ ( C H 2 ) I , 0 ( C H ~ C H z 0 ) I 2 . S H
F e The procedure of Example 5 was repeated with the exception that as the polyethylene glycol, polyethylene glycol having an average molecular weight of 1,000 was used.

l For the purified product obtained, the yield was 31~ and the amount was 2.15 g. The results of measurement of H-NMR oE the purified product are as shown in Fig. 10.
From the above results, it can be seen that the above purified product is a ferrocene derivative having the following structure:

( C H z) , I O ( C H 2 C H ~ O ) , 7 H
F e 10 ~

The procedure of Example 5 was repeated with the exception that 6 g of polyethylene glycol (average molecular weight, 600) and 0.1 cc of concentrated sulfuric acid were added to 0.29 g of ferrocenyldodecanic acid and reacted at 80 C for 6 hours. For the purified product obtained, the yield was 62% and the amount was 0.44 g. The results of measurement of H-NMR of the purified product are as shown in Fig. 11.
From the above results, it can be seen that the above purified product is a ferrocene derivative having the following structure:

132~622 .~ ( C H z ), I C -- O -- ( C H z C H z O ), z . 5 H
F e O

To 31.5 ml of water, 1.13 mg of the ferrocene derivative obtained in Example 5 as a surfactant (micelle forming agent) was added, and lO mg of phthalocyanine was added and dispersed and dissolved by stirring for 10 minutes with supersonic waves. The mixture was further stirred for two days and nights by the use of a stirrer, and then the micelle solution thus obtained was subjected to centrifugal separation at 2,000 rpm for one hour. A visible absorption spectrum of the supernatant is shown in Fig.
12 (indicated by A). This confirmed that the phthalocyanine was made soluble in the micelle solution. The solution was 4.4 mM/4 mM micelle forming agent solution.

The procedure of Example 8 was repeated with the exception that the phthalocyanine was replaced by a phthalocyanine-iron complex. A visible absorption spectrum of the supernatant is shown in Fig. 12 (indicated by B).
This confirmed that the phthalocyanine was made soluble in the micelle solution. The solubility was 0.72 mM~4 mM
micelle forming agent solution.

1~29~2 The procedure of Example 8 was repeated with the exception that the phthalocyanine was replaced by a phthalocyaninecobalt complex. A visible absorption spectrum of the supernatant is shown in Fig. 12 (indicated by C).
This confirmed that the phthalocyanine was made soluble in the micelle solution. The solubility was 0.22 mM/4 mM
micelle forming agent solution.

The procedure of Example 8 was repeated with the exception that the phthalocyanine was replaced by a phthalocyanine-copper complex. A visible absorption spectrum of the supernatant is shown in Fig. 12 (indicated by D).

This confirmed that the phthalocyanine was made soluble in the micelle solution. The solubility was 0.11 mM/4 mM

micelle forming agent solution.

The procedure of Example 8 was repeated with the exception that the phthalocyanine was replaced by a phthalocyanine-zinc complex. A visible absorption spectrum of the supernatant is shown in Fig. 12 (indicated by E).
This confirmed that the phthalocyanine was made soluble in the micelle solution. The solubility was 0.41 mM/4 mM

micelle forming agent solution.

To 10 ml of the micelle solution prepared in Example 8 was added 0.22 g of lithium sulfate (Li2S04) to l obtain a 0.44 mM phthalocyanine/2 mM micelle forming agent/
0.2 M lithium sulfate solution. Using this solution as an electrolyte, ITO as the anode, platinum as the cathode and a saturated calomel electrode as a reference electrode, constant voltage electrolysis of applied voltage 0.5 V and current 7 ~A was performed at 25C for 2 hours. As a result, a coloring matter thin film having primary particles having an average particle size of 1,000 A was formed on the ITO.

A SEM photograph (magnification, 20,000, using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the coloring matter thin film is shown in Fig. 14.
A visible absorption spectrum of the coloring matter thin film on the ITO is shown in Fig. 13 (indicated by A). Since the visible absorption spectra shown in Fig. 13 (indicated by A) and Fig. 12 (indicated by A) were in agreement with each other, it was confirmed that the coloring matter thin film on the ITO was made of the phthalocyanine.

The procedure of Example 13 was repeated with the exception that the electrolytic time was changed to 40 minutes.
A visible absorption spectrum of the coloring matter thin film thus formed is shown in Fig. 13 (indicated by A). By comparison of A of Fig. 13 with B of Fig. 13, it can be seen that the thin film formed has a small absorption spectrum as compared with Example 13, and the film thickness can be controlled by the electrolytic time.

l EXAMPLE 15 The procedure of Example 4 was repeated with the exception that platinum was used as the anode and the current density was changed to 38 ~A/cm .
A UV absorption spectrum of the formed thin film dissolved in ethanol is shown in Fig. 15 (Curve B). A UV
absorption spectrum of the coloring matter (l-phenylazo-2-naphthol) dissolved in ethanol is shown in Fig. lS (Curve C), and a UV absorption spectrum of the thin film formed in Example 4, as dissolved in ethanol is shown in Fig. 15 (Curve D).

The procedure of Example 4 was repeated with the exception that glassy carbon was used as the anode and the current density was changed to 40 ~Atcm2.
An ultraviolet absorption spectrum of the formed thin film dissolved in ethanol is shown in Fig. 15 (Curve A).

The procedure of Example 4 was repeated with the exception that as the micelle forming agent, a compound having the formula:

C H
C H 3 \/ N ~--C H 2 C 1 2 H zs F e 1 was used, and the current density was changed to 30 ~A/cm2.
A SEM photograph (magnification, 35,000, using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the thin film formed is shown in Fig. 16.

A thin film wzs formed on ITO in the same manner as in Example 4 except that as the coloring matter, 1,1'-didodecyl-4,4'-bipyridinium dibromide was used, and the current density was changed to 58 ~A/cm2.
A UV absorption spectrum of the formed thin film dissolved in methanol is shown in Fig. 17 (Curve B). A UV
absorption spectrum of the above coloring matter dissolved in methanol (concentration, 0.042 m mol/l) is shown in Fig.

17 (Curve A). Since the absorption peaks of Curves A and B are in agr~ement with each other, it can be seen that the thln film on the ITO is made of the above coloring matter.

A thin film was formed in the same manner as in Example 18 except that glassy carbon was used as the anode, and the current density was changed to 60 ~A/cm2. A SEM
photograph (magnification, 1,000, using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the thin film is shown in Fig. 18.

0.02 mol (concentration, 0.2 M) of lithium sulfate as a supporting salt was dissolved in 100 cc of secondary 1 distilled water, and 0.3 m mol (concentration, 3 mM) of the same surfactant (micelle forming agent) comprising a ferrocene derivative, as used in Comparative Example 1 was added thereto and dispersed by stirring to form a micelle.
0.82 nano mol (concentration, 8.2 nM) of a water insoluble copolymer of methyl methacrylate and methacrylic acid (molecular weight, 1 x 10 ) was added to the micelle solution and incorporated in the micelle by application of supersonic waves and stirring for one day and night.
Using ITO as the anode, platinum as the cathode, and a saturated calomel electrode as a reference electrode, electrolytic treatment was performed under the conditions of temperature 25C applied voltage 0.3 V and current density 10 ~A/cm to obtain a polymer film on the ITO. This ITO
was washed with water and then, upon application of cyclic voltammetry in an aqueous solution containing only a supporting salt (lithium sulfate, concentration 0.2 M), an oxidation reduction wave due to the micelle forming agent incorporated in the film was observed. However, by sweeping continuously 20 times 0 to + 0.5 V (against the saturated calomel electrode) at a sweeping speed of 20 mV/sec in the above aqueous solution, the height of the wave was decreased to 10~ of the initial value. That is, 90% of the micelle forming agent incorporated in the film could be removed by this post-treatment.

A SEM photograph (magnification, 20,000, using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the polymer 132~522 1 film formed is shown in Fig. 19 (a), (b). Fig. l9(a) is a photograph of the film before post-treatment, and Fig.
l9(b) is a photograph of the film after post-treatment (film thickness- 1,800 A amount of electricity: 0.1 Coulomb/cm2;
film area: 0.91 cm2).
A Fourier transformation infrared (FT-IR) absorption spectrum of the polymer film is shown in Fig.
20 (film thickness: 5,600 A; amount of electricity: 0.31 Coulomb /cm2; film area: 1.64 cm2), and an IR absorption spectrum with a KBr pellet of the polymer used as the material is shown in Fig. 21. Since the absorption peaks of Figs. 20 and 21 are in agreement with each other, it can be seen that the film on the ITO is made of the above polymer.
A relation between the film thickness and the amount of electricity having passed per unit area of the ITO is shown in Fig. 22. Since, as can be seen from Fig.
22, there is a straight line relation (parallel relation) between the film thickness and the amount of electricity having passed, it can be seen that the film thickness can also be controlled at will by controlling the amount of electricity.

The procedure of Example 20 was repeated with the exception that as the polymer, poly (4-vinylpyridine)(molecular weight, 50,000, concentration, 7.9 ~M produced by Polyscience Inc.) was used, and the 1 concentration of the micelle forming agent was changed to 2.0 mM.
A UV absorption spectrum of the formed film (film thickness: 400 A; amount of electricity: 0.019 Coulomb/cm2;
film area: 1.05 cm2) dissolved in 5 ml of ethanol is shown in Fig. 23 (Curve a). A SEM photograph (magnification, 20,000, using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the formed thin film is shown in Fig. 24. A UV absorption spectrum of the above polymer dissolved in ethanol (polymer concentration, 0.25 ~M) is shown in Fig. 23 (Curve b).
Since the absorption peaks and wave forms of Curves a and b are in agreement with each other, it can be seen that the film on the ITO is made of the above polymer. Curve c of Fig. 23 is a W absorption spectrum of a washing liquid resulting from washing of ITO with 5 ml of ethanol, said ITO having been obtained by electrolysis of a micelle solution not containing a polymer.
A relation between the film thickness and the amount of electricity having passed through per unit area of the ITO is shown in Fig. 22. Since, as can be seen from Fig. 22, there is a straight line relation (parallel relation) between the film thickness and the amount of electricity having passed, it can be seen that the film thickness can also be controlled at will by controlling 2S the amount of electricity.

To 31.5 ml of water was added 1.13 mg of the 132~622 1 ferrocene derivative obtained in Example 7, as a surfactant (micelle forming agent), and 10 mg of phthalocyanine was added and dispersed and dissolved by stirring for 10 minutes with supersonic waves. The mixture was further stirred for two days and nights by the use of a stirrer, and micelle solution thus obtained was subjected to centrifugal separation at 2,000 rpm for one hour. A visible absorption spectrum of the supernatant confirmed that the phthalocyanine was made soluble in the micelle solution. The solubility was 8.9 mM/4 mM micelle forming agent solution.

