JPH03107861A - Photoreceptive member for electrophotography having photoreceptive layer containing polysilane compound - Google Patents

Abstract

PURPOSE:To improve photosensitivity and to expand a photosensitive wavelength region by providing a photoreceptive layer consisting of a material mixture composed of a specific polysilane compd. and fine particles of non-single crystalline silicon contg. hydrogen or/and halogen atoms. CONSTITUTION:This member is constituted by mixing the polysilane compd. which is expressed by formula I and has 6,000 to 20,000 weight average mol. wt. and the fine particles of non-SiHX. In the formula I, R1 denotes 1 or 2C alkyl group; R2 denotes 3 to 8C alkyl group, cycloalkyl group, etc.; R3 denotes 1 to 4C alkyl group; R4 denotes 1 to 4C alkyl group, respectively. A, A' are respectively 4 to 12C alkyl group, cycloalkyl group, etc., and both may be the same or different; n and m denote the molar ratio which indicates the ratio of the respective monomer numbers to the total monomer in the polymer; n+m=1; 0<n<=1, 0<=m<1. The improved sensitivity, the decreased residual potential and ghosts and the expanded spectral sensitivity region are attained in this way.

Description

Detailed description of the invention [Technical field to which the invention pertains] The present invention relates to non-single crystal silicon (hereinafter referred to as rnon) containing hydrogen and/or halogen atoms in a polysilane compound.
-3i It is abbreviated as HXJ. The present invention relates to a novel electrophotographic light-receiving member having a light-receiving layer made of a mixed material in which fine particles of the following are dispersed.

[Description of prior art]

Polysilane was reported to be solvent-insoluble [The Journal of the American Chemical Society 125 2291pp (+924)], but in recent years it has been reported that polysilane is solvent-soluble and can be easily formed into a film. [The Journal of American Ceramic Society launched 504pp (197B
)) began to attract attention. Furthermore, since polysilane photodecomposes when irradiated with ultraviolet rays, research has been reported to apply it to resists [JP-A-6098431, JP-A-6O
-119550).

In addition, polysilane has the property of a photosemiconductor in which charge can be transferred through the σ-bonds in the main chain [Physical Review B Main 5, 2818pp (1987)], and its application to electrophotographic photoreceptors is also expected. Ta. However, in order to be applied to such electronic materials, polysilane compounds must not only be soluble in solvents and have the ability to form films, but must also be able to form films without minute defects and with high homogeneity. . Since even minute defects are unacceptable in electronic materials, there is a demand for high-quality polysilane compounds that have clear substituent structures and do not cause abnormalities in film formation.

Although there have been various reports on synthetic research on polysilane compounds, there are still problems with their use in electronic materials.

Among low-molecular-weight polysilane compounds, a structure in which all Si groups are substituted with organic groups has been reported [The Journal of the American Chemical Society (J
our own of A+werican Chemic
al 5ociety, 9↓(11).

3806pp, 1972), Special Publication No. 63-38033)
.

The structure described in the former publication has a structure in which the terminal group of dimethylsilane is substituted with a methyl group, and the structure described in the latter publication has a structure in which the terminal group of dimethylsilane is substituted with an alkoxy group. It also has a degree of polymerization of 2 to 6, and does not exhibit the characteristics of a polymer. In other words, due to its low molecular weight, it does not have film-forming ability as it is, and is difficult to use industrially.

A high molecular weight polysilane compound with a structure in which all Si groups are substituted with organic groups has recently been reported [Nikkei New Materials August 15 issue, page 46 (1988)], L
However, since it involves a special reaction intermediate, a decrease in the synthesis yield is expected, making industrial mass production difficult.

In addition, the method for synthesizing polysilane compounds was published in The Journal.
Op Organometallic Chemistry 198pp
C27 (1980) or The Journal of Polymer Science, Polymer Chemistry Edisilane Vol, 22159-170pp (1984)
Reported by.

However, all of the reported synthesis methods involve only the condensation reaction of the polysilane main chain, and there is no mention of the terminal groups, and in all of the synthesis methods, unreacted chlorine groups and byproducts are generated due to side reactions. Therefore, it is difficult to consistently obtain the desired polysilane compound.

Examples of using the above-mentioned polysilane compounds as photoconductors have also been reported (U, S, P, ll&h461
8551, U, S, P, 4772525, JP-A-62
-269964>, the influence of unreacted chlorine groups and by-products due to side reactions is presumed.

In U, S, P, NQ4618551, the above polysilane compound is used as an electrophotographic photoreceptor, but -m
In the copying machine, the applied potential is only 500 to 800■,
An abnormally high applied potential of 1000V is used. This is thought to be because, at a normal potential, structural defects in polysilane cause defects in the electrophotographic photoreceptor, and the abnormal spot-like phenomenon on the image disappears. Also, JP-A No. 62-269964
An electrophotographic photoreceptor was fabricated using the above-mentioned polysilane compound and its photosensitivity was measured, but the photosensitivity is slow and it has no advantage over conventionally known selenium photoreceptors or organic photoreceptors. .

There are still many problems that need to be solved before they can be used in such electronic materials, and the reality is that no industrially usable polysilane compound has yet been provided.

On the other hand, electrophotographic light-receiving members using non-5jHX have been put into practical use due to their advantages such as high durability, high stability, and high sensitivity, and have been highly evaluated.

However, non-3iHX electrophotographic light-receiving members are made by decomposing raw material gas using a glow discharge decomposition method and dissolving non-3iHX onto a support.
-S i HX is manufactured by uniformly depositing it, but the technology is so advanced that it is currently only possible to put it into practical use by some companies with very advanced technology. Therefore, the actual situation is that the cost is somewhat higher than conventionally known selenium photoreceptors and organic photoreceptors.

[Purpose of the invention]

The present invention has a weight average molecular weight of 6000 to 200 as described below.
000, a photoreceptive layer composed of a specific mixture of non-3i HX1 particles dispersed in a previously unknown polysilane compound in which all of the substituents and terminal groups of polysilane are substituted with specific organic groups. An object of the present invention is to provide a light-receiving member for electrophotography.

Another object of the present invention is to provide an electrophotographic light-receiving member that is more sensitive and sensitive to a wider wavelength range than conventional electrophotographic light-receiving members using polysilane compounds.

Still another object of the present invention is to provide an electrophotographic light-receiving member that has higher charging ability than conventional inorganic electrophotographic light-receiving members such as a-5e.

A further object of the present invention is to provide an electrophotographic light-receiving member using a polysilane compound, which is shallower and has less afterimage than conventional electrophotographic light-receiving members using polysilane compounds.

[Structure and effects of the invention]

The electrophotographic light-receiving member of the present invention that achieves the above object includes:
It is represented by the following general formula (1) and has a weight average molecular weight of 6000.
200,000 to 200,000, and a novel polysilane compound previously unknown, and
1) ■ Rt Ra [However, in the formula, R3 is an alkyl group having 1 or 2 carbon atoms, R
2 is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group,
R8 is an alkyl group having 1 to 4 carbon atoms, R4 is an alkyl group having 1 to 4 carbon atoms, A and A' are each an alkyl group having 4 to 12 carbon atoms, It is a cycloalkyl group, an aralkyl group, or an aralkyl group, and both may be the same or different.

n and m are molar ratios indicating the ratio of the number of each monomer to the total monomers in the polymer, n+m=1, and Q<n≦1.0≦rl<l. ) non-
It is characterized by having a light-receiving layer composed of a mixed material with fine particles of 3i HX.

