JP2002080785A - Electroconductive organic and inorganic hybrid film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electroconductive organic and inorganic hybrid film having flexibility and mold release property of toner. SOLUTION: This electroconductive organic and inorganic hybrid film is obtained by dispersing electroconductive filler into an organic and inorganic hybrid film composed of a metallic and/or metalloid alkoxy formed by sol and gel method and an organosilicon compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive organic / inorganic hybrid film.

[0002]

2. Description of the Related Art Conventionally, a conductive metal oxide film (JP-A-8-272189) in which a conductive material such as titanium oxide and metal fine particles is dispersed in a metal oxide has been provided by a sol-gel method.

[0003]

When a conductive film is formed by a sol-gel method, a sol obtained by dispersing a conductive filler in an alkoxide solution of a metal or metalloid is applied to the surface of a substrate, and gelled by heating to form a film. However, there is a problem that the metal oxide film easily shrinks in the heating step, and the film is easily cracked. In addition, the conductive film made of a metal oxide film does not have a large contact angle with water,
Therefore, there is a problem that the toner releasability is poor.

[0004]

According to the present invention, there is provided an organic-inorganic hybrid film comprising a metal and / or metalloid alkoxide and an organosilicon compound formed by a sol-gel method. The present invention provides a conductive organic / inorganic hybrid film in which a conductive filler is dispersed.

The conductive organic / inorganic hybrid coating is formed on a substrate, and the substrate is preferably a conductive roll substrate or a conductive belt substrate for an electrophotographic apparatus.

[0006]

By using an organic / inorganic hybrid film in the conductive film, the adhesion of the film to the substrate is improved, and shrinkage due to heating is reduced.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The conductive organic / inorganic hybrid film of the present invention is an organic / inorganic hybrid film composed of a metal and / or semimetal alkoxide and an organosilicon compound, wherein a conductive filler is dispersed in the organic / inorganic hybrid film. Is what it is.

As a step of producing a conductive organic / inorganic hybrid coating, first, an organic / inorganic hybrid sol solution comprising a metal and / or semimetal alkoxide and an organosilicon compound is prepared.

The metal or metalloid forming the alkoxide includes aluminum, silicon, titanium,
Metals or metalloids capable of forming an alkoxide such as vanadium, manganese, iron, cobalt, zinc, germanium, yttrium, zirconium, niobium, cadmium, and tantalum are mentioned, and these may be used alone or in combination of two or more. .

The type of alkoxide is not particularly limited, and includes, for example, methoxide, ethoxide, propoxide, isopropoxide, butoxide and the like. Further, part of the alkoxy group may be β-diketone, β-ketoester. Or an alkoxide derivative substituted with an alkanolamine, an alkylalkanolamine or the like.

The above-mentioned organosilicon compound includes, for example,
Dialkyl dialkoxysilane, terminal silanol polydimethylsiloxane and the like can be used. Examples of the dialkyldialkoxysilane include, for example, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, dipropyl Examples include dimethoxysilane, dipropyldiethoxysilane, dipropyldipropoxysilane, dipropyldibutoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldipropoxysilane, diphenyldibutoxysilane, and the like. The terminal silanol polydimethylsiloxane preferably has a weight average molecular weight of 400 to 10,000.

In addition to the above-mentioned organosilicon compound, a fluorine-substituted organosilicon compound in which hydrogen of an organosilicon compound is substituted with fluorine may be used. For example, CF ₃ CH ₂ CH
_{2 -Si (OC 2 H 5)} 3 and the like.

The hydrolyzate of the metal and / or metalloid alkoxide is reacted with an organic component such as the organosilicon compound to prepare an organic / inorganic hybrid sol solution. The organic component may be mixed with the alkoxide before hydrolysis or with the hydrolyzed alkoxide.

The solvent to be used at this time is not particularly limited as long as it is a solvent capable of uniformly dispersing and dissolving the alkoxide and the organic component. For example, in addition to various alcohols such as methanol and ethanol, acetone, toluene and xylene Etc. are commonly used. In order to accelerate the hydrolysis reaction of the alkoxide, a catalyst such as hydrochloric acid, phosphoric acid, and acetic acid may be appropriately used.