INDUSTRIAL APPLICABILITY
The f~rrocene derivatives of the present invention are novel compounds and can be used in various applications, for example, as surfactants, catalysts, auxiliary fuels, depressors, dispersants and the like. The novel ferrocene derivatives, when used as surfactants, form micelles in an aqueous solution system and, therefore, coloring matters such as phthalocyanine, having a wide variety of applications and water-insoluble polymers can be made soluble.
If the process of the present invention is carried out using the novel ferrocene derivatives or other ferrocene derivatives as surfactants (micelle forming agents), an organic thin film greatly small in thickness can be formed by aqueous solution electrolysis and utilizing the gathering or scattering of micelles. This process for production of an organic thin film can be utilized, as well as coating and coloring of various products, in production of electronic 132~22 1 materials such as photoconductor materials, solar batteries, secondary batteries, electric power apparatus materials, display device materials and the like, and further in production of light-sensitive materials, insulating materials, light memory materials, light sensor materials, gas sensor materials and the like.

In addition to the subject matter described in the principal disclosure, this invention includes the following subject matter.

- 36 ~

132~22 DESCRIPTION
FERROCENE DERIVATIVES, SURFACTANTS CONTAINING THEM
AND PROCESS FOR PRODUCING ORGANIC THIN FILMS
Technical Field The present invention relates to ferrocene derivatives, surfactants containing them and a process for producing organic thin films, and more particularly to novel ferrocene derivatives containing a pol~oxyethylene chain, surfactants containing said ferrocene derivatives and capable of making coloring matter, e.g. phthalocyanine, soluble, and a process for producing a thin film of a hydrophobic organic substance using these surfactants.
Background Art In general, coloring matter such as phthalocyanine or its derivatives are insoluble in water, and although they are soluble in organic solvents such as dimethylformamide (DMF~
or tetrahydrofuran (THF), their soluble amounts are small and the solubility is only several milligrams (mg).
Surfactants to dissolve ohthalocyanine and the like in water have heretofore been investigated, but no satisfactory surfactant has been developed. It is reported that functional group-substituted phthalocyanine derivatives can be dissolved in water to some extent by using sulfone-based surfactants. However, the solubility is not always sufficiently high, and furthermore they cannot dissolve at all unsubstituted phthalocyanines.
In connection with water-insoluble polymers, surfactants 3 ~

1~9622 to make them soluble in water have been investigated in the same manner as above. In fact, however, no satisfactory results have been obtained.
The present inventors have made extensive investigations to develop surfactants to make coloring matters such as phthalocyanine or its derivatives, or water-insoluble polymers and the like soluble in water.
In the course of the study, it has been found that ferrocene derivatives are promising as surfactants having the aforementioned performance. As a result of further investigations based on the above findings, the present inventors have discovered that new ferrocene derivatives obtained by introducing a specified substituent containing a polyoxyethylene chain in ferrocene or its derivatives can achieve the object. At the same time, they have discovered that a water-insoluble (hydrophobic) organic thin film can be efficiently produced by applying an electrochemical technique using the above new ferrocene derivatives.
The present invention has been completed after the study as described above.
Disclosure of Invention That is, the present invention provides ferrocene derivatives represented by the general formula (A):

t C H ~ O -t C H , ~ H ~ O ). H
F.e t ~ ) ( R ' ) .--X

.. . . . . .

132~S22 (wherein Rl and R are independently hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, m is an integer of 1 to 4, n is an integer of 1 to 5, r is an integer of 11 to 18, and s is a real number of 2.0 to 70.0), or the general formula ( B!:

( C H 2 ~Y C - 0 -( C N 2 C H z O ), H
F e 0 ( B

( R ~) n~

(wherein w is an integer of 2 to 20, and Rl, R2, m, n and s are the same as above), and also provides, surfactants containing ferrocene derivatives represented by the general formula (A) or (B ).
Moreover, the present invention provides a process for production of an organic thin film which comprises making a hydrophobic organic substance soluble in an aqueous medium with surfactants containing ferrocene derivatives represented by the general formula (A) or (B ), or ferrocene derivatives represented by the general formula (A ):

~~ ( C H ~ ~ ~ Q--( C H 2 C H 2 0 ~s H
F e ~ ( A

( R 2)~
(wherein t is an integer of 2 to 10, and Rl, R2, m, n and s .

132~622 are the same as above), and electrolyzing the resulting micelle solution to form a thin film of the above hydrophobic organic substance on an electrode.
Brief Description of Drawings Fig. 1 is an explanation view schematically illustrating the principle of the process of the present invention, wherein 1 indicates a ferrocene derivative; 2, a hydrophobic organic substance 3, a micelle; 4, an oxidized ferrocene derivative; 5, an anode; 6, a cathode; Fc, ferrocene and e , an electron.
Fi. 9 is a lH-MMR spectrum of the ferrocene derivative obtained in Example 5, Fig. lOis a H-MMR spectrum of the ferrocene derivative obtained in Example 6, Fig.25 is a H-MMR spectrum of the ferrocene derivative obtained in Example 7, Fig. æ is a lH-MMR spectrum of the ferrocene derivative obtained in Example 24 Fig. D is a H-NMR spectrum of the ferroc~ne derivative obtained in Example ~, Fig.~ is a lH-NMR spectrum of the ferrocene derivative obtained in Example 25, and Fig. 23 is a lH-NMR spectrum of the ferrocene derivative obtained in Example a~
Fig~ 12 is a visible absorption spectrum of the supernatants obtained in Examples 8 to 12, and Fig.13 is a visible absorption spectrum of coloring matter thin films on I~O as obtained in Examples 13 and 14.
Fig. 30 indicates a visible absorption spectrum of the supernatant obtained in Example 27 and a visible absorption spectrum of the coloring matter thin film on ITO, Fig.~l `X

--- 132~622 indicates a visible absorption spectrum of the supernatant obtained in Example 28 and a visible absorption spectrum of the coloring matter thin film on ITO, Fig. 32 indicates a visible absorption spectrum of the supernatant obtained in Example 25 and a visible absorption spectrum of the coloring matter thin film on ITO, Fig. 33 indicates a visible absorption spectrum of the supernatant obtained in Example 30 and a visible absorption spectrum of the coloring matter thin film on ITO, Fig. 34 indicates a visible absorption spectrum of the supernatant obtained in Example 31 and a visible absorption spectrum of the coloring matter thin film on ITO, Fig. 35 indicates a visible absorption spectrum of the supernatant obtained in Example 32 and a visible absorption spectrum of the coloring matter thin film on ITO, and Fig. 36 indicates a visible absorption spectrum of the supernatant obtained in Example 33 and a visible absorption spectrum of the coloring matter thin film on ITO.
Fig. 14 is an SEM photograph illustrating the surface structure of the thin film formed in Example 25, Fig. 37 is an SEM photograph illustrating the surface structure of the thin film formed in Example 27, Fig. 38 is an SEM photograph illustrating the surface structure of the thin film formed in Example 28, and Fig. 39 is an SEM photograph illustrating the surface structure of the thin film formed in Example 29.

X

l Figures A2 to A9 indicate visible absorption spectrums obtained from Examples A; Figures Bl to B6 indicate visible absorption spectrums obtained from Examples B;-and Figures Cl, C2 and C4 indicate visible absorption spectrums obtained from Examples C.

Best Mode for Carrying Out The Invention The ferrocene derivatives of the present invention are represented by the general formula (A~ or (~) . In the iX

~329622 general formula (A), Rl and R2 are independently hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, m is an integer of 1 to 4, n is an integer of 1 to 5, r is an integer of 11 to 18, and s is a real number of 2.0 to 70Ø Since r is, as described above, an integer of 11 to 18, an alkylene group (polymethylene group) having 11 to 18 carbon atoms, e.g. an undecamethylene group, a dodecamethylene group or a tridecamethylene group is present between a ring-constituting carbon atom and an ether oxygen atom nearest said carbon atom. s means not only an integer between 2.0 and 70.0 but also a real number including them, and indicates a mean value of a repeating number of an oxyethylene group ~-CH2CH20-~ constituting a ferrocene derivative.
On the other hand, since w of the general formula (B ) indicates an integer of 2 to 20, an alkylene group (polymethylene group) having 2 to 20 carbon atoms, e.g. an ethylene group or a propylene group is present between a ring-constituting carbon atom and an oxycarbonyl group. Rl, R2, m, n and s are the same as described abo~e.
These ferrocene derivatives represented by the general formula (A) or ( ~) can be prepared by various methods. For example, the ferrocene derivatives represented by the general formula ~ ) are prepared as follows. That is, an alkali metal (metallic sodium, metallic potassium, etc.) is added to polyethylene glycol represented by the ~eneral formula:
HO--~CH2CH2 ~ ...~. (III) (wherein s is the same as described above), s.irred at ordinary temperature to 200C for several min~tes to several days, and then a halogen-containing ferrocene compound represented by the general formula:

(R ')~ ~
( C H 2 ) r X
F e -- ( IV ) ( R Z) n~

(wherein X is a halogen atom, and Rl, R2, m, ~ and r are the same as described above) is added and reacted while stirring.
Thereafter, upon extraction and purification, a ferrocene derivative represented by the general formula (A) is obtained. A halogen-containing ferrocene com~ound of the general formula (IV) can be prepared, for exa~ple, by convertingW -halogenocarboxylic acid represen~ed by the general formula: HOOC(CH2)r lX
(wherein r and X are the same as described ab~ve) into acid halide (acylated product) represented by the general formula:
X OC(CH2)r lX (wherein Xl is a halogen atom resulting from a halogenating atent, and r and X are the same as described above) by the use of a suitable halogenating agent (thionyl chloride, etc.), reacting the acid halide with ferrocene or its derivative represented by the general for~ula:

( R ' ) .,~

F o - ~ V
( P~ ~ ) .~

- 132~622 (wherein Rl, R2, m and n are the same as described above) to obtain a ferrocenylketone derivative represented by the general formula:

( R ' ) ~
~ 0~ C ( C H z ), , X

,.~
( R Z) (wherein Rl, R , m, n and r are the same as described above), and further reducing the ferrocenylketone derivative.
On the other hand, a ferrocene derivative represented by the general formula (B ) can be obtained by adding concentrated sulfuric acid to polyethylene glycol represented by the general formula (III), stirring at ordinary temperature to 200C for several minutes, then adding a carboxyl group-containing ferrocene compound represented by the general formula:

( R ')~
~~( C H 2 )~ C O O H
F e ( Yll ( R ~) ,.~

(wherein Rl, R2, m, n and w are the same as described above) and reacting while stirring, and then extracting and purifying. A carboxyl group-containing ferrocene compound of the general fo,rmula (VII) can be prepared, for ex~mple, as 132~S22 follows: that is, the carboxyl group-containing ferrocene compound represented by the general formula (VII) can be prepared by reacting alkoxycarbonylic acid halide represented by the general formula: X OC(CH2)w 1COOR (wherein X is a halogen atom, R is an alkyl group, and w is the same as described above) with ferrocene or its derivative represented by the general formula (V) to obtain ferrocenoylcarboxylic acid ester represented by the general formula:

O
( R ' ) ~
~C ( C H 2)~-1 C O O R
F e ( R 2) ~

(wherein Rl, R2, m, n and w are the same as described above), then hydrolyzing to obtain the corresponding carboxylic acid, and then reducing or alternatively reducing and then hydrolyzing.
The ferrocene derivatives of the present invention as represented by the general formula (A) or ( B~ can be produced as described above. In production of these ferrocene derivatives, the polyethylene glycol of the general formula (III) can be replaced by similar polyethers.
Extraction treatment after the reaction can be carried out using alcohol, THF and the like, and purification can be carried out by chromato purification and so forth.
~ he ferrocene derivatives represented by the general -~ - 132~622 formula (A) or (B ) as obtained by the method as described above are effective as surfactants and can be used particularly as surfactants (micelle forming agents) to make hydrophobic organic substances soluble in water or an aqueous medium.
The surfactants of the present invention contain the ferrocene derivatives of the general formula (A) or (8 ) as the major component, and other various additives can be added, if necesary. Use of the surfactants of the present invention permits to make various hydrophobic organic substances soluble in water or an aqueous medium. There are various hydrophobic organic substances. Examples are coloring matters and organic coloring matters for light memory, e.g. phthalocyanine, phthalocyanine derivatives, metal complexes of phthalocyanine, metal complexes of phthalocyanine derivatives, naphthalocyanine, naphthalocyanine derivatives, metal complexes of naphthalocyanine, metal complexes of naphthalocyanine derivatives, porphyrin, porphyrin derivatives (tetraphenylporphyrin and the like), metal complexes of porphyrin, and metal complexes of porphyrin derivatives;
electrochromic materials, e.g. l,l'-diheptyl-4,4'-bipyridinium dibromide, and l,l'-didodecyl-4,4'-bipyridinium dibromide; light-sensitive materials (photochromic materials) and light sensor materials, e.g. 6-nitro-1,3,3-trimethylspiro-(2'H-l'-benzopyran-2,2'-indoline) (commonly called spiropyran) liquid crystal display coloring matters, 132~S22 e.g. p-azoxyanisole; organic electrically conductive materials and gas sensor materials, e.g. a 1:1 complex of 7,7,8,8-tetracyanoquinonedimethane (TCNQ) and tetrathiafulvalene (TTF); light-curable paints, e.g.
pentaerythritol diacrylate; insulating materials, e.g.
stearic acid, and diazo type light-sensitive materials and paints, e.g. 1-pheny~azo-2-naphthol. Other examples include water-insoluble polymers, for example, general purpose polymers such as polycarbonate, polystyrene, polyethylene, polypropylene, polyamide, polyphenylene sulfide (PPS), polyphenylene oxide (PPO), and polyacrylonitrile (PAN), or polyphenylene, polypyrrole, polyaniline, polythiophene, acetyl cellulose, polyvinyl acetate, polyvinyl butyral and other various polymers (polyvinylpyridine and the like) or copolvmers (a copolymer of methyl methacrylate and methacrylic acid, and the like).
In use of the ferrocene derivatives of the present invention as surfactants, there are various embodimetns.
Particularly in production of the organic thin film of the present invention, they are effectively used as micelle forming agents. In the process of the present invention, a surfactant (micelle forming agent) comprising a ferrocene derivative represented by the general formula (~) or (B ), or a ferrocene derivative represented by the general formula (A ), a supporting salt, and a hydrophobic organic substance are placed in an aqueous medium and thoroughly dispersed by ~ha use of supersonic waves, a homogenizer, or a stirrer, for .~

132~622 example, to form a micelle. Thereafter, if necessary, an excessive hydrophobic organic substance is removed, and the micelle solution thus obtained is subjected to electrolytic treatment using the aforementioned electrode while allowing to stand or somewhat stirring. During the electrolytic treatment, the hydrophobic organic substance may be supplementarily added to the micelle solution, or there may be provided a recycle circuit in which the micelle solution in the vicinity of the anode is withdrawn out of the system, the hydrophobic organic substance is added to the withdrawn micelle solution and throughly stirred, and then the resulting solution is returned to the vicinity of the cathode. Electrolytic conditions are determined appropriately depending on various circumstances. Usually, the liguid temperature is O to 70C and preferably 20 to 30C, the voltage is 0.03 to 1.5 V and preferably 0.1 to 0.5 V, and the current density is not more than 10 mA/cm and preferably 50 to 300~ A/cm .
On performing this electrolytic treatment, the reaction proceeds as illustrated in Fig. 1. Explaining in connection with the behavior of Fe ion in the ferrocene derivative, Fe2 is converted into Fe on an anode 5, leading to the break-down of the micelle, and particles (about 600 to 900 ~) of a hydrophobic organic substance are deposited on the anode. On the other hand, on a cathode 6, Fe oxided on the anode 5 is reduced to Fe2 , recovering the original micelle 3 and, therefore, a film forming operation can be carried out ~9 /

132~622 repeatedly using the same solution.
Electrolytic treatment as described above forms a thin film comprised of about 600 to 900 ~ particles of the desired hydrophobic organic substance on the anode.
The supporting salt (supporting electrolyte) to be used in the process of the present invention is added, if necessary, in order to control the electrical conductance of the aqueous medium. The amount of the supporting salt added is usually about 10 to 300 times, preferably about 50 to 200 times that of the above surfactant (micelle forming agent).
The type of the supporting salt is not critical as long as capable to control the electric conductance of the aqueous medium without inhibiting the formation of the micelle and the deposition of the above hydrophobic organic substance.
More specifically, sulfuric acid salts (salts such as lithium, potassium, sodium, rubidium or aluminum) and acetic acid salts (salts such as lithium, potassium sodium, rubidium, beryllium, magnesium, potassium, strontium, barium or aluminum), which are generally widely used as supporting salts, are suitable.
The electrode to be used in the process of the present invention is sufficient to be a metal more noble than the oxidation potential lagainst +0.15 V saturated calomel electrode) of ferrocene, or an electrically conductive substance. ~ore specifically, ITO (mixed oxide of indium oxide and tin oxide), platinum, gold, silver galassy carbon, electrically conductive metal oxides, electrically conductive organic polymers, and the like can be used.
Example The present invention is described in greater detail with reference to examples.
Preparation Example 1 (1) ll-undecanic acid chloride prepared from SO.O g of 11-bromoundecanic acid and 90.0 g of thionyl chloride, 37.6 g of anhydrous aluminum chloride, and 35.0 g of ferrocene were reacted at 5C for 3 hours in a methylene chloride solvent.
After the completion of the reaction, the reaction mixture was treated with diluted hydrochloric acid and then purified with a silica gel column to obtain 56.9 g of 10-bromo undecanyl ferrocenyl ketone represented by the following formula:

--C ---( C H z), O B r F e (2) In the presence of amalgam prepared from 65.4 g of zinc and 27.2 g of mercuric chloride, 56.9 g of 10-bromodecanyl ferrocenyl ketone prepared in (1) above was refluxed for 6 hours in a mixed solvent of concentrated hydrochloric acid and ethanol to perform a reduction reaction.
After the completion of the reaction, the reaction mixture was extracted with ethyl acetate and purified on a silica gel column to obtain 42.1 g of l-ferrocenyl-ll--- 1329~22 bromoundecane represented by the following formula:
-- ( C H 2) ', B r F e Example 5 0.064 g of metallic sodium was added to 6.5 g of polyethylene glycol (average molecular weight, 600) and stirred at 70C for one day and night. Then, 1.1 g of 1-ferrocenyl-ll-bromoundecane (obtained in Preparation Example 1) was added thereto and reacted at 110C for 10 hours. This reaction mixture was extracted with a mixture of equal amounts of water and n-butanol. The extract was washed with water and then was subjected to chromatographic purification by developing on a silica gel column using a mixture of ~enzene and ethanol (benzene: ethanol=5:1) as a solvent. For the purified product obtained after drying, the yield was 41%
and the amount was 0.96 g. The elemental analytical values were: carbon, 60.21% hydrogen, 9.46%; nitrogen, 0.00%. The results of measurement of proton nuclear magnetic resonance spectrum (lH-MMR) were as shown in Fig. 9.
From the above results, it can be seen that the above purified product was a ferrocene derivative having the following structure.

--( C H 2~ ~. O ~ C H 2 C H 20)12. ~ H
F e 13296~2 Example 6 The procedure of Example 5 was repeated with the exception that polyethylene glycol having an average molecular weight of 1,000 was used as the polyethylene glycol. For the purified product obtained, the yield was 31%
and the amount was 2.15 g. The results of H-NMR measurement were as shown in Fig. lO.
From the above results, it can be seen that the above purified product was a ferrocene derivative having the following structure:

- ( C H z) , , O ( C H z C H z O ) 1 7 H
F e C~

Preparation Example 2 (1) In the presence of 9.6 g of anhydrous aluminum chloride, 13.5 g of ferrocene and 19.9 g of ll-ethoxycarbonylundecanic acid chloride (known as described in J. Amer. Chem. Soc., 69, 2350 (1947)) were reacted at room temperature for 2 hours in a methylene chloride solvent.
After the completion of the reaction, the reaction mixture was treated ~ith diluted hydrochlorice acid and then purified with a silica gel column to obtain 13.7 g of ethyl ferrocenoylundecanate represented by the following formulas O O
~ e_( c H ~,~e O c ~ H 5 F e (2) 12.4 g of ethyl ferrocenoylundecanate prepared in (1) above and 2.9 g of potassium hydroxide were refluxed for 2 hours in an ethanol solvent and then was subjected to acid treatment to obtain 11.3 g of ferrocenoylundecanic acid represented by the following formula;
Ol O
--C --( C H z ~, O - C O H
F e ~ . .