The novel polysilane compound represented by the general formula (+) and having a weight average molecular weight of 6,000 to 200,000 used in the present invention has no chlorine group or side reaction product group,
All St groups are substituted with specific organic groups that do not have oxygen, are non-toxic, and are compatible with aromatic solvents such as toluene, benzene, xylene, dichloromethane, dichloroethane, chloroform, carbon tetrachloride, etc. halogenated solvent,
It is easily soluble in other solvents such as tetrahydrofuran (THF) and dioxane, and has excellent film-forming ability. The film formed using the polysilane compound of the present invention is homogeneous and has a uniform thickness, has excellent heat resistance, and has high hardness and toughness.
ss).

As mentioned above, the novel polysilane compound represented by the general formula (1) used in the present invention has a weight average molecular weight of 6,000 to 200,000, but from the viewpoint of solubility in solvents and film-forming ability. It is more preferable to have a weight average molecular weight of 500 to 1200.
00, and the optimal one has a weight average molecular weight of to
oo.

80,000 to 80,000.

Regarding the weight average molecular weight, those with a weight average molecular weight of 6,000 or less do not exhibit the characteristics of polymers and have no film-forming ability, while those with a weight average molecular weight of 200,000 or more have poor solubility in solvents and cannot be used to form the desired film. Difficult to form.

In addition, when the above-mentioned polysilane compound represented by the formula (r) is particularly desired for the film to be formed, the terminal groups A and A' may be an alkyl group having 5 to 12 carbon atoms, or an alkyl group having 5 to 12 carbon atoms. The group is preferably selected from the group consisting of a cycloalkyl group, an aralkyl group, and an aralkyl group.

The most preferred polysilane compound of the present invention in this case is:
This is the case where the terminal groups A and A' are groups selected from alkyl groups having 5 to 12 carbon atoms and cycloalkyl groups having 5 to 12 carbon atoms.

The above-mentioned polysilane compound used in the present invention can be synthesized as follows. That is, under a high-purity inert atmosphere free of oxygen and moisture, a dichlorosilane monomer is brought into contact with a condensation catalyst made of an alkali metal to perform halogen elimination and condensation polymerization to synthesize an intermediate polymer.
The obtained intermediate polymer is separated from unreacted monomers, and a predetermined halogenated organic reagent is reacted with the intermediate polymer in the presence of a condensation catalyst consisting of an alkali metal to form an organic group at the end of the intermediate polymer. It is synthesized by condensing.

In the above synthesis operation, the dichlorosilane monomer as the starting material, the intermediate polymer, the halogenated organic reagent, and the alkali metal condensation catalyst are all highly reactive with oxygen and moisture, so these oxygen and moisture are present. The above-mentioned polysilane compound used in the present invention cannot be obtained under such an atmosphere.

Therefore, it is necessary that the above-mentioned operations be carried out in an atmosphere free of both oxygen and moisture. For this reason, care must be taken regarding the reaction vessel and all reagents used to ensure that neither oxygen nor moisture is present in the reaction system.For example, regarding the reaction vessel,
Vacuum suction and argon gas replacement are performed in the blow box to prevent moisture and oxygen from being adsorbed into the system. In any case, the argon gas used is previously passed through a silica gel column to dehydrate it, and then the copper powder is passed through a column heated to 100° C. for deoxidation treatment.

The dichlorosilane monomer as a starting material is introduced into the reaction system after being distilled under reduced pressure using the above-mentioned argon gas which has been deoxygenated immediately before introduction into the reaction system.

The halogenated organic reagent and the solvent used for introducing a specific organic group are also deoxidized in the same manner as the dichlorosilane monomer before being introduced into the reaction system.

Note that the solvent is deoxidized by distilling it under reduced pressure using the deoxygenated argon gas described above, and then further dehydrating it with metallic sodium.

The above condensation catalyst is used in the form of wires or chips, and the wires or chips are formed in an oxygen-free paraffinic solvent to prevent oxidation.

The dichlorosilane monomer as a starting material used in producing the polysilane compound represented by the above-mentioned general formula (1) is a silane compound represented by the general formula: RtRtSiC1g described later, or a silane compound represented by the general formula: RtRtSiC1g, or a combination thereof.
Silane compounds of the designation i Clt are selectively used.

As the above-mentioned condensation catalyst, an alkali metal capable of causing a condensation reaction by eliminating halogen is preferably used, and specific examples of the alkali metal include lithium, sodium, and potassium, with lithium and sodium being preferred.

The above-mentioned halogenated organic reagents are for introducing substituents represented by A and A', and include halogenated alkyl compounds, halogenated cycloalkyl compounds, halogenated teryl compounds, and halogenated aralkyl compounds. A suitable compound selected from the group consisting of compounds, i.e. formula -i:
It is represented by A-X and/or the formula: A'-X (where X is CI or Br), and an appropriate compound among the specific examples described below is selectively used.

General formula used in synthesizing the above-mentioned intermediate polymer: R+RzSiC[, or - formula: R5Ra
The dichlorosilane monomer represented by 5iC1x is dissolved in a predetermined solvent and introduced into the reaction system, and a paraffinic nonpolar hydrocarbon solvent is preferably used as the solvent. Preferred examples of the solvent include n-hexane, n-octane, n-nonane, n-dodecane, cyclohexane and cyclooctane.

Since the resulting intermediate polymer is insoluble in these solvents, it is convenient to separate the intermediate polymer from unreacted dichlorosilane monomers.The separated intermediate polymer is then treated with the above-mentioned halogenated organic reagent. In this case, both are dissolved in the same solvent and subjected to the reaction. In this case, aromatic solvents such as benzene, toluene, and xylene are preferably used as the solvent.

When condensing the above-mentioned dichlorosilane monomer using the above-mentioned alkali metal catalyst to obtain a desired intermediate, the degree of polymerization of the resulting intermediate polymer can be controlled appropriately by adjusting the reaction temperature and reaction time. . However, the reaction temperature at that time is preferably set between 60°C and 130°C.

A preferred method for producing the above-mentioned polysilane compound represented by the general formula (1) described above will be described below.

That is, the method for producing the above-mentioned polysilane compound used in the present invention includes (i) the step of producing an intermediate polymer, and (ii> adding substituents A and A' to the terminals of the cough intermediate polymer.
It consists of a process of introducing.

The step (i) above is performed as follows.

That is, the reaction system in the reaction vessel is completely free of oxygen and moisture and is dominated by argon and maintained at a predetermined internal pressure.
Add an oxygen-free paraffinic solvent and an oxygen-free condensation catalyst,
Next, an oxygen-free dichlorosilane monomer is added, and the whole is heated to a predetermined temperature while stirring to effect condensation of the monomer. At this time, the degree of condensation of the dichlorosilane monomer is
The reaction temperature and reaction time are adjusted to produce an intermediate polymer with a desired degree of polymerization.

In this reaction, as shown in the reaction formula (i) below, the chloro group of the dichlorosilane monomer and the catalyst cause a desalting reaction, and the Si groups repeat condensation to form a polymer, producing an intermediate polymer. do.

R+ Rs CI-ESt-1-1st-st, Cl...
(i) R's R4 The specific reaction procedure here is to prepare a condensation catalyst (alkali metal) in a paraffinic solvent,
Dichlorosilane monomer is added dropwise while stirring under heat. The degree of polymerization is confirmed by sampling the reaction solution.

Polymerization can be easily confirmed by determining whether or not a film can be formed by volatilizing the sampling liquid.