When dialkylalkoxysilane is used as the organic component, the mixing ratio with the alkoxide as the inorganic component is such that the molar ratio of organic component / (organic component + inorganic component) is 0.5 to 0.95. It is preferred that
If the molar ratio is less than 0.5, the resulting film may peel off or crack, and the molar ratio may be 0.9.
If it exceeds 5, the surface hardness of the resulting film may be significantly reduced.

When the silanol-terminated polydimethylsiloxane is used as the organic component, the mixing ratio with the alkoxide as the inorganic component is as follows: organic component / (organic component +
The molar ratio of the (inorganic component) is preferably in the range of 0.1 to 0.7. If the molar ratio is less than 0.1, the resulting film may be hard and brittle, and may not be elastically deformed.
If the molar ratio exceeds 0.7, the reaction product of the organic component and the inorganic component may not gel.

When this silanol-terminated polydimethylsiloxane is reacted with an alkoxide, the alkoxy group of the alkoxide is replaced by a hydroxyl group, and the hydroxyl group causes a dehydration / condensation reaction with the silanol group at the end of the silanol-polydimethylsiloxane. An elastomer is formed.

The organic / inorganic hybrid sol liquid sufficiently hydrolyzes the alkoxide by stirring or the like, and partially performs dehydration polymerization.

The organic / inorganic hybrid sol obtained as described above is further mixed with a conductive filler and mixed to prepare a coating liquid in which the conductive filler is dispersed.

The conductive filler is a filler added to the organic / inorganic hybrid sol liquid to impart conductivity to the organic / inorganic hybrid film, and is, for example, graphite, acetylene black, Ketjen black, furnace black. , Carbon black such as channel black, graft carbon obtained by grafting a hydrophobic oligomer (oligomer such as styrene, acrylic acid, methacrylic acid, methyl methacrylate) to a functional group present on the carbon surface, conductive titanium oxide, zinc oxide , Tin oxide, conductive metal oxides such as antimony oxide, conductive barium sulfate, aluminum borate, conductive metal salts such as quaternary ammonium salts, ionic conductive agents such as surfactants, polypyrrole, polyaniline, Polyacetylene, polyparaphenylene, polythiof Emissions, polyfuran, powdery product of a conductive polymer polyphenylene vinylene and the like, mixtures of more of these alone or two or are used as the conductive filler. The average particle size of the conductive filler is 0.01 to
Those having a range of 10 μm are preferred.

The amount of the conductive filler to be added depends on the type of the conductive filler, the conductivity of the target conductive organic-inorganic hybrid film, and the like. A range of from 10 to 10% by weight is preferred.

The organic / inorganic hybrid sol to which the conductive filler has been added is stirred by a desired stirring device, and the conductive filler is uniformly dispersed in the organic / inorganic hybrid sol to prepare a coating solution.

The prepared coating liquid is applied to the surface of a substrate. Examples of the substrate include synthetic resin, glass, metal, and ceramics. The present invention is particularly usefully applied to, for example, a conductive roll substrate or a conductive belt substrate for an electrophotographic apparatus. With the conductive roll substrate,
It is a roll base material used for a charging roll, a developing roll, a cleaning roll, a transfer roll, and the like, and the conductive belt base material is a belt base material used for a transfer belt, a transfer fixing belt, and the like. Are, for example, polyimide resin (PI), polycarbonate resin (P
C), polybutylene terephthalate (PBT), polyarylate (PAR), polyethylene naphthalate (PE)
N), a thermoplastic resin such as a polyester resin such as polyethylene terephthalate (PET), a polyurethane resin (PU), and a polyamide resin (PA). These are used alone or in combination, or used as a polymer alloy. In some conductive base materials, conductive fillers are dispersed.

When the substrate is made of a resin material,
Before applying the coating liquid on the member, the surface of the member is cleaned in advance and subjected to ultraviolet irradiation treatment or Na
It may be processed by OH chemical etching.

As a method of applying the coating liquid on the surface of the base material, known methods can be used, for example, dip coating, spray coating, roll coating,
A method such as flow coating can be used.