(3) In the presence of zinc amalgam prepared from 6.5 g of zinc and 2.7 g of mercuric chloride, 6.0 9 of ferrocenoylundecanic acid prepared in (2) above was reacted at 80C for 3 hours in a mixed solvent of.concentrated hydrochloric acid and ethanol.
After the completion of the reaction, the reaction mixture was extracted with ethyl acetate and purified with a silica gel column to obtain 4.8 g of ferrocenyldodecanic acid repre~sented by the following formula:

o ( C H ~ ) r~ C O H
F e Example 7 The procedure of Example 5 was repeated with the exception that 6 g of polyethylene glycol (average molecular ' ~` 1329622 weight, 600) and 0.1 cc of concentrated sulfuric acid were added to 0.29 g of ferrocenyldodecanic acid (obtained in Preparation Example 2) and reacted at 80C for 6 hours. For the purified product obtained, the yield was 62% and the amount was 0.44 g. The results of H-MMR measurement were as shown in Fig. 25.
From the above results, it can be seen that the above purified product was a ferrocene derivative having the following structure:

( C H z ), I C -- O -- ( C H 2 C H 2 0 ) I 2 . ~ H
Fe O

Preparation Example 3 (1) In the same manner as in Preparation Example 2 (1) except that in place of ll-ethoxycarbonylundecanic acid chloride shown in Preparation Example 2 (1), 35.0 g of 10-ethoxycarbonyldecanic acid chloride was used, and 17.7 g of anhydrous aluminum chloride was used and 24.7 g of ferrocene was reactedS 23.0 g of ethyl ferrocenoyldecanate represented by the formula shown below was obtained.

O O
li 11 C ( C H 2) ~ C O C 2 H, F e X

132~62~
(2) In the same manner as in Preparation Example 2 (2) except that in place of ethyl ferrocenoylundecanate shown in Preparation Example 2 (2~, 5.0 g of ethyl ferrocenoyldecanate (obtained in (1) above) was used, and 1.2 g of potassium hydroxide was used; 4.7 g of ferrocenoyldecanic acid represented by the formula shown below was obtained.
O O
--C -( C H 2 ) 9 C O H
F e (3) In the same manner as in Preparation Example 2 (3) except that in place of ferrocenoylundecanic acid shown in Preparation Example 2 (3), 4.7 g of ferrocenoyldecanic acid (obtained in (2) above) was used, and 6.6 g of zinc and 2.7 g of mercuric chloride were used; 3.4 g of ferrocenylundecanic acid represented by the formula shown below was obtained.

( C H ~ ) r~C O H
F e Example 23 The procedure of Example 5 was repeated with the exception that 39~14 g of polyethylene glycol (average ~Z .

132~622 molecular weight, 600) and 0.1 cc of concentrated sulfuric acid were added to 3.02 g of ferrocenylundecanic acid obtained in Preparation Example 3, and reacted at 80C for 6 hours. For the purified product obtained, the yield was 51.5~ and the amount was 4.00 g. The results of lH-NMR
measurement were as shown in Fig. 26. Elemental analytical values were as follows:
Carbon Hydrogen Nitrogen t%) 61.03 8.68 0.00 59.82 8.71 0.00 (Calculated) From the above results, it can be seen that the above purified product was a ferrocene derivative having the following structure.

( C H 2 ) I o C - O -- t C H 2 C H 2 0 ) I ~ . 2 H
Fe O

Preparation Example 4 (1~ In the same manner as in Preparation Example 2 (1) except that in place of ll-ethoxycarbonylundecanic acid chloride shown in Preparation Example 2 (1), 19.3 g of 9-ethoxycarbsnylnonanic acid chloride was used, and 10.4 g of anhydrous aluminum chloride was used and reacted with 14.0 of ferrocene; 23.4 9 of ethyl ferrocenoylnonanate represented by the formula shown below was obtained.

o o --C--( C H 2)~C O C 2 H 5 F e (2) In the same manner as in Preparation Example 2 (2) except that in place of ethyl ferrocenoylundecanate shown in Preparation E~ample 2 (2), 20.5 of ethyl ferrocenoylnonanate (obtained in (1) above) was used, and 5.1 g of potassium hydroxide was used 19.7 g of ferrocenoylnonanic acid represented by the formula shown below was obtained.

O O

~ C--( C H 2 ) 8 C O H

(3) In the same manner as in Preparation Example 2 (3) except that in place of ferrocenoylundecanic acid shown in Preparation Example 2 (3), 11.1 g of ferronoylnonanic acid (obtained in (2) above) was used, and 13.1 g of zinc and 5.5 g of mercuric chloride were used; 8.3 g of ferrocenyldecanic acid represented by the farmula shown belo~ was obtained.

( C H 2 ) ~ --C O H

132~622 Example 24 The procedure of Example 5 was repeated with the exception that 82.7 g of polyethylene glycol (average molecular weight, 600) and 0.1 cc of concentrated sulfuric acid were added to 8.19 g of ferrocenyldecanic acid obtained in Preparation Example 4 and reacted at 80C for 6 hours.
For the purified product obtained, the yield was 49.2~ and the amount was 10.60 g. The results of H-NMR measurement were as shown in Fig. ~. Elemental analytical values were as follows:
Carbon Hydrogen Nitrogen (~
60.02 8.63 0.00 59.43 8.63 0.00 (Calculated) From the above results, it can be seen that the above purified product was a ferrocene derivative having the following structure:

( C H 2 ~ ~ C -- O -- ( C H 2 C H 2 0 ~ . 2 H
Fe o Preparation Example 5 (1) In the same manner as in Preparation Example 2 (1) except that in place of ll-ethoxycarbonylundecanic acid chloride shown in Preparation Example 2 (1), 29.0 g of 5-ethoxycarbonyl~aleric acid chloride was used, and 32.4 g of anhydrous aluminum chloride was used and reacted with 45.2 _ 59 _ of ferrocene; 44.1 g of ethyl ferrocenoylvalerate represented by the formula shown below was obtained.
O O
Il 11 C--( C H z ) ~ C O C z H s F e (2) In the same manner as in Preparation Example 2;(2) except that in place of ferrocenoylundecanic acid shown in Preparation Example 2 (2), 44.1 g of ethyl ferrocenoylvalerate (obtained in (1) above), and 13.3 g of potassium hydroxide was used; 36.0 g of fe~rocenoylvaleric acid represented by the formula shown below was obtained.
O
C ( C H z ) ~ - C O H
F e (3) In the same manner as in Preparation Example 2 (3) except that in place of ferrocenoylundecanic acid shown in Preparation Example 2 (3), 9.4 g of ferrocenoylvaleric acid (obtained in (2) above) was ~sed, and 13.1 g of zinc and 5.5 g of mercuric chloride were used; 6.9 g of ferrocenylhexanic acid represented by the formula shown below was obtained.

( C H 2 ) 5 C O H
F e 6c>

1~29622 Example 25 The procedure of Example 5 was repeated with the exception that 184.80 g of polyethylene glycol (average molecular weight, 1,000) and 0.1 cc of concentrated sulfuric acid were added to 6.90 g of ferrocenylhexanic acid obtained in Preparation Example 5 and reacted at 80C for 6 hours.
For the purified product obtained, the yield was 39.5~ and the amount was 11.68 g. The results of H-MMR measurement were as shown in Fig. ~. Elemental analytical values were as follows:
Carbon Hydrogen Nitrogen (~) _ 56.25 9.38 0.00 56.85 9.40 0.00 ~Calculated) From the above results, it can be seen that the above purified product was a ferrocene derivative having the following structure:

( C H z ) s C -- O -- ( C H z C H 2 0 ) 2 Z . ~ H
F e O

Preparation Example 6 Il) In the same manner as in Preparation Example 2 (lj except that 16.0 g of octamethylferrocene (known as described in Chem. Ztg., 19?6, 100 (3), 143 (Ger)~ was used in place of ferrocene shown in Preparation Example 2 (1), 13.3 g of 9-ethoxycarbonylnonanic acid chloride was used in place of 11-ethoxycarbonylundecanic acid chloride, and further 7.2 g of anhydrous aluminum chloride was used and reacted with 16.1 g of ferrocene 6.4 g of ethyI octamethylferrocenoylnonanate represented by the formula shown below was obtained.
O O

~ C ( C H 2 ) 8 C O C z H s (2) In the same manner as in Preparation Example 2 (2) except that in place of ethyl ferrocenoylundecanate shown in Preparation Example 2 (2), 6.4 g of ethyl octamethylferrocenoylnonanate (obtained in (1) above) was used, and 1.1 g of potassium hydroxide was used 6.0 g of octamethylferrocenoylnonanic acid represented by the formula shown below was obtained.
O O
~ C --( C H z ) ~ C O H

(3) In the same manner as in Preparation Example 2 (3) except that in place of ferrocenoylundecanic acid shown in Preparation Example 2 (3), 6.0 g of octamethylferrocenoylnonanic acid (obtained in (2) above) was used, and 8.1 g of zinc and 3.3 g of mercuric chloride were used; 2.1 g of octamethylferrocenyldecanic acid represented by the formula shown below was obtained.
O
~> ( C H z ) q C O H
,~

Example 26 The procedure of Example 5 was repeated with the exception that 86.64 g of polyethylene glycol (average molecular weight, 2,000) and 0.1 cc of concentrated sulfuric acid were added to 2.03 g of octamethylferroçenyldecanic acid obtained in Preparation Example 6 and reacted at 80C for 6 hours. For the purified product obtained, the yield was 15.2~ and the amount was 1.61 g. The results of lH-NMR
measurement were as shown in Fig. 29- Elemental analytical values were as follows:
Carbon Hydro~en Nitrogen (~) 58.51 9.23 0.00 57.84 9.15 0.00 (Calculated) From the above results, it can be seen that the above purified product was a ferrocene derivative having the following structure.