As the condensation progresses and a polymer is formed, it becomes a white solid that precipitates out of the reaction system. Here, it is cooled, and the solvent containing the monomer is separated from the reaction system by decantation to obtain an intermediate polymer.

Then, the step (b) above is performed. That is, the chloro group at the end group of the obtained intermediate polymer is subjected to desalting condensation using a halogenated organic agent and a condensation catalyst (alkali metal), and the polymer end group is replaced with a predetermined organic group.

The reaction at this time is represented by the following reaction formula (ii).

R+ Rs CI -壬Si→KO"-1,000 St→1- CPRt
Ra Now, specifically, an aromatic solvent is added to dissolve an intermediate polymer obtained by condensation of dichlorosilane monomers, a condensation catalyst (alkali metal) is added, and a halogenated organic agent is added dropwise at room temperature. . At this time, in order to compete with the condensation reaction between polymer terminal groups, a halogenated organic agent is added in an excess amount of 0.01 to 0.1 times the starting monomer. Gradually heat and stir at 80°C to 100°C for 1 hour to carry out the desired reaction.

After the reaction is completed, the mixture is cooled and methanol is added to remove the alkali metal of the catalyst. 8. Next, the polysilane compound produced is extracted with toluene and purified using a silica gel column. The desired polysilane compound used in the present invention is thus obtained.

(Margin below) R3 R3 A -+Si÷n--±Si+1- A'... (i
i) 2 R1 R+Rt 5iCj! 2 R, R, 5iCj! z
Note): Among the following compounds, a-2 to 16, 18, 20
, 21° 23.24 is used for Il, R, 5iCj' z, a-1° 2.11, 17, 19, 22, 23.2
5 is used for R2Ra, SiCIt z.

(013) zsic Itz -1 Gls(Oh)">5iCIlt l3 0h(Oh)"n5..

H3 (a10'H>S,.,.

H3 Island (C1h) “\Si14g OI3/ -9 -10 -11 -12 0“0”ゝ゛〉5. . ,2 island 0'1゛n5iC1z island (OIJ*cO1>s+.7, Possible.

0Is(Oli)s>3.6. .

0, (α).

-16 -17 -18 -19 ((CIIJ zoo) zsic ta-η -C1 island-o-C1 island+CI =O-O-C- ((OIJ 2C) zsic 1 tA-X and A
' -X concrete second (C1h) ZCIIOIZCI Cl1z (C1h) aCI CII+ (C1l□), CI C) I: + (aIz) + eCI! ku, FuC1 Q and 1oCj2 b-12 departure (Chapter (,1b-13 -25 C1l, (island), Br b-14C
Ils(CHz)+aBr b-1,
5gΣBr b46 GBrb-17 -5 As the catalyst, an alkali metal is preferable.

Lithium, sodium, and potassium are used as alkali metals. It is preferable that the shape is wire-like or chip-like to increase the surface area.

Book in Polysilanizer used shellfish example island C1l.

01x (012) s-+Si +T(Of2)sQ
(3-18 Of(CH3)t CI(CH3)2 Island CH3 II3 C113 CHl Cll3 C1(.

113 Oh (Oh) 3 CI(.

Cll.

(Of□).

Cll3 l13 CI-1゜ C11゜ 13 Cll.

Note) 2. Both X and Y in the above structural formula represent polymerized units of monomers. Then, n is determined by the formula of X/(x+Y), and m is determined by the formula of Y/(X+Y).

[Synthesis example]

The polysilane compound used in the present invention will be explained in more detail below using synthesis examples, but the present invention is not limited by these synthesis examples.

Synthesis Example 1 A polysilane compound represented by the following formula was synthesized by the following procedure.

CI'h A three-way flask was prepared in a blow box that had been vacuum-suctioned and replaced with argon, a reflux condenser, a thermometer, and a dropping funnel were attached to it, and argon gas was passed through the bypass pipe of the dropping funnel. 00 g of dehydrated dodecane and 0.3 mol of wire-shaped sodium metal were placed in this Mitsuro flask and heated to 100° C. with stirring.

Next, 0.1 mol of dichlorosilane monomer (manufactured by Chisso ■) shown by the following formula was dissolved in 30 grams of dehydrated dodecane, and the prepared solution was slowly dropped into the reaction system. 10 after dripping
A white solid was precipitated by condensation polymerization at 0° C. for 1 hour. This was followed by cooling, decanting the dodecane, adding 100 grams of dehydrated toluene to dissolve the white solid, and adding 0.01 mole of sodium metal. Next, n-hexyl chloride (CHs(C
A solution prepared by dissolving 0.01 mol of sCj (manufactured by Tokyo Kasei) in 1 Oml of toluene was slowly added dropwise to the reaction system with stirring, and heated at 100° C. for 1 hour.

After this, it is cooled and the excess metal sodium is disposed of.
Methanol 50mj! was slowly dripped.

This produced a suspended layer and a toluene layer. Next, the toluene layer was separated, concentrated under reduced pressure, and purified by developing with silica gel column chromatography to obtain a polysilane compound. The yield was 62%.

The weight average molecular weight of this polysilane compound was 77.000 as measured by THF development using the GPC method (
polystyrene as standard).

For identification, IR produced a KBr pellet and N1cole
t FT-I R750 (-Kore-Japan type)
It was measured by As a result, L250cn-' and 800cm-' which are attributed to the bond between the Si atom and the methyl group, and 1430 which is attributed to the bond between the Si atom and the phenyl group
Absorption peaks were confirmed around c1' and around 1100 cm-', around 2900 cm-' and around 1470 am-' which belong to the -methyl group, and around 1450c+++-' and around 730c+g-' which belong to the methylene group.

In addition, for NMR, the sample is dissolved in CD (1!3) and FT
-NMR, measured by FX-POQ (JEOL Ltd.). As a result, 0, which belongs to the bond between Si atom and methyl group,
Around 60 ppm, around 7 and 21 ppa attributed to the bond between Si atom and phenyl group, methyl group or 5t-CH3
- around 1, 10 pp+ll belonging to the group, and f
An absorption peak near 1,61 pp+i, which is attributed to the CHZ group, was confirmed.

In addition, in the polysilane compound obtained by the present invention,
Around 530 cm-' attributed to unreacted 5i-CI group,
1 assigned to the 5i-0-3i and 5iO-R groups of the by-products. There was no IR absorption peak near OOcm-'.

Bottom unevenness 1 A polysilane compound shown by the following formula was synthesized by the procedure shown below.

A three-way flask was prepared in a blow box that had been vacuum-suctioned and replaced with argon, a reflux condenser, a thermometer, and a dropping funnel were attached to it, and argon gas was passed through the bypass pipe of the dropping funnel. 100 grams of dehydrated n-hexane and 0.3 mole of metal sodium in 1 fl cube were charged into this Mitsuro flask, and heated to 80°C while stirring.
Dichlorosilane monomer (
0.1 mole (manufactured by Chisso) was dissolved in 30 grams of dehydrated n-hexane, and the prepared solution was slowly dropped into the reaction system.
A white solid was precipitated by condensation polymerization at ℃ for 1 hour. After cooling, the n-hexane was decanted and 100 grams of dehydrated toluene was added to dissolve the white solid, and 0.01 mole of sodium metal was added. Next, a solution prepared by dissolving cyclohexyl chloride (manufactured by Tokyo Kasei > o, oi mol) shown in the following formula in 10 ml of toluene was slowly added dropwise to the reaction system with stirring, and heated at 80°C for 1 hour. After cooling, 5 methanol was added to remove excess metal sodium.
0ml was slowly added dropwise. This produced a suspended layer and a toluene layer. Next, the toluene layer was separated, concentrated under reduced pressure, and purified by developing with silica gel column chromatography to obtain a polysilane compound. The yield was 55%. The weight average molecular weight of this polysilane compound is 30
,000.