The coating liquid applied to the substrate surface is
Heat treatment forms a conductive organic / inorganic hybrid film.

The conditions for the heat treatment vary depending on the conditions such as the type and thickness of the conductive organic / inorganic hybrid film.
The heating time and the heating temperature are set so that cracks do not occur in the film, and are usually 100 to 400 ° C. × 0.5 to 1 ° C.
Time.

Since the conductive organic / inorganic hybrid film contains an organic silicon compound as an organic component, for example, the shrinkage is smaller than that of a metal oxide containing no organic component. Cracks that occur at the time are prevented.

The conductive organic / inorganic hybrid film thus obtained is a conductive organic / inorganic hybrid film using, as an organic component, a silanol polydimethylsiloxane having a terminal silanol.
The inorganic hybrid film exhibits excellent flexibility and elasticity due to the flexible siloxane bond serving as the main skeleton of polydimethylsiloxane, and exhibits good adhesion to the above-mentioned substrate.

The conductive organic / inorganic hybrid film of the present invention has a contact angle with water of 100 ° or more, and is excellent in toner releasability.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples. [Example 1] Tetraisopropoxytitanium was used as an inorganic component, and silanol-terminated polydimethylsiloxane (weight average molecular weight 6,000) was used as an organic component.
Using ethanol as a solvent, silanol-terminated polydimethylsiloxane: tetraisopropoxytitanium: ethyl acetoacetate: water is mixed at a mixing ratio of 0.25: 1: 2: 2 (molar ratio) and sufficiently stirred for 0.5 hours. Thus, sufficient hydrolysis of the tetraisopropoxytitanium and partial condensation polymerization with the terminal polydimethylsiloxane were carried out to prepare an organic / inorganic hybrid sol solution. In addition, the organic
1.5 wt% of carbon having an average particle diameter of 16 nm as a conductive filler was added to the inorganic hybrid sol solution, and the mixture was stirred to prepare a coating solution.
In the mixing and stirring, the organic / inorganic hybrid sol to which the conductive filler was added was stirred for 10 minutes by a planetary stirrer. The base material to which the coating liquid was applied was an aluminum shaft. The surface of the aluminum shaft was sufficiently cleaned, and the surface was set on a flow coat machine, and the coating liquid was applied on the base material. Then, under air atmosphere, 2
Heat treatment was performed at 00 ° C. for 0.5 hour and at 350 ° C. for 0.1 hour to form a conductive organic / inorganic hybrid film on the surface of the substrate.

The thickness of the conductive organic / inorganic hybrid film obtained in Example 1 was 23.0 μm, the contact angle with water was 111.7 °, and the volume resistivity was 7.99 log Ω · cm.
Met.

Example 2 Tetraisopropoxytitanium was used as an inorganic component, and silanol-terminated polydimethylsiloxane was used as an organic component (weight average molecular weight: 6,000).
It was used. Using ethanol as a solvent, silanol-terminated polydimethylsiloxane: tetraisopropoxytitanium: ethyl acetoacetate: water is mixed at a mixing ratio of 0.25: 1: 2: 2 (molar ratio) and sufficiently stirred for 0.5 hours. Thus, sufficient hydrolysis of the tetraisopropoxytitanium and partial condensation polymerization with the terminal polydimethylsiloxane were carried out to prepare an organic / inorganic hybrid sol solution.
Further, 3.0 wt% of carbon having an average particle diameter of 16 nm as a conductive filler was added to the organic / inorganic hybrid sol solution, and the mixture was stirred to prepare a coating solution. In the mixing and stirring, the organic / inorganic hybrid sol to which the conductive filler was added was stirred for 10 minutes by a planetary stirrer. The base material to which the coating liquid was applied was an aluminum shaft. The surface of the aluminum shaft was sufficiently cleaned, and the surface was set on a flow coat machine, and the coating liquid was applied on the base material. Then, in an air atmosphere, at 200 ° C. for 0.5 hour and at 350 ° C.
Heat treatment was performed for one hour to form a conductive organic / inorganic hybrid film on the surface of the substrate.

The conductive organic / inorganic hybrid film obtained in Example 2 had a thickness of 24.0 μm, a contact angle with water of 111.7 °, and a volume resistivity of 5.70 log Ω · cm.
Met.