C H , ) . ICI -- O --( C H , C H . O ) ~ . H

13~9622 Example 8 1.13 g of the ferrocene derivative obtained in Example5 was added to 31.5 ml of water as a surfactant (micelle forming agent), and 10 mg of phthalocyanine was added and dispersed or dissolved by stirring for 10 minutes by the use of supersonic waves. The resulting mixture was stirred for two days and nights with a stirrer, and the micelle solution thus obtained was subjected to centrifugal separation at 2,000 rpm for one hour. A visible absorption spectrum of the supernatant is shown in Fig. 12 (Curve A). This confirmed that phthalocyanine was soluble in the micelle solution. The solubility was 4.4 mM/4 mM micelle forming agent solution.
Example 9 The procedure of Example 8 was repeated with the exception that phthalocyanine iron complex was used in place of phthalocyanine. A visible absorption spectrum of the supernatant is shown in Fig. 12(Curve B). This con~inmed that the phthalocyanine was soluble in the micelle solution.
The solubility was 0.72 mM/4 mM micelle forming agent solution.
Example 10 The procedure of Example 8 was repeated with the exception that phthalocyanine cobalt complex was used in place of phthalocyanine. A visible absorption spectrum of the supernatant is shown in Fig. ~ (Curve C). This con~irmed ~hat the phthalocyanine was soluble in the micelle solution.
The solubility was 0.22 mMJ4 mM micelle forming agent 1~29622 solution.
Example 11 The procedure of Example 8 was repeated with the exception that phthalocyanine copper complex was used in place of phthalocyanine. A visible a~sorption spectrum of the supernatant is shown in Fig. ~(Curve D). This confirmed that the phthalocyanine was soluble in the micelle solution.
The solubility was 0.11 mM/4 mM micelle forming agent solution.
Example 12 The procedure of Example 8 was repeated with the exception that phthalocyanine zinc complex was used in place of phthalocyanine. A visible absorption spectrum of the supernatant is shown in Fig. ~ (Curve E). This confirmed that the phthalocyanine was soluble in the micelle solution.
The solubility was 0.41 mM/4 mM micelle forming agent solution.
Example 13 0.22 g of lithium sulfate (Li2SO4) was added to 10 ml of the micelle solution prepared in Example 8 to prepare a 0.44 mM phthalocyanine/2 mM micelle forming agent/0.2 M lithium sulfate solution. Using this solution as an electrolyte, and ITO as an anode, platinum as a cathode and a saturated calomel electrode as a reference electrode, constant-electric potential electrolysis of applied voltage 0.5 V and current 7 ~ A was carried out at 25-C for 2 hours. As a result, a coloring matter thin film having primary particles 1,000 ~ in ` 1329622 average particle diameter was formed on the ITO. A scanning electron microscope (SEM) photograph (magnification: 20,000 using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the coloring matter thin film is shown in Fig. 14. A visible absorption spectrum of the coloring matter thin film on ITO
is shown in Fig. 13 (Curve AJ. By agreement of Fig. 13 (Curve A) with Fig. ~ (Curve A) in visible absorption spectrum, the coloring matter thin film on ITO was identified to be composed of phthalocyanine.
Example 14 The procedure of Example 13 was repeated with the exception that the term of electrolysis time was changed to 40 minutes.
A visible absorption spectrum of the formed coloring matter thin film is shown in Fig. 13(Curve A). By comparison of curve A with curve B in Fig. 13 it can be seen that the formed thin film had a small absorption spectrum as compared with Example 13 and the film thickness could be controlled by the electrolysis time.

1329~22 Example 27 0.193 g of the ferrocene derivative obtained in Example 7 was added to 100 cc of water as a surfactant (micelle forming agent), and 100 mg of phthalocyanine was added thereto and dispersed or dissolved by stirring for 10 minutes with supersonic waves. The mixture was further stirred for two days and nights with a stirrer, and then the micelle solution (dispersed solution) thus obtained was subjected to centrifugal separation at 2,000 rpm for 30 minutes. A
visible absorption spectrum of the supernatant obtained is shown in Fig. 30 (Curve A). This confirmed that phthalocyanine was soluble (dispersed) in the micelle solution. The solubility was phthalocyanine 6.4 mM/2 mM
micelle forming agent solution. To this solution, LiBr as a supporting salt was added in such a manner that the concentration was 0.1 M and stirred for 10 minutes with a stirrer.
Using the obtained solution as an electrolyte, and an ITO transparent glass electrode as an anode, platinum as a cathode and a saturated calomel electrode as a reference electrode, constant electric potantial electrolysis of applied voltage 0.5 V and current density 45~ ~/cm2 was carried out at 25-C for 30 minutes. The amount of electricity passed in this case was 0.09 coulomb.
As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. A visible absorption spectrum of pkthalocYanine on the ITO transparent glass electrode is shown in Fig. 30 (Curve B). 8y agreement of Fig. 30 (Curve A) with Fig. 30 (Curve B), it was confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. An ultraviolet (UV) absorption spectrum showed that the thickness of the thin fiLm was 0.31~ m.
An SEM photograph (magnification: 30,000; using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the thin film obtained is shown in Fig. 37.
Example 28 0.190 g of the ferrocene derivative obtained in Example was added to 100 cc of water as a surfactant (micelle forming agent), and 100 mg of phthalocyanine was added thereto and dispersed or dissolved by stirring for 10 minutes with supersonic waves. The mixture was further stirred for two days and nights with a stirrer, and then the micelle solution (dispersed solution) thus obtained was subjected to centrifugal separation at 2,000 rpm for 30 minutes. A
visible absorption spectrum of the supernatant obtained is shown in Fig. ~1 (Curve A). This confirmed that phthalocyanine was soluble (dispersed1 in the micelle solution. The solubility was phthalocyanine 7.8 mM/2 mM
micelle ~orming agent solution. To this solution, LiBr as a supporting salt was added in such a manner that the concentration was 0.1 M and stirred for 10 minutes with a stirrer.
Using the obtained solution as an electrolyte, and an ITO transparent glass electrode as an anode, platinum as a 1329~22 cathode and a saturated calomel electrode as a reference electrode, constant electric potantial electrolysis of applied voltage 0.5 V and current density q8~ A/cm2 was carried out at 25~C for 30 minutes. The amount of electricity passed in this case was 0.09 coulomb.
As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. A vi5ible absorption spectrum of phthalocyanine on the ITO transparent glass electrode is shown in Fig. 31 (Curve B). By a~reement of Fig. 31 (Curve A) with Fig. 31 (Curve B), it was confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. An W absorption spectrum showed that the thickness of the thin film was l.OS~ m.
An SEM photograph (magnification: 30,000; using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the thin fiLm obtained is shown in Fig. 38.
Example 29 0.187 g of the ferrocene derivative obtained in Example ~ was added to 100 cc of water as a surfactant (micelle forming agent), and 100 mg of phthalocyanine was added thereto and dispersed or dissolved by stirring for 10 minutes with sup~rsonic waves. The mixture was further stirred for two days and nights with a stirrer, and then the micelle solution (dispersed solution) thus obtained was subjected to centrifugal separation at 2,000 rpm for 30 minutes. A
visible absorption spectrum of the supernatant obtained is shown in Fig.. 32 (Curve A). This confirmed that phthalocyanine was soluble (dispersed) in the micelle solution. The solubility was phthalocyanine 8.2 mM/2 mM
micelle forming agent solution. To this solution, LiBr as a supporting salt was added in such a manner that the concentration was 0.1 M and stirred for 10 minutes with a stirrer.
Using the obtained solution as an electrolyte, and an ITO transparent glass electrode as an anode, platinum as a cathode and a saturated calomel electrode as a reference electrode, constant electric potantial electrolysis of applied voltage 0.5 V and current density 72~ A/cm2 was carried out at 25C for 30 minutes. The amount of electricity passed in this case was 0.13 coulomb.
As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. A visible absorption spectrum of phthalocyanine on the ITO transparent glass electrode is shown in Fig. 32 (Curve B). By agreement of Fig. 32 (Curve A) with Fig. 32 (Curve B), it was confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. An UV absorption spectrum showed tAat the thickness of the thin film was 1.85~ m.
An SEM photograph ~magnification: 30,000; using JSM-T220 produced by Nippon Denshi Co., Ltd.) of the thin film obtained is shown in Fig. 39.
Example 30 0.176 g of the ferrocene derivative obtained in Example 2~as added to 100 cc of water as a surfactant (micelle forming a~ent), and 100 mg of phthalocyanine was added thereto and dispersed or dissolved by stirring for 10 minutes with supersonic waves. The mixture was further stirred for two days and nights with a stirrer, and then the micelle solution (dispersed solution) thus obtained was subjected to centrifugal separation at 2,000 rpm for 30 minutes. A
visible absorption spectrum of the supernatant obtained is shown in Fig. 33 tcurve A). This confirmed that phthalocyanine was soluble (dispersed) in the micelle solution. The solubility was phthalocyanine 1.8 mM/2 mM
micelle forming agent solution. To this solution, LiBr as a supporting salt was added in such a manner that the concentration was 0.1 M and stirred for 10 minutes with a stirrer.
Using the obtained solution as an electrolyte, and an ITO transparent glass electrode as an anode, platinum as a cathode and a saturated calomel electrode as a reference electrode, constant electric potantial electrolysis of applied voltage 0.5 V and cùrrent density 17~ A/cm was carried out at 25-C for 30 minutes. The amount of electricity passed in this case was 0.04 coulomb.
As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. A visible absorption spectrum of phthalocyanine on the ITO transparent glass electrode is shown in Fig. 33 (Curve 8). By agreement of Fig. 33 (Curve A) with Fig. 33 (Curve B), it was confirmed that the thin film on the ITO transparent glass electrode was - 132~622 phthalocyanine. An UV absorption spectrum showed that the thickness of the thin film was 0.04 ~m.
Example 31 0.210 g of the ferrocene derivative obtained in Example was added to 100 cc of water as a surfactant (micelle forming agent), and 100 mg of phthalocyanine was added thereto and dispersed or dissolved by stirring for 10 minutes with supersonic waves. The mixture was further stirred for two days and nights with a stirrer, and then the micelle solu~ion (dispersed solution) thus obtained was subjected to centrifugal separation at 2,000 rpm for 30 minutes. A
visible absorption spectrum of the supernatant obtained is shown in Fig. 34 (Curve A). This confirmed that phthalocyanine was soluble (dispersed) in the micelle solution. The solubility was phthalocyanine 4.0 mM/2 mM
micelle forming agent solution. To this solution, LiBr as a supporting salt was added in such a manner that the concentration was 0.1 M and stirred for 10 minutes with a stirrer.
Using the obtained solution as an electrolyte, and an ITO transparent glass electrode as an anode, platinum as a cathode and a saturat~d calomel electrode as a reference electrode, constant electric potantial electrolysis of applied voltage 0.5 V and current density 124 ~A/cm2 was carried out at 25C for 30 minutes. The amount of electricity passed in this case was 0.23 coulomb.
As a result, a thin film of phthalocyanine was obtained on the ITO transparent glass electrode. A visible absorption spectrum of phthalocyanine on the ITO transparent glass electrode is shown in Fig. 34 (Curve B). By agreement of Fig. 34 (Curve A) with Fig. 34 (Curve B), it was confirmed that the thin film on the ITO transparent glass electrode was phthalocyanine. An UV absorption spectrum showed that the thickness of the thin film was 4.6~ m.
Example 32 0.188 g of the ferrocene derivative obtained in Example 5 was added to 100 cc of water as a surfactant (micelle forming agent), and 100 mg of phthalocyar.ine iron complex was added and dispersed or dissolved by stirring for 10 minutes with supersonic waves. The mixture was further stirred for two days and nights with a stirrer, and then the micelle solution (dispersed solution) thus obtained was subjected to centrifugal separation at 2,000 rpm for 30 minutes. A
visible absorption spectrum of the supernatant obtained is shown in Fig. 35 ~Curve A). This confirmed that the phthalocyanine iron complex was soluble (dispersed) in the micelle solution. The solubility was phthalocyanine iron complex 4.1 mM/2 mM micelle forming a~ent solution. To this solution, Li8r as a supporting salt was added in such a manner that the concentration was 0.1 M and stirred for 10 minutes with a stirrer.
Using the obtained solution as an electrolyte, and an ITO transparent glass electrode as an anode, platinum as a cathode and a saturated calomel electrode as a reference - 73 ~