As a result of IR measurement, the Si
1450 cm attributed to the bond between an atom and a cyclohexyl group
Absorption peaks around -' and around 1150 cm-' were confirmed.

In addition, as a result of NMR measurement, the Q attributable to the bond between the Si atom and the methyl group is around 60 ppm, the Q attributable to the bond between the Si atom and the cyclohexyl group is around 1, 58 ppIl, and around 2.04 ppn+, and the Q attributable to the bond between the Si atom and the phenyl group is around 1,58 ppIl and 2.04 ppn+. The absorption peak near 7,2ipp... which is attributed to the bond is i! It has been certified.

In addition, in the polysilane compound obtained by the present invention,
There was no rR absorption peak around 530c1-, which is attributed to the unreacted 5i-C1 group, and around 1100 cm-', which is attributed to the 5i-0-3i group and Si-〇-R group of the by-products.

Synthesis Example 1 except that 0.05 mol of each of the two types of dichlorosilane monomers (nitrogen type) shown in the following formula was used and the same chlorobenzene as in Synthesis Example 2 was used as the end group treatment material. A polysilane compound represented by the following formula was synthesized using a similar procedure. The yield was 58%.

The weight average molecular weight of this polysilane compound is 55.000
Met.

As a result of IH measurement, 1 is attributed to the bond between the Sr atom and the methyl group, around 250cm-' and around 800c11-', and 14 is attributed to the bond between the Si atom and the cyclohexyl group.
Absorption peaks near 50(s-' and 1150al-', near 1430e@-' and near 1100cm-', which are attributed to the bond between the Si atom and the phenyl group) were confirmed.

In addition, as a result of NMR measurement, around 0 and 60 ppm are attributed to the bond between Si atom and methyl group, around 1 and 58 ppm and around 2.0411p are attributed to the bond between Si atom and cyclohexyl group, and around 2.0411p are attributed to the bond between Si atom and phenyl group. Attribute to the bond? , the absorption peak around 21pp- is i! It has been certified.

Further, the copolymerization ratio of the silane monomer was determined from the number of protons in NMR.

In addition, in the polysilane compound obtained by the present invention,
The IRI around 5301-1 attributed to the unreacted 5j-C1 group, and around l l 00cm-' attributed to the s + -o-s + group and 5iO-R group of the by-products! All Jl yield peaks were not present.

In Synthesis Example 2, a polysilane compound represented by the following formula was prepared in the same manner as in Synthesis Example 2, except that 0.01 mol of benzyl chloride (Kanto Chemical type) represented by the following formula was used as the terminal group treatment material. Obtained. The yield was 67%.

The weight average molecular weight of this polysilane compound is 63.000
Met.

As a result of IR measurement, 1250c1' and 800cm-' which are attributed to the bond between Si atom and methyl group,
1450 attributed to the bond between Si atom and cyclohexyl group
Absorption peaks were observed near a1-' and around 1150 cm-', around 1450 well-' which is attributed to the bond between the Si atom and the methylene group, and around 1600 well-' which is attributed to the benzyl group.

In addition, as a result of NMR measurement, around 0.60 flp- is attributed to the bond between the Si atom and the methyl group, around 1.58 ppm+ is attributed to the bond between the Si atom and the cyclohexyl group, and 2. Absorption peaks were observed around O4 ppm, around 1,78 pp+II, which is attributed to the bond between the Si atom and the methylene group, and around 7,25 ppm, which is attributed to the benzyl group.

In addition, in the polysilane compound obtained by the present invention,
Around 530 cm-' attributed to unreacted 5i-CI2 group, by-product (7) S i -0-3i group and St-〇-
There was no IR absorption peak near 1100 cm-' attributed to the R group.

The non-3t HXi particles used in the present invention are produced as follows.

Non-S i Hxi powder particles used in the present invention, R
Preferably, it is produced by a glow discharge decomposition method such as an F glow discharge decomposition method or a microwave glow discharge decomposition method.

Examples of substances that can be used as the Si supply gas used in the glow discharge decomposition method include SiH.

Gaseous or gasifiable silicon hydride (silanes), such as 5ixH*, 5isHs, and 5iaH+o, can be used effectively, and they are also easy to handle during layer fabrication work, have good Si supply efficiency, etc. In terms of S i H
Preferred examples include 4,5jzHi. In addition, these Si supply gases may be converted into H, He, He,
It may be used after being diluted with a gas such as Ar or Ne.

Effective gases for supplying halogen used in the present invention include many halogen compounds, such as halogen gases, halides, interhalogen compounds, halogen-substituted silane derivatives, etc., in gaseous or gasified form. Examples include halogen compounds.

Furthermore, silicon hydride compounds containing halogen atoms (X), which are in a gaseous state or can be gasified and whose constituent elements are silicon atoms (St) and halogen atoms (X), are also effective in the present invention. can be mentioned.

Specifically, halogen compounds that can be suitably used in the present invention include halogen gases such as fluorine, chlorine, bromine, and iodine, BrF, Cj! F, Cj! Fs.

BrF5. BrF7. IFF, IFt, Ice.

Interhalogen compounds such as IBr can be mentioned.

Specifically, silicon compounds containing a halogen atom (X), so-called silane derivatives substituted with a halogen atom (X), include, for example, S i F4, 5izF* +5IC
Preferred examples include silicon halides such as Ila and 5iBra.

By employing such a silicon compound containing a halogen atom (X) and using a glow discharge method, the characteristic non-3 of the present invention can be produced.
In order to form iHX fine particles, halogen atoms <
> can be formed.

According to the glow discharge method, no containing halogen atoms (X)
In the case of forming n-3i fine particles, non-31 fine particles can basically be formed by using silicon halide as a Si supply gas, but when hydrogen atoms (H) In order to make the introduction ratio easier, a desired amount of hydrogen gas or a silicon compound gas containing hydrogen atoms may be mixed with these gases.

Moreover, each gas may be used not only as a single species but also as a mixture of multiple species at a predetermined mixing ratio.

In the present invention, the above-mentioned halogen compounds or silicon compounds containing halogen atoms (X) are effectively used as the halogen atom supply gas, but in addition, HFHCj! , HBr, hydrogen halides such as Hl, 5tHsF, 5iH1F, 5iHFs,
5iHzlz.

S i H2CAz, S i HCl2, S
Materials in a gaseous state or capable of being gasified, such as halogen-substituted silicon hydrides such as i HzBrzSiHBrt, can also be mentioned as effective raw materials for forming fine particles.

Among these substances, halides containing hydrogen atoms (H) are extremely effective for controlling electrical or optical properties at the same time as introducing halogen atoms (X) into fine particles during formation of fine particles. Since H) is also introduced, it is used as a suitable halogen supply gas in the present invention.

In order to structurally introduce hydrogen atoms (H) into fine particles, in addition to the above, ■ (2, or S L Ha, 5i2Ha
.

This can also be carried out by causing a discharge by causing silicon hydride such as 5isH*, 5i4H+o, and the above-mentioned Si supply gas to coexist in the deposition chamber.