Comparative Example 1 Tetraisopropoxytitanium was used as an inorganic component, and silanol-terminated polydimethylsiloxane was used as an organic component (weight average molecular weight: 6,000).
It was used. Using ethanol as a solvent, silanol-terminated polydimethylsiloxane: tetraisopropoxytitanium: ethyl acetoacetate: water is mixed at a mixing ratio of 0.25: 1: 2: 2 (molar ratio) and sufficiently stirred for 0.5 hours. Thus, sufficient hydrolysis of the tetraisopropoxytitanium and partial condensation polymerization with the terminal polydimethylsiloxane were carried out to prepare an organic / inorganic hybrid sol solution.
The substrate to which the coating liquid is applied is an aluminum shaft, and sufficiently removes dirt on the surface of the aluminum shaft,
The substrate was set on a flow coat machine, and the organic / inorganic hybrid sol solution was applied onto the substrate. Thereafter, heat treatment was performed in an air atmosphere at 200 ° C. for 0.5 hour and at 350 ° C. for 0.1 hour to form an organic-inorganic hybrid film on the substrate surface.

The thickness of the organic-inorganic hybrid film obtained in Comparative Example 1 was 38.0 μm, and the contact angle with water was 10
The volume resistivity was 8.1 ° and the volume resistivity was 8.36 log Ω · cm.

Example 3 A conductive organic / inorganic hybrid film containing Ti, Si and terminal silanol polydimethylsiloxane (weight average molecular weight: 1500) as main components is manufactured. Using ethanol as a solvent, terminal silanol polydimethylsiloxane: tetraisopropoxytitanium: ethyl acetoacetate: water: tetraethoxysilane 0.375:
The mixture was mixed at a mixing ratio (molar ratio) of 1: 2: 2: 0.125 and sufficiently stirred for 0.5 hour to prepare an organic / inorganic hybrid sol solution. Further, 3.0 wt% of carbon having an average particle diameter of 16 nm as a conductive filler was added to the organic / inorganic hybrid sol solution, and the mixture was stirred to prepare a coating solution. In the mixing and stirring, the organic / inorganic hybrid sol to which the conductive filler was added was stirred for 10 minutes by a planetary stirrer. The base material to which the coating liquid was applied was an aluminum shaft. The surface of the aluminum shaft was sufficiently cleaned, and the coating liquid was set on a flow coat machine, and the coating liquid was applied to the base material. Thereafter, a heat treatment was performed at 120 ° C. for 0.5 hours in an air atmosphere to form a conductive organic / inorganic hybrid film on the surface of the substrate.

The thickness of the conductive organic-inorganic hybrid film obtained in Example 3 was 15.0 μm, the contact angle with water was 103.8 °, and the volume resistivity was 3.49 log Ω · cm.
Met. The conductive organic / inorganic hybrid film of Example 3 can lower the temperature of the heating step as compared with Examples 1 and 2, and therefore can more reliably prevent the occurrence of cracks. Further, the film of Example 3 can be formed on a substrate having low heat resistance.

Comparative Example 2 An organic / inorganic hybrid film containing Ti, Si and terminal silanol polydimethylsiloxane (weight average molecular weight: 1500) as main components is manufactured.
Using ethanol as a solvent, terminal silanol polydimethylsiloxane: tetraisopropoxytitanium: ethyl acetoacetate: water: silicon 0.375: 1: 2: 2: 0.125
And the mixture was sufficiently stirred for 0.5 hours to prepare an organic / inorganic hybrid sol solution. The substrate to which the coating solution was applied was an aluminum shaft. The surface of the aluminum shaft was sufficiently cleaned, and the aluminum-shaft was set on a flow coat machine, and the organic-inorganic hybrid sol solution was applied onto the substrate. Then under air atmosphere,
Heat treatment was performed at 120 ° C. for 0.5 hour to form an organic-inorganic hybrid film on the surface of the substrate.

The thickness of the organic-inorganic hybrid film obtained in Comparative Example 2 was 25.0 μm, and the contact angle with water was 10
3.7 °, the volume resistivity was 8.81 log Ω · cm.