132~622 electrode, constant electric potantial electrolysis of applied voltage 0.5 V and current density 14~ A/cm2 was carried out at 25C for 30 minutes.
As a result, a thin film of phthalocyanine iron complex was obtained on the ITO transparent glass electrode. A
visible absorption spectrum of the phthalocyanine iron complex on the ITO transparent glass electrode is shown in Fig. 35 icurve B). Because of agreement of Fig. 35(Curve A) with Fig. 35 ~Curve ~), it was confirmed that the thin film on the ITO transparent glass electrode was the phthalocyanine iron complex. An UV absorption spectrum showed that the thickness of the thin film was 0.16~ m.
Example.21 0.188 g of the ferrocene derivative obtained in Example 5 was added to 100 cc of water as a surfactant (micelle forming agent), and 100 mg of phthalocyanine copper complex was added thereto and dispersed or dissolved by stirring for 10 minutes with supersonic waves. The mixture was further stirred for two days and nights with a stirrer, and then the micelle solution ~dispersed solution) thus obtained was subjected to centrifugal separation at 2,000 rpm for 30 minutes. A ~-isible absorption spectrum of the supernatant obtained is shown in Fig. 36 ~urve A). This confirmed that phthalocyanine copper complex was soluble (dispersed) in the micelle solution. The solubility was phthalocyanine copper complex 3.8 mM/2 mM micelle forming agent solution. To this solution, LiBr as a supporting salt was added in such a 13296~2 manner that the concentration was 0.1 M and stirred for 10 minutes with a stirrer.
Using the obtained solution as an electrolyte, and an ITO transparent glass electrode as an anode, platinum as a cathode and a saturated calomel electrode as a reference electrode, constant electric potantial electrolysis of applied voltage 0.5 V and current density 43~ A/cm2 was carried out at 25C for 30 minutes. The amount of electricity passed in this case was 0.11 coulomb.
As a result, a thin film of phthalocyanine copper complex was obtained on the ITO transparent glass electrode.
A visible absorption spectrum of the phthalocyanine copper complex on the IT0 transparent glass electrode is shown in Fig. 36 (Curve B). ~ecause of agreement of Fig. 36 (Curve A) with Fig. 36 (Curve B), it was confirmed that the thin film on the ITO transparent glass electrode was the phthalocyanine copper complex. An UV absorption spectrum showed that the thickness of the thin film was 0.08~ m.
Industrial A~e~ica ~
The ferrocene derivatives of the present invention are novel compounds and can be used in various applications, for example, as surfactants ~micelle forming agents), catalysts, auxiliary fuels, depressors or dispersants. The novel ferrocene dervativec, when used particularly as surfactants, form micelles in an aqueous solution system and, therefore, coloring matters such as phthalocyanine, having a wide variety of applications and various hydrophobic polymers are 1~29~22 made soluble. In accordance with the process of the present invention in which the above surfactant (micelle forming agent) is used and at the same time~ gathering or scattering of the micelles is utilized, an organic thin film having a greatly small film thickness can be formed.

This application includes directly following this page:
~a) Examples A disclosed on pages A1 to A6, following and described with reference to Figures A2 to A9;
(b) Examples B disclosed on pages Bl to B8; following and described with reference to Figures Bl to B6;
and (c) Examples C disclosed on pages Cl to C3, following and described with reference to Figures Cl, C2 and C4.

here are no Figures Al or C3.

~ 32962'~

Example~ to~35 To a prescribed amount of water, micelle forming agent was added to make a 2 mM solution, a hydrophobic organic substance having a prescribed particle diameter was added thereto, and the mixture was stirred with application of supersonic waves fcr 10 minutes. The micelle solution thus obtained was subjected to centrifugal separation at 2000 rpm for one hour. A visible absorption spectrum of the supernatant of the said solution is shown in Figs.~2 toA9 (indicated by A) (Examples~5,6,11,15,18,19,25 and 26).
The above results confirmed that these hydrophobic organic substances are solubilized to the micelle solution.
To the said micelle solution, a prescribed supporting electrolyte was added to prepare an electrolyte, and constant potential electrolysis was performed under the conditions of a temperature of 25C, an applied vol~age of 0.5 V so as to reach the prescribed amount of electricity, by us~ of ITO or GC (glassy carbon) as the anode, platinum as the cathode, and a saturated calomel electrode as the reference electrode.
As the result, a thin film of the hydrophobic organic substance used was formed on the anode. The visible absorption spectrum on the anode is shown in Figs.A2 to~9 (indicated by B) (ExamplesA5,6,11,15,}8,19,25 and 26). Since the absorption peaks of A and B are coincident, it was confirmed that the thin film on the anode was made of the hydrophobic organic substance used.
The thickness of the thin film was determined by UV
absorption spectrum.
The conditions and result of the operation mentioned above are shown in Table~l.

?~

~ ~ 1329622 C C c c c E E~ a) ~ o, a.
n ~ c e ~o c ~ ,~
s O~ c c 3 3 ~ ~ 3 E~ ~ 3 E~ m o o~ .
c c E ` ^' ~ ` '~ ~ ~ ~ ` ~ ~ ~ r7 ,~ ~ ~o O c o ~ o o o o oo ~ _~ ' o E~
~
o~ I ~ O ~D
c L- E o ~ O ~ ~` O ~ ~ O o _, ., ~
Eo o _i o o o, o o o o o 0 0 0 0 0 0 0 ~ I
~ol ~
~C ~ 1 H 1~ H ~--1 ~ O
~0 r~
~C-- OOOOOOOOOOOOOOOO
C C
~ ~ ~1 ~ ~ ' ,., L~ 5.~ 0~
~ Y m * * N ID * * m ~N m * u~ o ~ N
E'~ ~ ~ J ,~ V ~ _l Z
0 Cn r- 0 -~ e v _~ _ _1- c ~ ¢ ~S ~ 6 ¢ ¢ ¢ ¢ ¢ ¢
U Ll cn L~ 2 ~ ~o ¢

,,~ ~ O 11~ O ~ ~ ~ X N I X X
~0v ~~ ~r _ o n 0 ~n_~
U ~ V E E o o _ _ o _ _ --I _ _ o o --I o o o c~ ~ a_ o o o o o o o o o o o o o o o o u ~
- ~ o ~ :1 ¢ ~ o c ca m m o C 5: ~ It C .C L O o _I

E ol _ ~ ~ ~ ," ~ ~~ o ~ ~ ~ _ ~

7q l ~1 3 3 132962~ 3 IE O ~
_l E~ ~ ~ c o o ~ ~ ~ 0 ~ ID C
C O v v v v v v ~ ~D C t~, v ~ v V V v .,~ O c l' c r c ~ c ~1 c .
~ ~J 3 3 3 3 3 3 ~ ~ 0 a m 3 ~ 3 3 3 3 . ~EI 0 ~ - 0 ~
~ _ --~ ~ O _~ N _~ _1 E-' (~ v E
V O D ~ 1~ ~ N (''t ~` ~ 1` _ 0~ ~ U~ 1~ ~ ~ ~r N ~1 c 1~ E O O O 'O O _ ~1~ N O~
E U--I 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 o O o O
~U
al EO~
~:~ 1~ 1 ~ W ~ ~ H ~ ~ ~ 1-~
O
.
vV ~ N ~ N ~ N ~ N
__l~O~ O OO O O O O O O O O O O O O O
_~ .~ ~.1 ,o ~ ~1 ~ ~ ~ ~ ' ~ ~J ~1o ~
_~ I N m o ~ N m Oc m" ~ m ~ O m m ,~ ~ O ~ N
cn ~ z v ~ z ~ ~ ~, Z Z ~ Z
D ~I C V
E~ lU E 11~ ¢ ~ ~ .
U ~I -- ~ E~ E~ E~ ~ E~ ~ ~ E'~ E'' ~ ~ ~ ~ D~ D. G E~
'~ ~ ~ ~ ~ ~ ~
~ .
V~
_~_ ~C ~ o ~:qJ 1~ ~ E~ o O N O O o o 3 o N o 1-~ _I N 'D N O O
N

~ ~U~D4 Ul~ V ~0 1` N ~ N O
E-- r~ ~o ~~ N N 0 '1 0 E~_ O O O O O' O O O O O o O O ~ 7 0 _ u-O
U , ,0, o ~c ~ ^ Y ~ O ~ ~~

.1 v u~ ~E E -~
_ ,n D- ~O 1` --I ~ ~ Il~ C ,e _ _, N 1~- S m ~ c Ll c ' _ _ _ o ~ ~ ~ mm ~ ~ ~ ~ v ~ ~ u ~ a-.C ~: ~ N ~ ~ O O O~ ~ C N ~ ~1 al ~ C O
U ~ ~ ~ ~ C

_ O 1~ ~^V ~ O-- N1'1~r1/7 'O 1-- ~ ~ O --~ N t~
~ Z _ _ _ N ~ N N ~ N ~ NN ~ 1~1 I't l''t rl 1'1 1`'1 W ~ C ~ ~
8~

1329~22 *l produced by Tokyo Kasei Kogyo Co., Ltd.
*2 produced by Kanto Chemical Co., Inc.
~3 distearyldimethylammonium chloride produced by Tokyo Kasei Kogyo Co., Ltd.
*4 1,1'-didodecyl-4,4'-bipyridiniumdibromide produced by Tokyo Kasei Kogyo Co., Ltd.
*5 1,3,3-trimethylindolino-6'-nitrobenzopyrylospiran produced by Tokyo Kasei Kogyo Co., Ltd.
*6 poly(4-vinylpyridine), weight average molecular weight:
50000, produced by Polyscience Co.
*7 poly(2-vinylpyridine) produced by Aldrich Chemical Co., Inc.
*8 polyvinylbutylal, weight average molecular weight:
85000, 19% hydroxyl group/1% acetate group/80% butylal group produced by Scientific Polymer Products Co.
*9 produced by Aldrich Chemical Co., Inc.
*10 4,4'-azoxyanisole produce by Aldrich Chemical Co., Inc.
*il dibenzo-18-crown-6 produced by Nisso Co., Ltd.
*12 poly(4-vinylpyridine), weight average molecular weight:
50000, produced by Polyscience Co.
~13 manganese tetraphenylporphyrin *14 3.~ mM in monom~r unit *15 1.0 mM in monomer unit ~16 1.2 mM in monomer unit ~1 .