In order to control the amount of hydrogen atoms (H) and/or halogen atoms (X) that can be contained in the present invention, for example, the support temperature and/or hydrogen atoms (H) or halogen atoms (X) can be controlled. The amount of raw material used for this purpose introduced into the deposition apparatus system, the discharge power, etc. may be controlled.

In the present invention, hydrogen atoms (H) contained in fine particles
The amount is preferably 1 to 40 at%, more preferably 5 at%.
~30at%, optimally 5-20at%.

Further, the amount of halogen atoms (X) contained in the fine particles is preferably 0.01 to 40 at%, more preferably 0.
．． 01 to 30 at%, optimally 0.01 to 10 at%.

Furthermore, the hydrogen content and the halogen content are organically related, and when the hydrogen content is large, the halogen content should be as small as possible.

In addition, the bonding state of hydrogen atoms and silicon atoms is non-3
This has a great influence on the optical and electrical properties of iHX particles. The desirable bonding state between a hydrogen atom and a silicon atom is -5r-H, where one hydrogen atom is bonded to a silicon atom.
The structure is The bond state is 2 in the measurement of infrared absorption.
An absorption peak is observed near 000as-'. When the non-S i HX fine particles are mixed and dispersed in the polysilane compound represented by formula (1),
The average particle size of the 3i HXli particles is preferably 1 to 10 μm from the viewpoint of obtaining electrophotographic properties and economical effects.

Further, the proportion of non-5i HXlt particles dispersed in polysilane is preferably 1 to 30% by weight based on polysilane, in order to effectively achieve the object of the present invention. If the dispersion ratio of non-S i HX fine particles into polysilane increases further, polysilane and non-S
i The number of interfaces between HXi powder particles increases, and non-S
The transportability of photoexcited carriers generated in iHX after they move to polysilane deteriorates, and electrophotographic properties such as residual frost and afterimage deteriorate.

On the other hand, if the proportion of non-3i HX is lower than the above range, the generation rate of photoexcited carriers will decrease, resulting in a decrease in electrophotographic sensitivity.

non-SiHX having characteristics that can achieve the purpose of the present invention
In order to form fine particles consisting of, it is necessary to appropriately set the gas pressure in the deposition chamber and the temperature of the support as desired.

The optimum range for the gas pressure in the deposition chamber is selected as appropriate, but usually I x 10-' to 1. O Torr - preferably l x 10"' to 3 Torr S optimally l x l
It is preferable to set it as 0-' to I Torr.

Amorphous silicon (a-5
(abbreviated as iHX), the support temperature (Ts) is appropriately selected in the optimum range according to the particle design, but is usually 50 to 400°C, preferably 10°C.
It is desirable to set it as 0-300 degreeC. Non-3 fine particles
i HX as poly 5i(I(.

When X) is selected and configured, there are various methods for forming the fine particles, including the following methods.

One method is to adjust the support temperature and high temperature, specifically 40
In this method, the temperature is set at 0 to 600° C., and a film is deposited on the support by plasma CVD.

In the present invention, when fine particles consisting of non-3t are produced by the glow discharge method, the optimal range of discharge power supplied into the deposition chamber is selected as appropriate according to the fine particle design, but in normal cases, it is 5X10-' to 10W. /3, preferably 5X10-'~5W/cm', optimally IX
It is desirable to set it as 10-3-2 X 10-'W/cm3.

In the present invention, the above-mentioned ranges are mentioned as desirable numerical ranges for the gas pressure in the deposition chamber, the support temperature, and the discharge power supplied into the deposition chamber for producing fine particles, but the fine particle production factor usually depends on the Rather than being determined separately, it is preferable to determine the optimum value of the particle production factor based on mutual and organic relationships in order to form particles with desired characteristics.

In the present invention, non-S i HXi particles are formed by a glow discharge decomposition method as follows. A non-3iHX film is deposited on the support by glow discharge decomposition.

Next, the support on which the non-3iHX film has been deposited is taken out from the deposited film forming apparatus while the temperature of the support is still high, and is rapidly cooled to remove the non-S i I (X film from the support by W, I P
,'J let. The non-3iHX film peels off as fine particles.

In this way, non-3i Hxa particles are
3iHX film was deposited on the support and its ilt M
Since the non-3i Hxm particles are formed at a distance of 1 liter, the adhesion between the non-3i Hx film and the support is very important for the formation of non-3i Hxm particles.

In the present invention, the support used for forming the non-3iHX deposited film may be either electrically conductive or electrically insulating. Examples of the conductive support include metals such as NiCr, stainless steel, Cr, Mo, and PC, and alloys thereof.

Examples of the electrically insulating support include polyimide, Teflon, glass, ceramics (Altos, etc.), and the like.

In the present invention, non-3i HX from the above support
In order to facilitate the peeling of the film and reduce the width of particle size dispersion of the fine particles, it is necessary to
It is desirable that the HXl1l layer be deposited to a thickness of 1100 cr or more.

Next, an outline of the apparatus used for producing the non-3iHX film particles of the present invention and the production method using the same will be explained.

An example of an apparatus for producing non-3iHX fine particles is shown in FIGS. 2 to 4.

FIG. 2 shows a raw material gas supply device 1020 and a deposition device 100.
This is an apparatus for producing non-3iHX particles consisting of 0 by high frequency (hereinafter abbreviated as rRFJ) glow discharge decomposition method, and the following describes non-3i!
(The method for producing Xp particles will be explained.

In the gas cylinders 1071 and 1072 in the figure, raw material gas for forming the non-3iHX fine particles of the present invention is sealed, and 1071 is SiH4 gas (purity 99.9
9%) cylinder, 1072 is H2 gas (purity 99.999
9%) It is a cylinder. Moreover, when attaching the gas cylinders 1071 to 1072 to the raw material gas supply device 1020 in advance, each raw material gas is introduced from the valves 1051 to 1052 into the gas piping between the inflow valves 1031 to 1032.

In the figure, 1005 is a cylindrical stainless steel support, which is heated to a desired temperature by a heater 1014.

First, the valve 1051 of the gas cylinders 1071 to 1072
~1052, leak valve 1015 of deposition chamber 1001,
Make sure that the exhaust valve 1093 is closed, and also check that the inlet valves 1031 to 1032 and the outlet valve 1041 are closed.
~1042, auxiliary valve 1018, gate valve 100
Make sure that valve 7 is open, and then open main valve 1.
016 is opened and the deposition chamber 100 is opened by a vacuum pump (not shown).
1. Evacuate the storage chamber 1094 and gas piping.

Next, when the reading of the vacuum gauge 1017 becomes approximately lXl0T orr, the auxiliary valve 1018, the inflow valve
1032, close the outflow valves 1041-1042.

Thereafter, SiH gas is introduced from the gas cylinder 1071, and H gas is introduced from the gas cylinder 1072 by opening the valves 1051 to 1052 as appropriate, and the pressure of each gas is adjusted to 2 kt/cd by the pressure regulators 1061 to 1062.

Next, gradually open the inflow valves 1031 to 1032,
Mass flow controller 1021-1
022 as appropriate.

Next, gradually open the outflow valves 1041 to 1042 and the auxiliary valve 1018 to release 5IH4 gas and H! Gas is introduced into the deposition chamber 1 through the gas discharge hole 1009 of the gas introduction pipe 1008.
001 as appropriate. At this time, the mass flow controllers 1021 to 1022 adjust the SiH4 gas flow rate, H gas flow rate, and H gas flow rate to desired gas flow rates, respectively.