Comparative Example 3 A conductive film composed of a metal oxide film was prepared in order to compare the contact angle of the conductive organic / inorganic hybrid film with water. A mixed solution A in which tetraisopropoxytitanium and ethanol are mixed at a molar ratio of 1: 4, and water, ethanol and hydrochloric acid at a molar ratio of 1: 4: 0.
08, and a mixed solution B was slowly added dropwise to the mixed solution A while stirring with a stirrer to hydrolyze the tetraisopropoxy titanium,
A Ti sol solution was used. The sol was further stirred for 0.5 hour to sufficiently hydrolyze the tetraisopropoxytitanium and partially polymerize it by dehydration. The sol solution after hydrolysis is further provided with an average particle diameter of 16 nm as a conductive filler.
Was added to the sol solution at 1.5% by weight and mixed and stirred to prepare a coating solution. The mixing and stirring
The organic / inorganic hybrid sol solution to which the conductive filler was added was stirred for 10 minutes by a planetary stirrer. The base material to which the coating liquid was applied was an aluminum shaft. The surface of the aluminum shaft was sufficiently cleaned, and the surface was set on a flow coat machine, and the coating liquid was applied on the base material. Then, at 120 ° C under air atmosphere.
Heat treatment was performed for 5 hours at 350 ° C. for 0.1 hour to form a conductive metal oxide film on the substrate surface.

The thickness of the conductive metal oxide film obtained in Comparative Example 3 was 5.0 μm, and the contact angle with water was 76 °.

Comparative Example 4 In the same manner as in Comparative Example 3, a conductive metal oxide film containing silicon as an inorganic component was prepared.

The thickness of the conductive metal oxide film obtained in Comparative Example 4 was 5.0 μm, and the contact angle with water was 66 °.

The conductive organic-inorganic hybrid coatings of Examples 1, 2 and 3 are flexible with little shrinkage due to heating, so that cracks can be prevented from occurring. Further, the conductive organic / inorganic hybrid film has a contact angle with water of 100 ° or more, and is excellent in toner releasability as is clear from comparison with Comparative Examples 3 and 4.

The conductive organic / inorganic hybrid film of this embodiment is a conductive film in which the conductive filler is uniformly dispersed in the film and the volume resistivity is uniform.

[0047]

According to the present invention, the sol-gel method provides flexibility,
It is possible to provide a conductive film excellent in adhesion to a substrate and toner release properties, that is, a conductive organic / inorganic hybrid hybrid film.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 15/02 101 G03G 15/02 101 4D075 15/08 501 15/08 501D 4J002 15/16 103 103/16 103 4J038 15/20 102 15/20 102 5G301 21/10 H01B 1/14 5G307 H01B 1/14 1/18 1/18 5/14 Z // H01B 5/14 G03G 21/00 312 (72) Inventor Shinto Takuya 1900, Ifuna-cho, Suzuka-shi, Mie F-term (reference) in Suzuka Fuji Xerox Co., Ltd. DB13 DB14 DB48 DB50 DB53 DC19 DC21 DC24 EA12 EB16 EB43 EC08 EC13 4J002 BM002 CE002 CM012 CP031 CP051 CQ031 DA026 DA036 DE106 DE126 DE136 DG046 DK006 FA082 FA086 FB266 FD112 FD116 GH00 4J038 AA011 CK022 CR072 DL031 DM021 HA026 HA216 HA441 KA12 KA15 MA02 NA20 PC02 PC03 PC08 5G301 DA18 DA19 DA23 DA28 DA32 DA42 5G307 GA01 GC

Claims (3)

[Claims] 1. An organic / inorganic hybrid film comprising a metal and / or metalloid alkoxide and an organosilicon compound formed by a sol-gel method, wherein a conductive filler is dispersed in the film. Organic / inorganic hybrid coating 2. The conductive organic / inorganic hybrid coating according to claim 1, wherein said conductive organic / inorganic hybrid coating is formed on a substrate. 3. The conductive organic / inorganic hybrid film according to claim 2, wherein said substrate is a conductive roll substrate or a conductive belt substrate for an electrophotographic apparatus.