*17 compound represented by the formula:

~ ?~, I H 2 Z ~0 C H z C H 2) ~ z . ~ O H

*18 compound represented by the formula:

C H 3 \/ N ~--C " H 2Z~
C H3 Fe Example~l To 20 ml of water, 198 mg of a compound (FPEG) represented by the formula:

~C ~ I H 2Z tO C H 2 C H 2)12. zO H
F e was added as a nonionic micelle forming agent, 115 mg of Pc-Cu (alpha-type, produced by Dainichiseika Color & Chemicals Mfg. Co., Ltd.) was added, and stirred with the application of supersonic waves for 10 minutes. The micelle solution thus obtained was subjected to centrifugal separation at 2000 rpm for one hour. A visible absorption spectrum of the supernatant is shown in Fig.Bl (indicated by A). From the above results, it was confirmed that Pc-Cu (alpha-type) is solubilized to the micelle solution. The solubility was 5.3 mM/2 mM micelle forming agent solution.
To 20 ml of the said micelle solution, 0.210 g of LiBr was added as a supporting electrolyte to form 5.3 mM Pc-Cu (alpha-type)/2 mM micelle forming agent/0.1 M LiBr solution.
By use of the resulting solution as an electrolytic solution, ITO as the anode, platinum as the cathode and a saturated calomel electrcde as a reference electrode, constant potential electrolysis was performed for 30 minutes under the conditions of a temperature of 25-C, an applied voltage of ~3 0.500 V, and a current density of 8.5 ~A/cm . The amount of electricity passed was 0.021 coulomb.
As the result, a thin film of Pc-Cu (alpha-type) was formed on the anode. A visible absorption spectrum of the said thin film on the anode is shown in Fig.81 (indicated by B). Since the absorption peaks of A and B in Fig.Bl are coincident, it was confirmed that the thin film of coloring matter on the anode consists of Pc-Cu (alpha-type) used.
The thickness of the thin film was found to be 0.8 ~m ~rom the measurement of UV absorption spectrum.

Example B2 To 20 ml of water, 198 mg of FPEG used in Examplee~ was added as nonionic micelle forming agent, and 115 mg of Pc-Cu (beta-type) (produced by Dainichiseika Color & Chemicals Mfg.
Co., Ltd.) was added thereto, and then stirred with the application of supersonic waved for 10 minutes. The resulting micelle solution was subjected to centrifugal separation at 2000 rpm for one hour. A visible absorption spectrum of the supernatant of the solution is shown in Fig.B
2 (indicated by A). The above confirms that Pc-Cu (beta-type) is solubilized into micelle solution. The solubility was 5.1 mM/2 mM micelle forming solution.
Next, to 20 ml of the said micelle solution, 0.210 g of LiBr was added as a supporting electrolyte to obtain a solution of 5.1 mM Pc-Cu (beta-type)/2 mM micelle forming agent/0.1 M LiBr. By the use of the above solution as an e7ectrolytic solution, I~O zs the anode, platinum as the cathode and a saturated calomel electrode as a reference el~ctrode, constant potential electrolysis was performed for 30 minutes under the conditions of a temperature of 25C, an applied voltage of 0.500 V, and a current density of 4.3 ~A/cm2. The amount of the electricity passed was 0.012 coulomb.
As the result, a thin film of Pc-Cu (beta-type) was formed on the anode. The visible absorption spectrum of the thin film on the anode is shown in Fig.B2 (indicated by B).
Since the absorption peaks of A and B in Fig.~2 are coincident, it was confirmed that the thin film of the coloring matter on the anode consists of Pc-Cu (beta-type) used.
The thickness of the said thin film was found to be o . 3 ~m by the measurement of UV absorption spectrum.

Example B3 To 20 ml of water, lg8 mg of FPEG used in Exampleal was added as nonionic micelle forming agent, and 229 mg of C116-Pc-Cu (Phthalocyanine Green) (produced by Tokyo Kasei Kogyo Co., Ltd.) was added thereto, and then stirred with the application of supersonic waved for 10 minutes. The resulting micelle solution was subjected to centrifugal separation at 2000 rpm for one hour. A visible absorption spectrum of the supernatant of the solution is shown in Fig.B
3 (indicated by A). The above confirms that C116-Pc-Cu is solubilized into micelle solution. The solubility was 1.5 mM/2 mM micelle for~ing solution.

Next, to 20 ml of the said micelle solution, 0.210 g of LiBr was added as a supporting electrolyte to obtain a solution of 1.5 mM C116-Pc-Cu/2 mM micelle forming agent/0.1 M LiBr. By the use of the above solution as an electrolytic solution, ITO as the anode, platinum as the cathode and a saturated calomel electrode as a reference electrode, constant potential electrolysis was performed for 30 minutes under the conditions of a temperature of 25C, an applied voltage of 0.500 V, and a current density of 12.6 ~A/cm2.
The amount of the electricity passed was 0.023 coulomb.
As the result, a thin film of C116-Pc-Cu was formed on the anode. The visible absorption spectrum of the thin film on the anode is shown in Fig.~3 (indicated by B). Since the absorption peaks of A and B in Fig.a3 are coincident, it was confirmed that the thin film of the coloring matter on the anode consists of C116-Pc-Cu used.
The thickness of the said thin film was found to be 0.1 ~m by the measurement of UV absorption spectrum.
Example~4 To 20 ml of water, 198 mg of FPEG used in ExampleBl was added as nonionic micelle forming agent, and 122 mg of Cl-Pc-Cu (Phthalocyanine Blue) (produced by Tokyo Kasei Kogyo Co., Ltd.) was added thereto, and then stirred with the application of supersonic waved for 10 minutes. The resulting micelle solution was subjected to centrifugal separation at 2000 rpm for ore hour. A visible absorption spectrum of the supernatant of the solution is shown in Fig~ B

4 (indicated by A). The above confirms that Cl-Pc-Cu is solubilized into micelle solution. The solubility was 4 . 2 mM/2 mM micelle forming solution.
Next, to 20 ml of the said micelle solution, 0.210 g of LiBr was added as a supporting electrolyte to obtain a solution of 4.2 mM Cl-Pc-Cu/2 mM micelle forming agent/0.1 M
LiBr. By the use of the above solution as an electrolytic solution, IT0 as the anode, platinum as the cathode and a saturated calomel electrode as a reference electrode, constant potential electrolysis was performed for 30 minutes under the conditions of a temperature of 25~C, an applied voltage of 0.500 V, and a current density of 27 ~A/cm . The amount of the electricity passed was 0.05 coulomb.
As the result, a thin film of Cl-Pc-Cu was formed on the anode. The visible absorption spectrum of the thin film on thç anode is shown in Fig. B4 ( indicated by B). Since the absorption peaks of A and B in Fig. B4 are coincident, it was confirmed that the thin film of the coloring matter on the anode consists of Cl-Pc-Cu used.
The thickness of the said thin film was found to be 0.8 ~m by the measurement of ~V absorption spectrum.
Example~5 To 20 ml of water, 198 mg of FPEG used in Exampl~Bl was added as nonionic micelle forming agent, and 282 mg of CllOBr6-Pc-Cu (Heliogen Green) (K8730) (produced by BASF
Japan Co., Ltd.) was added thereto, and then stirred with the application of supersonic waved for 10 minutes. The ~7 resulting micelle solution was subjected to centrifugal separation at 2000 rpm for one hour. A visible absorption spectrum of the supernatant of the solution is shown in Fig.

5 tindicated by A). The above confirms that Cl1OBr6-Pc-Cu is solubilized into micelle solution. The solubility was 4.2 mM/2 mM micelle forming solution.
Next, to 20 ml of the said micelle solution, 0.210 g of LiBr was added as a supporting electrolyte to obtain a solution of 4.2 mM CllOBr6-Pc-Cu/2 mM micelle forming agent/0.1 M LiBr. By the use of the above solution as an electrolytic solution, ITO as the anode, platinum as the cathode and a saturated calomel electrode as a reference electrode, constant potential electrolysis was performed for 30 minutes under the conditions of a temperature of 25C, an applied voltage of 0.500 V, and a current density of 8.2 ~A/cm2. The amount of the electricity passed was 0.015 coulomb.
As the result, a thin film of CllOBr6-Pc-Cu was formed on the anode. The visible absorption spectrum of the thin film on the anode is shown in Fig.B5 (indicated by B). Since the absorption peaks of A and B in Fig.~5 are coincident, it was confirmed that the thin film of the coloring matter on the anode consists of Cl1OBr6-Pc-Cu used.
The thickness of the said thin film was found to be 0.9 ~m by the measurement of UV absorption spectrum.

ExampleB6 To 20 ml of water, 198 mg of FPEG used in Example~l was ~3q added as nonionic micelle forming agent, and 300 mg of C18Br8-Pc-Cu (Heliogen Green) (K9360) (produced by BASF Japan Co., Ltd.) was added thereto, and then stirred with the application of supersonic waved for 10 minutes. The resulting micelle solution was subjected to centrifugal separation at 2000 rpm for one hour. A visible absorption spectrum of the supernatant of the solution is shown in Fig.

6 (indicated by A). The above confirms that C18Br8-Pc-Cu is solubilized into micelle solution. The solubility was 3.8 mM/2 mM micelle forming solution.
Next, to 20 ml of the said micelle solution, 0.210 g of Li8r was added as a supporting electrolyte to obtain a solution of 3.8 mM C18Br8-Pc-Cu/2 mM micelle forming agent/0.1 M LiBr. By the use of the above solution as an electrolytic solution, ITO as the anode, platinum as the cathode and a saturated calomel electrode as a reference electrode, constant potential electrolysis was performed for 30 minutes under the conditions of a temperature of 25~C, an applied voltage of 0.500 V, and a current density of 11.2 ~A/cm2. The amount of the electricity passed was 0~018 coulomb.
As the result, a thin film of C18Br8-Pc-Cu was formed on the anode. The visible absorption spectrum of the thin film on the anode is shown in Fig.B6 (indicated by B). Since the absorption peaks of A and B in Fig.B6 are coincident, it was confirmed that the thin film of the coloring matter on the anode consists of C18Br8-Pc-Cu used.

~0~

The thickness of the said thin film was found to be 0.7 ~m by the measurement of UV absorption spectrum.