Next, while watching the vacuum gauge 1017, the opening of the main valve l016 is adjusted so that the pressure in the deposition chamber 1001 becomes the desired pressure. After that, the power of the RF power source (not shown) is set to the desired power, and the high frequency matching box 1012
RF power is introduced into the deposition chamber 1001 through the cylindrical stainless steel support 100 to generate an RF glow discharge.
After forming the non-3i HX layer with the desired thickness, the RF glow discharge is stopped, and the outflow valves 1041 to 1043 are closed to enter the deposition chamber 1001. Stop the inflow of gas, no
Finish forming the n-3IHX layer.

In addition, if necessary, during layer formation, a cylindrical aluminum support 100 may be used to make the layer structure uniform.
5 is rotated at a desired speed by a drive device (not shown).

FIG. 4 shows a deposition apparatus 1000 for the RF glow discharge decomposition method shown in FIG. 2, and a deposition apparatus 1100 for the microwave (hereinafter abbreviated as "μW") glow discharge decomposition method shown in FIG. This is an apparatus for producing non-3iHX fine particles by the μW glow discharge decomposition method, which is connected to the raw material gas supply apparatus 1020 by replacing the
A method for producing on-S i HXX powder particles will be explained.

In the figure, 1107 is a cylindrical stainless steel support, which is heated to a desired temperature by a heater (not shown).

First, as in the manufacturing method using the RF glow discharge decomposition method described above, the inside of the deposition chamber 1101 and gas piping is
Evacuate until the pressure of 101 becomes 5 x 10'' Torr, and transfer each gas to mass flow controllers 1021 to 1021.
1022. However, instead of the Hz gas cylinder, an S i F gas cylinder (purity 99.999%) is used.

Next, the outflow valves 1041 to 1042 and the auxiliary valve 1018 are gradually opened to allow the 5iHa gas and 5iFa gas to appropriately flow into the deposition chamber 1101 through the unillustrated gas discharge hole of the gas introduction pipe 1110. At this time, S iHa
Each mass flow controller 1021 to 102 is connected so that the gas flow rate, SiF, and the gas flow rate become the desired gas flow rate.
Adjust with 2.

Next, the opening of the main valve (not shown) is adjusted so that the pressure in the deposition chamber 1101 becomes a desired pressure while checking a vacuum gauge (not shown). After that, the power of a μW power source (not shown) is set to a desired power, and the waveguide 1103 and dielectric window 11 are
μW power is introduced into the plasma generation region 1109 through 02 to generate μW glow discharge to start forming a non-3i HX layer on the cylindrical stainless steel support 1107 to form a non-3i HXJM with a desired thickness. When the μW glow discharge is formed, the μW glow discharge is stopped, and the outflow valve 1041
1042 is closed to stop the gas from flowing into the deposition chamber 1101, and the formation of non-3i HXWl is completed.

Further, during layer formation, the cylindrical stainless steel support 1107 is rotated at a desired speed by a drive device (not shown) in order to ensure uniform layer formation.

In this way, a non-3iHX layer is deposited on the support. Immediately after depositing the non-3i HX layer on the support and while the support temperature is sufficiently high, the non-3i HX layer is removed from the deposition apparatus while the support temperature is sufficiently high.
The support on which the HX layer is deposited is taken out, and the non-3iHX layer is peeled off from the support by rapid cooling and/or vigorous shaking. In this way, nonSiHXm particles are produced. The particle size of the non-3i HXa particles can be controlled by the support temperature and cooling rate, but if necessary, they may be made into fine particles using a pulverizer using a jet stream.

Polysilane and nonssHX produced as above
Dispersion and mixing of one particle is performed as follows.

Polysilane is dissolved in an organic solvent such as cyclohexane, hexane, THF, toluene, benzene, etc., and non-3iH
Add the required amount of X fine particles to the solvent and mix and disperse with a blender.

When forming an electrophotographic light-receiving member, the polysilane and non
A light-receiving member for electrophotography is formed by applying a solvent in which -S i Hx fine particles are dispersed.

Suitable methods for application include day, ping, and spray methods.

After coating in this manner, the solvent is evaporated to form an electrophotographic photoreceptive layer in which non-3i HXI particles are dispersed in polysilane on the support.

〔Example〕

The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.

A Mitsuro flask was prepared in a blow box that had been vacuum-suctioned and replaced with argon, a reflux condenser, a thermometer, and a dropping funnel were attached to it, and argon gas was passed through the bypass pipe of the dropping funnel.

100 crumbs of dehydrated dodecane and 0.3 mol of wire-shaped sodium metal were placed in this Mitsuro flask, and heated to 100° C. with stirring. Next, 30 g of dehydrated dodecane was dissolved with 0, t mol of dichlorosilane monomer (Tisso 1 & Ri (a-7)), and the prepared solution was slowly added dropwise to the reaction system.

After the dropwise addition, a white solid was precipitated by condensation polymerization at 100° C. for 1 hour. After this time it was cooled, the dodecane was decanted and an additional 100 grams of dehydrated toluene was added to dissolve the white solid and 0.01 mole of sodium metal was added.

Next, n-hexyl chloride (manufactured by Tokyo Kasei) (b3)
A solution prepared by dissolving 0.01 mol in 1 Qml of toluene was slowly added dropwise to the reaction system with stirring, and heated at 100° C. for 1 hour. After this, 50mj of methanol was added to cool it and treat the excess metal sodium! was slowly added dropwise. As a result, a suspended layer and a toluene layer were formed.

Next, the toluene layer was separated, concentrated under reduced pressure, and purified by development using a silica gel column and chromatography to obtain polysilane compound ml (C-1).

The yield was 65%.

The weight average molecular weight of this polysilane compound was 75.000 as measured by THF development using the GPC method (using polystyrene as a standard).

For identification, IR is made of KBrBr pellet, N1coet
The measurement was carried out using FT-I R750 (Cole Japan!). Also, for NMR, the sample was dissolved in CDC1s and measured using FT-NMRFX-90Q (JEOL Ltd.). The results are shown in Table 1.

In addition, in the polysilane compound obtained by the present invention,
Unreacted 5t-C1, by-products 5i-0-3i, 5i
There was no IR absorption assigned to -0-R.

In addition, in this polysilane compound, unreacted 5i-
There were no IR absorptions attributed to C1, by-products 5i-0-5i, and 5L-O-R.

Next, non-3i HXlk particles were produced as follows.

non-3S HXll! was deposited on a stainless steel substrate using a deposition apparatus 1000 using an RF glow discharge decomposition method shown in FIG.

First, a stainless steel cylindrical support 1005 is placed in the deposition chamber l0.
It was installed in the support holder 1004 in 01. The internal pressure in the deposition chamber 1001 was evacuated to a level of 10-'' Torr using a mechanical booster pump and a rotary pump (not shown).

A stainless steel cylindrical support 1 is heated by a heating heater 1014.
005 was heated to 250°C. After the support temperature becomes constant, 5tHn gas cylinder 1071 and H1 gas cylinder 1
072 to valves 1051 and 1031104 respectively]
, 1052.1032.1042, mass flow controller 1021.1022 and auxiliary valve 1018, 500 sccva of SiH4 gas is introduced into the deposition chamber 1001.
500 sccm of Hz gas was introduced. Deposition chamber 1 at that time
The internal pressure in the 001 was adjusted to 0.2"orr using a mechanical booster pump and a rotary pump (not shown).

After the internal pressure in the deposition chamber 1001 is stabilized, RF power is applied to the cathode electrode of the deposition chamber 1001 from an RF power source (not shown) via a high frequency munching box 1012, with a power density of 0.
．． 035W/cd was introduced. And deposition chamber 1001
A glow discharge was caused to occur, and a 100 μm thick non-3i HX film was deposited on the stainless steel support 1005. non
After depositing the -3i HX film, the 5iHa gas and Hz gas were stopped, and the inside of the deposition chamber 1001 was sufficiently purged with Ar gas. The deposition chamber 1001 was leaked while the support temperature remained at 250° C., the support 1005 was taken out, and the support was rapidly cooled with water. In this way, non-3i HXpIQ was removed from the support.
was peeled off to produce nc+n-3i HX fine particles.

The average particle diameter of the non-3i HX fine particles thus produced was measured using a Coulter counter.

In other words, the measuring device is Coulter counter TA.
- An interface (manufactured by Nikkaki) that outputs the number distribution and volume distribution using the n-type (manufactured by Coulter) and CX-1
A personal computer (manufactured by Canon) is connected, and a 1% NaCR aqueous solution is prepared using primary sodium chloride as the electrolyte. As a measurement method, the electrolytic aqueous solution lOO~15
At 0 mA, add 0.1 to 5 rrl of a surfactant, preferably an alkylbenzene sulfonate as a dispersant, and further add 2 to 20 g of the measurement sample. The electrolytic solution in which the sample was suspended was dispersed for about 1 to 3 minutes using an ultrasonic disperser, and the particle size distribution of the particles was measured using the Coulter Counter TA-■ model using a 100μ aperture as an aperture. It was measured.

The average particle size of non-3iHX was 2 μm. Non-3iHXi particles were dispersed in the above polysilane to construct the electrophotographic light receiving member shown in FIG. 1.

In FIG. 1, an electrophotographic light-receiving member 100 has an Ann support 101. A light-receiving layer 102 made of polysilane in which non-3iHX fine particles of the present invention are dispersed and a free surface 10
It consists of 4.

The photoreceptive layer was formed as follows.

The polysilane was dissolved in toluene, 10% by weight of non-3i HXm particles were added to the polysilane, and the mixture was thoroughly mixed and dispersed using a blender. After the nonSiHXa particles are sufficiently dispersed in the polysilane solution, A7! A 50 μm thick photoreceptive layer consisting of a polysilane layer in which non-S i HX was dispersed was formed on the supporting frame.

The electrophotographic light-receiving member obtained in this example was transferred to a copying machine (
A Canon NP-6150 (modified for experimental use) was set to measure sensitivity, residual frost, ghost, and spectral sensitivity. Compared to the following comparative example using the conventional technology, the sensitivity is 10
Double improvement, residual frost reduced to 1/10, ghost also l/10
As a result, the spectral sensitivity extended to light of 700 nm.

Polysilane compound 1 was synthesized in the same manner as in Example 1, except that dichlorosilane monomer (manufactured by Chisso) (a-7) was condensed and the end groups of the polymer were not treated.
kD-1 was obtained. The yield was 60% and the weight average molecular weight was 46.
,000. The identification results are shown in Table 1.

In this polysilane compound, IR absorption attributed to unreacted 5i-C1 and by-product 5t-0-R was observed in the terminal group.

Such a polysilane compound is dissolved in toluene, and A
A light-receiving member for electrophotography was prepared by coating 50 μm onto a support by dipping. This light-receiving member for electrophotography was inserted into a copying machine (a Canon NP6150 modified for experimental use), and the electrophotographic properties were measured.

Chise ■1 A three-solo flask was prepared in a blow box that had been vacuum suctioned and replaced with argon, and a Reflags condenser, thermometer, and dropping funnel were attached to it, and argon gas was passed through the bypass pipe of the dropping funnel. .

0 g of dehydrated dodecane I O' and 0.3 mol of metal lithium of 1 dragon's angle were charged into this Mitsuro flask, and heated to 100° C. with stirring. Next, a solution prepared by dissolving 0.1 mol of dichlorosilane monomer (Chisso 1J) (a-7) in 30 grams of dehydrated dodecane was slowly added dropwise to the reaction system. After the dropwise addition, a white solid was precipitated by line polymerization at 100° C. for 2 hours. After this, cool
The white solid was dissolved by decanting the dodecane and adding an additional 100 grams of dehydrated toluene, and 0.02 mole of metallic lithium was added.

Next, chlorobenzene (manufactured by Tokyo Kasei) (b-7) 0.0
A solution prepared by dissolving 2 mol in 10 ml of toluene was slowly added dropwise to the reaction system with stirring, and 100 ml of toluene was added.
Heated at ℃ for 1 hour. Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to remove excess metal lithium. Is this a concern? Er N and a toluene layer were formed.

Next, the toluene layer was separated, concentrated under reduced pressure, and purified by developing with a silica gel column and chromatography to obtain a polysilane compound Th2 ((, -3). The yield was 72
%, and the weight average molecular weight was 92.000. The identification results are shown in Table 1.

Next, non-3iHX fine particles to be dispersed in a polysilane compound, which is a feature of the present invention, were prepared as follows. FIG. 4 shows that the deposition apparatus 1000 of the manufacturing apparatus for the RF glow discharge decomposition method shown in FIG. 2 is replaced with the deposition apparatus 110o for μW glow discharge decomposition shown in FIG. This is an apparatus for producing non-SiHX fine particles using the μW glow discharge decomposition method. Non-3i HXI) particles were produced using this production apparatus.

A cylindrical stainless steel support 1107 is set, and the pressure inside the deposition chamber 1101 is increased to 5X using an oil diffusion pump, a mechanical booster pump, and a rotary pump (not shown).
The atmosphere was evacuated to 10-'' Torr, and the temperature of the support was set at 280° C. using a heater (not shown).

Next, the outflow valves 1041, 104.2 and the auxiliary valve 1
018 was gradually opened to allow 5tHn gas and SiFa gas to flow into the deposition chamber 11o1 through a gas discharge hole (not shown) of the gas introduction pipe 111o.

At this time, the S r Ha gas flow rate and the S i F4 gas flow rate were adjusted to 500 sec and 20 sec, respectively, using mass flow controllers 1.021 and 1022.

Next, the pressure inside the deposition chamber 1101 is reduced to 5×10-”T.
While checking a vacuum gauge (not shown), the opening of the main valve (not shown) was adjusted so that the temperature was 0.03. After that, μ (not shown)
The power of the W power supply is applied to the plasma generation region 1109 through the waveguide 1103 and the dielectric window 1102 at 0.6 W/cd.
was introduced at a power density of , to generate a μW glow discharge.

non-3i) on the cylindrical stainless steel support 1107
(The X layer was deposited to a thickness of 150 μm. Then, the μW glow discharge was stopped, and the outflow valves 1041 and 1042 were closed.
The flow of gas into the deposition chamber 1101 was stopped. Next, the inside of the deposition chamber 1101 was sufficiently purged with Ar gas. The support was taken out from the deposition chamber while the support temperature was still high, and water was flowed inside the cylindrical stainless steel support to rapidly cool the support. Then, the non-3iHX film on the support was subjected to ffiJI iJ to form fine particles.

When X-ray diffraction of the non-3i HX fine particles was measured, the non-3i Hx1 particles were found to be amorphous. In addition, the infrared absorption of the non-3i HX5i particles was measured using FTIR (PERKTN ELMER1720-X
), there was a peak near 2000cn+-', and non-S i HX calculated from this peak
The amount of hydrogen in the fine particles was 10 at%.

When the particle size of the non-3iHXa particles was measured in the same manner as in Example 1, the average particle size was 3 μm. The non-5i HXli particles were mixed and dispersed in an amount of 7% by weight with respect to the polysilane compound. The mixing method was the same as in Example 1.

Further, an electrophotographic light-receiving member using a polysilane compound in which non-3i HXfi particles of this example were dispersed was formed in the same manner as in Example 1, and the material was coated to a thickness of 60 μm on a cylindrical AJ support.

The electrophotographic light-receiving member thus formed was set in a copying machine (Canon NP-6150 modified for experimental use), and sensitivity, spectral sensitivity, shallow type, and ghost were measured. The light-receiving member had seven times better sensitivity than the comparative example, and its spectral sensitivity extended over the entire visible range. In addition, the shallow type was reduced to 1/1O, and the ghost was also reduced to 1/10.

A three-way flask was prepared in a blow box that had been vacuum suctioned and replaced with argon, a reflux condenser, a thermometer, and a dropping funnel were attached to it, and argon gas was passed through the bypass pipe of the dropping funnel.

100 grams of dehydrated n-hexane and 0.3 mol of 11-gonal metal sodium were charged into this Mitsuro flask, and heated to 80°C with stirring. A solution prepared by dissolving 1 mol of . After the dropwise addition, a white solid was precipitated by condensation polymerization at 80° C. for 3 hours. After this time, the mixture was cooled, the n-hexane was decanted, and 100 grams of dehydrated toluene was added to dissolve the white solid, and 0.01 mole of sodium metal was added. Next, 0.01 mol of benzyl chloride (manufactured by Tokyo Kasei) (b-12) was added to toluene IOmj! A prepared solution was slowly added dropwise to the reaction system with stirring, and the mixture was heated at 80° C. for 1 hour. Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to remove excess metal sodium. This produced a suspended layer and a toluene layer.

Next, the toluene layer was separated, concentrated under reduced pressure, and then developed using a silica gel column and chromatography to obtain a polysilane compound IIh3 (C-4). The yield was 61% and the weight average molecular weight was 47,000. The identification results are shown in Table 1.

In addition, in this polysilane compound, unreacted 5t-
CI, by-product Si OSi, 54-O-R (i
[There was no IR absorption.

In this example, n dispersed in a polysilane compound
On-3i HX fine particles were produced by the μW glow discharge decomposition method in the same manner as in Example 2.

The produced non-5i HX fine particles were separated using a classifier as shown in Table 2.

The classified non-3iHXfi particles were dispersed in the polysilane compound of this example in the same manner as in Example 2.

The ratio of non-3i Hx fine particles to the polysilane compound was set at 20% by weight.

In addition, as in Example 2, non-3 was added to the cylindrical AI support.
i HXI) 50μ of polysilane compound in which particles are dispersed
m was applied.

The electrophotographic light-receiving member thus formed was evaluated in the same manner as in Example 2.

The results are shown in Table 2. Good characteristics were obtained when the average particle size of non-3i HX was 1 to 10 μm.

Large thimble↓ Synthesis was carried out in the same manner as in Example 3 using 0.1 mol of dichlorosilane monomer (a-7) and the terminal group treatment material (b-8>0.01 mol.The yield of the synthesized polysilane, Weight average molecular weight, IR and NMR data are shown in Table 1.

Note that in this polysilane compound, unreacted S 1
-CI, the by-products 5l-0-3i and 5jO-R did not exhibit any IR absorption.

In this example, no.
n-5i HXi particles were produced in the same manner as in Example 2. Classified in the same manner as in Example 3 to obtain particles with an average particle size of 5 μm.
on-S i HX microparticles were screened.

The classified non-3i HX'R1 particles were dispersed in a polysilane compound in the same manner as in Example 2.

The mixing ratio of the non-3i HXli particles into the polysilane compound was as shown in Table 3.

Using such a polysilane compound, an electrophotographic light-receiving member was produced in the same manner as in Example 2.

All the layer thicknesses of the light-receiving member made of non-3i HXi particles and a polysilane compound were 50 μm.

Regarding such an electrophotographic light-receiving member, the electrophotographic characteristics were measured in the same manner as in Example 2.

The results are shown in Table 3. Good electrophotographic properties were obtained when the mixing ratio of non-3i HX to the polysilane compound was 1 to 30% by weight.

(The following is a blank space) (Summary of the effects of the invention) By forming the light-receiving member of the present invention with the specific layer structure as described above, various problems in conventional light-receiving members made of polysilane compounds can be solved, and in particular, it is extremely Excellent,
Indicates electrical properties, optical properties, photoconductive properties, image properties, durability, stability, and use environment properties.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining the layer structure of the electrophotographic light-receiving member of the present invention, and FIG. 2 is a non-3 for electrophotographic light-receiving member of the present invention.
i A schematic explanatory diagram of a production apparatus using an RF glow discharge decomposition method as an example of an apparatus for forming HX fine particles.
i A schematic explanatory diagram of a deposition apparatus when using a microwave glow discharge decomposition method to form HX fine particles, FIG.
FIG. 1 is a schematic explanatory diagram of a manufacturing device using a microwave glow discharge decomposition method, which is an example of a device for forming iHXa particles. In FIG. 1, 100... light receiving member for electrophotography of the present invention, 101...
... Support, 102 ... Photoreceptive layer, 104 ... Free surface. In FIG. 2, 1000...deposition device using RF glow discharge decomposition method;
1001... Deposition chamber, 1005... Cylindrical support,
1007...Gate valve, 1008...Gas introduction pipe, 1009...Gas discharge hole, 1012...High frequency masoching pofukus, 1014...
...Heating heater 1015...Leak valve, 1016...Main valve, 1017...Vacuum gauge,
1018... Auxiliary valve, 1020... Raw material gas supply device, 1021-1024... Mass flow controller 1
031-1034...Gas inflow valve, 1020...
- Raw material gas supply device, 1021-1024...mass flow controller 1
031-1034...Gas inflow valve, 1041-1
044...Gas outflow valve, 1051-1054...
・Valve of raw gas cylinder, 1061-1064...
Pressure regulator, 1071-1074... Raw material gas cylinder, 1093... Exhaust valve. In FIG. 3 and FIG. 4, 1100...Deposition device using microwave glow discharge decomposition method, 1101...Deposition chamber, 1102...Dielectric window, 1103...Waveguide section, 1107... Cylindrical support, 1109... Plasma generation region, 1110... Gas introduction tube.

Claims (1)

[Claims] 1. (a) It is represented by the general formula (I) and has a weight average molecular weight of 6.
000 to 200,000, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [However, in the formula, R_1 is an alkyl group having 1 or 2 carbon atoms,
R_2 represents an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group, an aryl group, or an aralkyl group, R_3 represents an alkyl group having 1 to 4 carbon atoms, and R_4 represents an alkyl group having 1 to 4 carbon atoms. A and A' each represent an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group having 4 to 12 carbon atoms, and they may be the same or different. n and m are molar ratios indicating the proportion of the number of each monomer to the total monomers in the polymer, and n
+m=1, 0<n≦1, 0≦m<1. (b) A photoreceptor for electrophotography, characterized by having a photoreceptor layer made of a mixture of (a) and (b) of non-single-crystal silicon fine particles containing hydrogen and/or halogen atoms. Element.