~a Example~l In 100 ml of water, 0.099 g of a compound (FPEG) represented by the formula-~C I, H 2 2 ~0 C H 2 C H 2~ 0 ~I
F e was dissolved as nonionic micelle forming agent to make a 1mM solution. Further, 0.52 g of LiBr as a supporting salt was added so as to have a concentration of 0.1 mM.
Then, an excess amount (1.0 g) of magnesium phtharocianine (Pc-Mg) was added to the solution, which was subjected to supersonic wave treatment for 10 minutes. After that, the solution was stirred for one day and night, and after the said operation was repeated, centrifugal separation was performed at 2000 rpm for one hour to prepare a micelle solution. A visible absorption spectrum of the supernatant of the said solution is shown in Fig.~l (indicated by the solid line). This confirmed that Pc-Mg is solubilized in micelle solution. A visible absorption spectrum of the ethanol solution of the said Pc-Mg is also shown in Fig.~l (indicated by the broken line).
Subsequently, the above micelle solution ~saturated solubilized aqueous solution of Pc-Mg) was electrolyzed for two hours with a voltage of ~.5 V applied on the I~O

transparent glass electrode against the saturated calonel electrode (SCE).
The visible absorption spectrum of the thin film resulted on ITO glass transparent electrode according to the above operation is shown in Fig.C2 (indicated by the solid line). The visible absorption spectrum of the supernatant is shown in Fig.C2 (indicated by the broken line) (which is the same as the solid line in Fig.~l) ExampleC2 In 100 ml of water, 0.198 g of the same FPEG as used in Example~l was dissolved as nonionic micelle forming agent to make a 2 mM solution. Further, 0.52 g of LiBr as a supporting salt was added so as to have a concentration of 0.1 mM.
subsequently, an excess amount (1.0 g) of chlorine-containing aluminum phtharocianine (Pc-AlCl) was added to the solution, which was subjected to supersonic wave treatment for 10 minutes. Then, the solution was stirred for one day and night, and after the said operation was repeated, centrifugal separation was performed at 2000 rpm for one hour to prepare a micelle solution.
Subsequently, the above micelle solution (saturated solubilized aqueous solution of Pc-AlCl) was electrolyzed for two hours with a voltage of ,0.5 V applied on the ITO
transparent glass electrode against SCE.
The visible absorption spectrum of the thin film resulted on ITO glass transparent electrode according to the `- 1329622 above operation is shown in Fig.C4 (indlcated by the solid line). The visible absorption spectrum of the supernatant of the micelle solution is shown in Fig.C4 (indicated by the broken line).

Claims (32)

1. A ferrocene derivative represented by the general formula:

(I) (wherein R1 and R2 are each independently a hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, R3 is a hydrogen, a methyl group, an ethyl group, a methoxy group, a carbomethoxy group, a hydroxyl group, carboxyl group or a sulfonic acid group, X
is a halogen, and CnH2n is a straight or branched hydrocarbon group having 4 to 16 carbon atoms other than an alkylene group); or the general formula:

(A) (wherein m is an integer of 2 to 4, n is an integer of 2 to 5, r is an integer of 11 to 18, s is a real number of 2.0 to 70.0, and R1 and R2 are the same as described above), or the general formula:

(B) (wherein w is an integer of 2 to 18, and m, n, s, R1 and R2 are the same as described above)

2. The ferrocene derivative according to claim 1, wherein in formula (I), R1, R2 and R3 are independently methyl, ethyl or methoxy groups.

3. The ferrocene derivative according to claim 1, wherein in formula (I), R3 is a carbomethoxy group, carboxyl group or sulfonic acid group.

4. The ferrocene derivative according to claim 1, wherein in formula (I) X is Br.

5. A surfactant consisting essentially of a ferrocene derivative represented by the general formula:

Claim 5 continued...

(I) (wherein R1 and R2 are each independently a hydrogen, a methyl group an ethyl group, a methoxy group or a carbomethoxy group, R3 is a hydrogen, a methyl group, an ethyl group, a methoxy group, a carbomethoxy group, a hydroxyl group, carboxyl group or a sulfonic acid group, X
is a halogen, and CnH2n is a straight or branched hydrocarbon group having 4 to 16 carbon atoms other than an alkylene group); or the general formula:

(A) (wherein m is an integer of 2 to 4, n is an integer of 2 to 5, r is an integer of 11 to 18, s is a real number of 2.0 to 70, and R1 and R2 are the same as described above), or the general formula:

(B) (wherein w is an integer of 2 to 18, and m,n, s, R1 and R2 are the same as described above.

6. A method of producing an organic thin film of a hydrophobic substance comprising:
forming an aqueous phase of (a) the hydrophobic substance and (c) a ferrocene derivative represented by the general formula:

(I) (wherein R1 and R2 are each independently a hydrogen, a methyl group an ethyl group, a methoxy group or a carbomethoxy group, R3 is a hydrogen, a methyl group, an ethyl group, a methoxy group, a carbomethoxy group, a is a halogen, and CnH2n is a straight or branched hydrocarbon group having 4 to 16 carbon atom other than an alkylene group); or the general formula:

(A) Claim 6 continued...

(wherein m is an integer of 2 to 4, n is an integer of 2 to 5, r is an integer of 11 to 18, s is a real number of 2.0 to 70, and R1 and R2 are the same as described above); or the general formula:

(B) (wherein w is an integer of 2 to 18, and m, n, s, R1 and R2 are the same as described above); or the general formula:

(A') (wherein t is an integer of 2 to 10, m is an integer of 1 to 4, n is an integer of 1 to 5, and R1, R2 and s are the same as above;

providing an electrode in contact with the aqueous phase; and electrolyzing the aqueous phase to form a thin film of the hydrophobic substance on a surface of the electrode.

7. The method according to claim 5, wherein the electrolyzing is conducted at a temperature of the aqueous phase of 0° to 70° C., a voltage of 0.03 to 1.5 V and a current density of not more than 10 mA/cm2.

8. The method according to claim 6, wherein the electrode is of a metal more noble than ferrocene.

9. The method according to claim 8, wherein the electrode is selected from the group consisting of a mixed oxide of indium oxide and tin oxide, platinum, gold, silver, glassy carbon, an electrically conductive metal oxide, and an electrically conductive organic polymer.

10. The method according to claim 6, wherein the electrolyzing is conducted at a temperature of the aqueous phase of 20° to 30° C., a voltage of 0.1 to 0.5 V and a current density of 50 to 300 µA/cm2.

11. A method of producing an organic thin film of a hydrophobic substance comprising:

forming an aqueous phase of (a) the hydrophobic Claim 11 continued....
substance, (b) a salt and (c) a ferrocene derivative represented by the general formula:

(I) (wherein R1 and R2 are each independently a hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, R3 is a hydrogen, a methyl group, an ethyl group, a methoxy group, a carbomethoxy group, a is a halogen, and CnH2n is a straight or branched hydrocarbon group having 4 to 16 carbon atoms other than an alkylene group); or the general formula:

(A) (wherein m is an integer of 2 to 4, n is an integer of 2 to 5, r is an integer of 11 to 18, s is a real number of 2.0 to 70, and R1 and R2 are the same as described above); or the general formula:

(B) (wherein w is an integer of 2 to 18, and m, n, s, R1 and R2 are the same as described above); or the general formula:

(A') (wherein t is an integer of 2 to 10, m is an integer of 1 to 4, n is an integer of 1 to 5, and R1, R2, and s are the same as above;

providing an electrode in contact with the aqueous phase; and electrolyzing the aqueous phase to form a thin film of the hydrophobic substance on a surface of the electrode.

12. The method according to claim 11 wherein the electrolyzing is conducted at a temperature of the aqueous phase of 0° to 70° C., a voltage of 0.03 to 1.5 V and a current density of not more than 10 mA/cm2.

13. The method according to claim 11, wherein the electrode is of a metal more noble than ferrocene.

14. The method according to claim 11, wherein (a), (b) and (c) are dispersed in the aqueous phase by supersonic waves, a homogenizer, or a stirrer.

15 . The method according to claim 14 , wherein the salt is lithium sulfate.

16 . The method according to claim 15 wherein the electrolyzing is conducted to a temperature of the aqueous phase of 20° to 30° C., a voltage of 0.1 to 0.5 V and a current density of 50 to 300 µA/cm2.

17. The method according to claim 11, wherein the film formed on the electrode surface comprises particles 600 to 900 A in size.

18. The method according to claim 11 further comprising controlling a thickness of the film by controlling current density during electrolyzing.

19. The method according to claim 11, wherein the hydrophobic substance is selected from the group consisting of phthalocyanine and 1-phenylazo-2-naphthol.

20. The method according to claim 11, wherein the hydrophobic substance is a phthalocyanine complex of a metal selected from the group consisting of iron, zinc, copper and cobalt.

21. The method according to claim 11, wherein the salt is at least one of a sulfuric acid salt of lithium, potassium, sodium, rubidium, or aluminum or an acetic acid salt of lithium, potassium, sodium, rubidium, aluminum, beryltium, magnesium, strontium or barium and wherein the amount of salt is 10 to 300 times the amount of the ferrocene derivative.

22. The method according to claim 21, wherein the amount of salt is 50 to 200 times the amount of the ferrocene derivative and wherein the salt is lithium sulfate or lithium bromide.

23. A method of improving the solubility of a hydrophobic substance comprising:

forming an aqueous phase of (a) the hydrophobic substance, and (b) a ferrocene derivative represented by the general formula:

(I) (wherein R1 and R2 are each independently a hydrogen, a methyl group, an ethyl group, a methoxy group or a carbomethoxy group, R3 is a hydrogen, a methyl group, an ethyl group, a methoxy group, a carbomethoxy group, a hydroxyl group, carboxyl group or a sulfonic acid group, X
is a halogen, and CnH2n is a straight or branched hydrocarbon group having 4 to 16 carbon atoms other than an alkylene group); or the general formula:

(A) (wherein m is an integer of 2 to 4, n is an integer of 2 to S, r is an integer of 11 to 18, s is a real number of 2.0 to 70, and R1 and R2 are the same as described above); or the general formula:

(B) (wherein w is an integer of 2 to 18, and m, n, s, R1 and R2 are the same as described above); or the general formula:

(A') (wherein t is an integer of 2 to 10, m is an integer of 1 to 4, n is an integer of 1 to 5, and R1, R2, n and s are the same as above); and dispersing (a) and (b) in the aqueous phase.

24 . The method according to claim 23, wherein the dispersing is by means of supersonic waves, a homogenizer, or a stirrer, wherein the aqueous phase comprises a salt and wherein the aqueous phase is at a temperature of 0° to 70°C.

25. The method according to claim 24, wherein the salt is at least one of a sulfuric acid salt of lithium, potassium, sodium, rubidium, or aluminum or an acetic acid of lithium, potassium, sodium, rubidium, aluminum, beryllium, magnesium, strontium or barium and wherein the amount of salt is 10 to 300 times the amount of the ferrocene derivative.

26. The method according to claim 24, wherein the amount of salt is 50 to 200 times the amount of the ferrocene derivative and wherein the salt is lithium sulfate or lithium bromide.

27. The method according to claim 23, wherein the hydrophobic substance is selected from the group consisting of phthalocyanine and 1-phenyhlazo-2-napthol.

28. The method according to claim 23 wherein the hydrophobic substance is a phthalocyanine complex of a metal selected from the group consisting of iron, zinc, copper, and cobalt.

29. The ferrocene derivative according to claim 1 of the formula:

30. The surfactant consisting essentially of a ferrocene derivative according to claim 5 wherein the ferrocene derivative is of the formula:

31. The method according to claim 11, wherein the ferrocene derivative is of the formula:

32. The method according to claim 23, wherein the ferrocene derivative is of the formula: