JPH03181563A - Novel polysilane composition - Google Patents

Abstract

PURPOSE:To obtain a composition suitable for various kinds of devices, controllable by conduction type, having excellent solubility in solvent, film forming properties by blending a specific polysilane compound with a specific amount of halogen compound. CONSTITUTION:(A) 100 pts.wt. polysilane compound shown by the formula (R1 is 1-2C alkyl; R2 is 3-8C alkyl, cycloalkyl, aryl, etc.; R3 and R4 are 1-4C alkyl; A and A' are 4-12C alkyl, aryl, aralkyl, etc.; n+m=1, 0<n<=1 and 0<=m<1) and 6,000-200,000, preferably 10,000-80,000 weight-average molecular weight is blended with (B) 1X10<-4>-10 pts.wt. halogen compound shown by the formula [M is element (N, P, Ae, etc.) of the group VA of the periodic table; X is halogen (F, Cl, Br, etc.); a is positive integer] as a substance for forming acceptor order.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a novel polysilane composition and a method for producing the same. More specifically, the present invention relates to a novel polysilane U paraboloid useful as an organic semiconductor and a method for producing the same.

[Description of prior art]

Polysilane was reported to be insoluble in solvents [The
Journal of the American Chemical Society; 125, 2291 pp (1924)) Recently, it has been reported that polysilane is soluble in solvents and can be easily formed into films [The Journal of American Ceramic Society; , 504pp (1978)
) began to attract attention. Furthermore, since polysilane photodecomposes when irradiated with ultraviolet rays, research has been reported to apply it to resists [JP-A-609843I, JP-A-6O-
119550).

In addition, polysilane has the property of a photosemiconductor in which charge can be transferred through the σ-bonds in its main chain, and its application to electrophotographic photoreceptors is also expected (Physical Review B; 35.2818pp (1987)). became. However, in order to be applied to such electronic materials, polysilane compounds must not only be soluble in solvents and capable of forming films, but also be capable of forming films without minute defects and with high homogeneity. . Since even minute defects are unacceptable in electronic materials, high-quality polysilane compounds are required 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
ourna 1or American Chea+1
cal 5ociety; 94+(11)3806p
(1972)), Japanese Patent 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. They have a structure in which an alkoxy group is substituted, but all have a degree of polymerization of 2 to 6 and do not exhibit the characteristics of a polymer. In other words, a high-molecular-weight polysilane compound with a structure in which all Si groups are replaced with organic groups has been recently reported, which is difficult to use industrially because it has no film-forming ability as it is due to its low molecular weight [Nikkei News] Material (August 15th issue, page 46 (1988)), since the process involves a special reaction intermediate, a decrease in the synthesis yield is expected, making industrial mass production difficult.

In addition, methods for synthesizing polysilane compounds are described in The Journal of Organometallic Chemistry; 198p.
p, C27, (1980) or The Journal of
Polymer Science, Polymer Chemistry Edition; Vow.

22.159-170pp (1984)). However, all of the reported synthesis methods involve only a condensation reaction of the polysilane main chain, and there is no mention of terminal groups. In any of the synthesis methods, unreacted chloro groups and by-products due to side reactions are produced, making it difficult to consistently obtain the desired polysilane compound.

Examples of using the above polysilane compounds as photoconductors have also been reported (U, S, P, It461
8551, U, S, P, Hiroshi 4772525, JP-A-62
-269964), the influence of unreacted chloro groups and by-products due to side reactions is presumed.

In U, S, P, 1k4618551, the above-mentioned polysilane compound is used as an electrophotographic photoreceptor, but in a general copying machine, the applied potential is only 500 to 800V, but an abnormally high applied potential of 1000V was used. There is. 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. In addition, in JP-A No. 62-269964, an electrophotographic photoreceptor was prepared using the above-mentioned polysilane compound and its photosensitivity was measured, but the photosensitivity was slow, and conventionally known selenium photoreceptors and organic photoreceptors has no advantage over .

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.

In particular, the ability to control the conductivity of polysilane compounds as so-called organic semiconductors is an important deciding factor in whether they can be used in place of conventional inorganic semiconductor materials, and urgent consideration is a social requirement. be.

For example, in Document 1 mentioned above, although there are specific examples of substances for forming donor ranks or acceptor ranks, there are no specific explanations or suggestions regarding electrical properties or adjustment methods, and further study is required in the future.

[Purpose of the invention]

The present invention has a weight average molecular weight of 6,000 to 200,000.
A polysilane compound or compound whose substituents and terminal groups are all substituted with a specific organic group and which makes it possible to control the conductivity type as an organic semiconductor by incorporating a specific substance into the polysilane compound, and a method for producing the same. Our goal is to provide the following.

Another object of the present invention is to provide the above-mentioned novel polysilane composition, which has good solvent solubility and enables formation of a semiconductor film having excellent properties, and a method for producing the same.

Still another object of the present invention is to provide the novel polysilane m-acid useful for producing various electronic devices and a method for producing the same.

[Structure and effects of the invention]

The present invention has been completed through intensive research by the present inventors in order to achieve the above-mentioned object, and the gist of the present invention is that the present invention is represented by the following general formula (+) and has a weight average molecular weight of 6000 to 200,000, and the polysilane compound 100,000 as an acceptor rank forming substance.
-g2MXa (where M is an element belonging to group VA of the periodic table, X is a halogen element, and a is a positive integer determined according to the valence of the element M, respectively. The present invention is a novel polysilane MiIIIi product containing 1X10-' to 10 parts by weight of a halogen compound represented by .).

RRs A −←−5i→−“−1+3 Toshi1−A′...(
1) Rz Ra (wherein, R1 is an alkyl group having 1 or 2 carbon atoms,
R2 is an alkyl group, cycloalkyl group, aryl group, or aralkyl group having 3 to 8 carbon atoms; R1 is an alkyl group having 1 to 4 carbon atoms;
and R4 each represent 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 ratio of the number of each monomer to the total monomers in the polymer, n+m=1, and Q<n≦1.05m<l. ) In the polysilane compound represented by formula -i (+), A and A' are an alkyl group having 5 to 12 carbon atoms or a cycloalkyl group.

The polysilane compound represented by the general formula (1) and having a weight average molecular weight of 6,000 to 200,000, which is preferably used in the present invention, has no chlorine group or side reaction product group, and all Si groups have no oxygen. Substituted with an organic group, non-toxic, aromatic solvents such as toluene, benzene, xylene, halogenated solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, etc.
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 is homogeneous, has a uniform thickness, has excellent heat resistance, is rich in hardness, and is rich in toughness.

For these reasons, the polysilane compound suitably used in the present invention is a polymeric substance that can be applied to electronic devices, medical equipment, etc. and has high industrial utility value.

Note that examples of the electronic device include organic photoconductors, electrical conductors, photoresists, optical information storage elements, and the like.

As mentioned above, the 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. More preferable ones have a weight average molecular weight of 8,000 to 120,000.
The optimal one has a weight average molecular weight of 1ooo
o to 80,000.

In addition, those having a weight average molecular weight of 6,000 or less do not exhibit the characteristics of a polymer and have no film-forming ability. Moreover, those having a molecular weight of 200,000 or more have poor solubility in solvents, making it difficult to form a desired film.

In addition, when the above-mentioned polysilane compound represented by the general formula (+>) preferably used in the present invention is desired to have particularly strong toughness in the film to be formed, the terminal groups A and A'
is an alkyl group having 5 to 12 carbon atoms, and an alkyl group having 5 to 12 carbon atoms.
Desirably, it is a group selected from the group consisting of a cycloalkyl group, an aryl group, and an aralkyl group. In this case, the most preferred polysilane compound of the present invention is one in which the terminal groups A and A' are groups selected from an alkyl group having 5 to 12 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms.

The above-mentioned polysilane compound suitably used in the present invention can be synthesized as follows. That is, under a high-purity inert atmosphere free of oxygen and moisture, 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 intermediate polymer is separated from unreacted dichlorosilane monomer, and the intermediate polymer is reacted with a predetermined halogenated organic reagent 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. The novel borinlane composition of the present invention is produced by further adding and containing an amine compound to the polysilane compound synthesized in this manner.

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; Under these conditions, the above-mentioned polysilane compound which is the object of the present invention cannot be obtained.

Therefore, the above-mentioned operation for obtaining the polysilane compound suitably used in the present invention needs to be carried out in an atmosphere in which neither oxygen nor moisture is present. Therefore, care must be taken regarding the reaction container and all reagents used so 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 a glove box to prevent adsorption of moisture and oxygen into the system.

In any case, the argon gas used is first passed through a silica gel column to dehydrate it, and then the copper powder is mixed with 1.
It is passed through a column heated to 00°C to deoxidize it before use.

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 dehydrated in the same manner as the dichlorosilane monomer before being introduced into the reaction system. Note that the solvent is dehydrated by distilling under reduced pressure using the deoxidized argon gas described above, and then further dehydrating with metallic sodium.

The above-mentioned condensation catalyst is preferably used in the form of wires or chips in order to increase its surface area, and the formation of wires or chips is carried out in a flooded paraffinic solvent to prevent oxidation. is desirable.

The dichlorosilane monomer used in the synthesis of the polysilane compound represented by the general formula (1) used in the present invention may be a dichlorosilane compound represented by the following format: R, RzSiC6z, or a dichlorosilane compound represented by the following format: R
A dichlorosilane compound represented by zR4SiC1z is selectively used.

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

The above-mentioned halogenated organic reagent is for introducing substituents represented by A and A', and is composed of a halogenated alkyl compound, a halogenated cycloalkyl compound, a halogenated aryl compound, and a halogenated aralkyl compound. A suitable compound selected from the group, i.e. -format:
It is represented by A-X and/or -format: A'-X (where X is CA or Br), and an appropriate compound from the specific examples described below is selectively used.

General formula used in synthesizing the intermediate polymers described above: R+ R2S I C1z or this - Format: R
The dichlorosilane monomer represented by 3R4S i CIt z is introduced into the reaction system after being dissolved in a predetermined solvent, 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 monomer. The separated intermediate polymer is then reacted with the above-mentioned halogenated organic reagent, in which case both are dissolved in the same solvent and subjected to the reaction. In this case, aromatic solvents such as Hensen, toluene, and xylene are preferably used as the solvent.

In condensing the above-mentioned dichlorosilane monomer using the above-mentioned alkali metal catalyst, the degree of polymerization of the resulting intermediate polymer can be appropriately controlled 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 desirable embodiment of the method for producing the above-mentioned polysilane compound represented by the general formula (1) used in the present invention will be described below.

That is, the method for producing the above-mentioned polysilane compound preferably used in the present invention includes (i) a step of producing an intermediate polymer; and (ii) a step of introducing substituents A and A' to the terminals of the 3g intermediate polymer. Consisting of

The step (i) above is performed as follows.

That is, oxygen and water in the reaction system of the reaction vessel are completely removed and replaced with argon, the internal pressure is maintained at a predetermined level, an anhydrous paraffinic solvent and a catalyst are added, and then an anhydrous dichlorosilane monomer is added. The monomers are condensed by heating the entire mixture to a predetermined temperature while stirring. At this time, the degree of polymerization of the dichlorosilane monomer is controlled by adjusting the reaction temperature and reaction time so that an intermediate polymer having a desired degree of polymerization is produced.

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 2 SiCi! .

+mR, Rs catalyst 5iCj! , → 3 Ce −%i□ 1−)−=−−C1−(i)R,
R.

The specific reaction procedure is as follows: a condensation catalyst (alkali metal) is placed in a paraffinic solvent, and a dichlorosilane monomer is added dropwise while heating and stirring. The degree of polymerization is
Confirm by sampling the reaction solution.

A simple confirmation of the degree of polymerization can be made by taking a sample liquid, evaporating the solvent, and determining whether a film can be formed. As the shrinkage progresses and a polymer is formed, it becomes a white solid that precipitates out of the reaction system.

Here, the reaction system is cooled, and the solvent containing the heptamer is separated from the reaction system by decantation to obtain an intermediate polymer.

Next, the step (bl) described above is carried out. That is, the chlorine group at the end group of the obtained intermediate polymer is subjected to desalting condensation using a halogenated organic reagent and a condensation catalyst (alkali metal) to convert the polymer end group to a predetermined amount. Substitution with an organic group.The reaction at this time is represented by the reaction formula below.

3 C7! -←5i→-"-111,000 3+-→ko"-e 2 4 Catalyst (2A X+A'
R4 Specifically, an aromatic solvent is added to and dissolved in an intermediate polymer obtained by condensation of dichlorosilane monomers. Next, a condensation catalyst (alkali metal) is charged, and a halogenated organic reagent is added dropwise at room temperature. Since this substitution reaction competes with the condensation reaction between polymer terminal groups, a halogenated organic reagent is added in an excess amount of 0.1 to 0.1 times the starting amount.

Gradually heat and stir at 80°C to 100°C for 1 hour,
Perform the desired reaction.

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

(Space below) Specifications of JRl SiCA 2 and R3Ra SiCn z) Among the following compounds, a-2 to 16.18, 2
0.21°23.24 is RIR25iCj! Used for z, a −1°2.11.17. +9.22.23.2
5 is used as R3Ra S+C+2.

(013) rsic 1 z -1 C31k ” ((Cl3)zCH) zsic l ga-g ((Cll+> 3C) zsic 1 za-ro 2 arrow two (and specific example of A' -X (C113) 2C1lCI+2 (, ACl13(c+
Iz)4ct:; Cl13(C1b)sfJ Q13(Q12) +. Cl αZOCβ Oh (CHz) 5Br C1b (CIlz) 1oBr Br -14 -15 -17 Examples of polysilane compounds suitable for producing integrated semiconductor properties Of.

Mouth C1b (Clh) s-45i +r-(Ch) s
Qh-18 CIl (C11,).

CH(CI+02 C11゜ CH.

C1l.

C11゜ CIl.

l3 C1l.

l13 b C11゜ h l13 113 C)(.

C113 (C11□)3 CI+3 C11゜(C)lx)z H3 (C)1□)3 Note): Neither X nor Y in the above structural formula shows a heavy tl-position. And n is X/ (X+Y), and m is Y/
They are each calculated using the calculation formula (X→Y).

[Synthesis example]

Since the polysilane compound was synthesized prior to the present invention,
A detailed explanation will be given below using synthesis examples.

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

100 g of dehydrated dodecane and 0.3 mol of wire-shaped sodium metal were placed in this Mitsurofask and heated to 100° C. with stirring. Next, dichlorosilane monomer (manufactured by Chisso ■) (a-7>0.1 mol) was dissolved in 30 grams of dehydrated dodecane, and the prepared solution was slowly added dropwise to the reaction system.

After completion of the dropping, condensation polymerization was carried out at 100° C. for 1 hour, and a white solid was precipitated. After cooling, dodecane was removed by decantation, 100 g of dehydrated toluene was added to dissolve the white solid, and 0.0 g of metallic sodium was added.
01 mol was added.

Next, while stirring this solution, 0.01 mol of n-hexyl chloride (manufactured by Tokyo Kasei) (b-3) was added to 10 mol of toluene.
Slowly drop the prepared solution dissolved in mj+,
Heating and stirring were continued at 100° C. for 1 hour. After this, cool
To dispose of excess sodium metal, methanol 50
ml was slowly added dropwise. This separated the suspended layer and toluene layer.

Next, the toluene layer was separated and extracted, concentrated under reduced pressure, and purified by developing with a silica gel column and chromatography to obtain 1 ml of a polysilane compound (C-1>. The yield was 6
It was 5%.

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

IR spectra were made from KBrBr pellets and N1col
et FT-IR750 (manufactured by Collet Japan). In addition, the NMR spectra were obtained using CD samples.
The polysilane compound was identified using FT-NMRFX-90Q (JEOL). The results are shown in Table 4.

In addition, in the polysilane compound synthesized in the wood synthesis example, unreacted 5i-CA and by-product Si-〇-3i
, 3+-〇-R was not present at all.

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

100 grams of dehydrated dodecane and 0.3 mol of metal lithium per square inch were charged into this Mitsuro flask, and heated to 100° C. with stirring. Next, dichlorosilane monomer
(manufactured by Chisso G1) A solution prepared by dissolving 0.1 mol of (a-7) in 30 grams of dehydrated dodecane was slowly dropped into the reaction system. After the dropwise addition was completed, condensation polymerization was carried out at 100° C. for 2 hours, and a white solid was precipitated. Thereafter, the mixture was cooled, and dodecane was removed with decane silane. 100 grams of dehydrated toluene was added to dissolve the white solid, and 0.02 mole of metallic lithium was added.

Next, while stirring this solution, a solution prepared by dissolving 0.02 mol of chlorobenzene (manufactured by Tokyo Kasei) (t+-7) in 10 ml of toluene was slowly added dropwise, and the mixture was heated to 100°C.
The mixture was heated and stirred for 1 hour.

Thereafter, the mixture was cooled, and 50 ml of methanol was slowly added dropwise to remove excess metal lithium. This allows Qi
It was separated into a layer and a toluene layer.

Next, the toluene layer was separated and extracted, concentrated under reduced pressure, and purified by developing with a silica gel column and chromatography.
Polysilane compound 1h2 (C-3) was obtained. Yield is 7
The weight average molecular weight was measured in the same manner as Synthesis Example 1 and found to be 92,000. Furthermore, the results of identification performed in the same manner as in Synthesis Example 1 are shown in Table 4.

Note that in this polysilane compound, unreacted S 1
-CA, by-product S i -0-3t, S i○
There was no IR absorption attributed to -R.

A Mitsuro flask was prepared in a glove box that had been vacuum-suctioned and replaced with argon, and a reflux condenser, thermometer, and 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 IR-metallic sodium were charged into this Mitsuro flask, and heated to 80° C. with stirring. Next, a solution prepared by dissolving 0.1 mole of dichlorosilane monomer (nitrogen type) (a-7) in dehydrated n-hexane was slowly dropped into the reaction system. After completion of the dropwise addition, condensation polymerization was carried out at 80° C. for 3 hours, and a white solid was precipitated. After that, it was cooled, n-hexane was removed with decanethisilane, and then dehydrated toluene was added to
0 grams were added to dissolve the white solid and 0.01 mole of sodium metal was also added. Next, while stirring this dissolution/night, benzyl chloride (manufactured by Tokyo Kasei) (b-12
) A solution prepared by dissolving 0.01 mol in 10 ml of toluene was slowly added dropwise, heated at 80°C for 1 hour,
Continue stirring, then cool, and add 50 ml of methanol to remove excess metal sodium! was slowly dripped. This separated the mixture into a turbid layer and a toluene layer.

Next, the toluene layer was separated and extracted, concentrated under reduced pressure, and purified by developing with a silica gel column and chromatography.
Polysilane compound 1 to 3 (C-4) was obtained. The yield was 61%, and the weight average molecular weight was measured in the same manner as Synthesis Example 1 and found to be 47,000. Furthermore, the results of identification performed in the same manner as in Synthesis Example 1 are shown in Table 4.

In addition, in this polysilane compound, unreacted (7)S
t-CI! , 5i-0-3i, and 5tO-R, which are by-products, did not exhibit any IR absorption.

Synthesis was carried out in the same manner as in Synthesis Example 3 using the dichlorosilane monomer and end group treatment agent shown in Table 1.

Table 4 shows the yield of the synthesized polysilane, and the results of measuring the weight average molecular weight, IR and NMR spectra in the same manner as in Synthesis Example 1.

In addition, in this polysilane compound, unreacted (7)S
i-C1, by-products Si-〇-3i, 5iO-R [R absorption was not present at all.

A dichlorosilane monomer (manufactured by Chisso ■) (a-7) was condensed in the same manner as in Synthesis Example 3, and a polysilane compound was synthesized in the same manner as in Example 3, except that the terminal groups of the polymer were not treated.
hD-1 was obtained. The yield was 60%, and the weight average molecular weight was measured in the same manner as in Synthesis Example 1 and found to be 46,000.

Furthermore, the results of identification performed in the same manner as in Synthesis Example 1 are shown in Table 4.

In addition, in this polysilane compound, unreacted 5i-Cj! is present in the terminal group. , IR absorption attributed to the by-product 5i-OR was observed.

Synthesis Examples 6 to IO The same condensation reaction operation and purification as in Synthesis Example 3 were performed except that the dichlorosilane monomer, reaction time, and end group treatment agent were changed as shown in Table 2, and a polysilane compound No. 6 was obtained. I got ~10.

Table 4 shows the yield of the synthesized polysilane compound, and the results of measuring the weight average molecular weight, IR and NMR spectra in the same manner as in Synthesis Example 1.

Note that in this polysilane compound, unreacted S 1
-C12, by-product S i -0-3t, S 1
There was no IR absorption attributed to OR.

Polysilane compound D-2 was synthesized in exactly the same manner as in Synthesis Example 6 except that the reaction time was changed to 10 minutes.

Table 4 shows the yield of the synthesized polysilane, and the results of measuring the weight average molecular weight, IR and NMR spectra in the same manner as in Synthesis Example 1.

Note that in this polysilane compound, unreacted 5i
-Cj! , by-product Si-〇-3t.

There was no IR absorption assigned to 5i-0-R.

Synthesis was carried out in the same manner as in Example 1 using the dichlorosilane monomer and end group treatment agent shown in Table 3.

Table 4 shows the yield of the synthesized polysilane, and the results of measuring the weight average molecular weight, IR and NMR spectra in the same manner as in Example 1.

The copolymerization ratio of the silane monomers was determined from the number of protons in NMR.

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

100 g of dehydrated dodecane and 0.3 mol of wire-shaped sodium metal were placed in this Mitsurofask and heated to 100° C. with stirring. Next, a solution prepared by dissolving 0.1 mole of dichlorosilane monomer (manufactured by Chisso ■) in 30 grams of dehydrated dodecane was slowly added dropwise to the reaction system. After dropping, heat at 100℃ for 1 hour! Upon polymerization, a white solid precipitated. Thereafter, the mixture was cooled, and 50 mJ of methanol was slowly added dropwise to remove excess metal sodium.

Next, the white solid was filtered and washed repeatedly with n-hexane and methanol to obtain polysilane compound mD3.

This polysilane compound contains toluene, chloroform, TH
Since it is insoluble in organic solvents such as F, identification was performed by rR spectrum. The results are shown in Table 4.

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

100 g of dehydrated dodecane and 0.3 mol of wire-shaped sodium metal were placed in this Mitsurofask and heated to 100° C. with stirring.

Next, a solution prepared by dissolving 0.1 mole of diphenyldichlorosilane monomer (manufactured by Natsutsu) in 30 grams of dehydrated dodecane was slowly dropped into the reaction system. After completion of the dropping, condensation polymerization was carried out at 100° C. for 1 hour, and a white solid was precipitated.

After this, it is cooled and the excess metal sodium is disposed of.
Methanol 5 Qrrz2 slowly? m down.

Next, the white solid was filtered and washed repeatedly with n-hexane and methanol to obtain Bo1J silane compound mD-4.

This polysilane compound contains toluene, chloroform, TH
Because it is insoluble in organic solvents such as F, identification was performed using IR spectroscopy. The results are shown in Table 4.

The polysilane compound synthesized in the above synthesis example has excellent moldability and can be molded into a film, particulate, or fiber shape.

Specific moldability includes a coating method, a spin coating method, a dip method, an electrodeposition method, a sublimation vapor deposition method, a compression molding method, a calendering method, and the like.

Furthermore, in the present invention, substances suitably used for controlling the conductivity of the polysilane compound, that is, for forming an acceptor level, so-called dopant agents, include:
-ff1 Halogen compound represented by the formula MXa (M is an element belonging to group VA of the periodic table, X is a halogen element, and a is a positive integer determined according to the valence of M.) can be mentioned. Specifically, the element M is N.

P, As, Sb are mentioned, and X is F, CLBr,
1 is mentioned. Further, specific examples of norogen compounds include NF3, NFS, and NCl3.

NCj! s + NBr5. NBs, NIs,
PF3 +PFs, PCl5, PCl5, PBr
+, PBrs.

P I 31 A s F ff+ A s F 5
+ A s C' z + A s B r s.

As rff , 5bFs , 5bFs , 5bC1x
.

5bCj! s, 5bBra, Sb 13, etc.

These halogen compounds may be used alone or in combination.

Next, in the present invention, as a method for producing a polysilane composition having a desired conductivity type by adding the halogen compound to the polysilane compound, that is, a doping treatment method,
Specifically, the following three methods can be mentioned.

+11 When the halogen compound is solid or liquid, the following method can be adopted.

First, a solution (hereinafter, this solution will be referred to as a "polysilane solution") is prepared by dissolving the polysilane compound synthesized in the above synthesis example in a sufficiently dehydrated organic solvent such as benzene, toluene, or THF. The concentration of the polysilane compound in the polysilane solution at this time is preferably lXl
0-'g/l to 2xlO'g/j! , more preferably IxlO-"g/# to 1xlO"g/l, optimally I
It is preferable that the range is from 10"g#! to 5xLO"gzl.

On the other hand, a solution in which the amine compound as a dopant agent is dissolved alone or in an organic solvent that is compatible with the organic solvent and has been sufficiently dehydrated (hereinafter, this solution is referred to as a "dopant solution") is prepared. Prepare. At this time, the concentration of the halogen compound in the dopant solution is preferably I
X 1.0-6g/A to 2xlO"g/l, more preferably 2xlO-'g/f to lXl0"g/l, optimally 1xlO-'g/Il to 5x], O'g/if
! It is desirable that this is done. Next, the dopant solution is added dropwise to the polysilane solution, and stirred thoroughly while being heated if necessary.

(Hereinafter, a solution subjected to such treatment will be referred to as a "treatment liquid.") The heating temperature at this time is preferably set to a temperature below the glass transition point of the polysilane compound.

Thereafter, the treatment liquid is transferred to a desired molding device and molded into a film, particles, fibers, etc. to obtain the polysilane composition of the present invention.

(2) When the halogen compound is solid or liquid and can be sublimed or vaporized, the following method can be adopted.

First, a polysilane solution is prepared by dissolving the polysilane compound synthesized in the above synthesis example in a sufficiently dehydrated organic solvent such as benzene, toluene, or THF. The concentration of the polysilane compound in the polysilane solution at this time is preferably 1X10-3 g// to 2X103 g/j! ,
More preferably IX10-"g, # to lXl0'
g/It, optimally I x 10-'g/A to 5 x 1
It is desirable to set it to 0''g/J.

Next, the polysilane solution is transferred to a desired molding device and the polysilane is molded into a film, particles, or fibers. Further, the molded product is transferred to a sealable doping treatment device, and exposed to the atmosphere of the halogen compound while heating if necessary to adsorb and impregnate the halogen compound to obtain a desired polysilane composition. The atmosphere of the halogen compound may be any one of pressurized, normal pressure, and reduced pressure. Further, the heat treatment temperature of the polysilane molded product at this time is preferably set to a temperature equal to or lower than the glass transition point of the polysilane compound.

(3) The polysilane compound of the present invention can be doped by an electrochemical method.

Specifically, a polysilane molded product molded by the same molding method as described in method (2) above was inserted into an appropriate electrolyte solution as one electrode, and a A doping treatment is performed by inserting another metal electrode and applying a voltage between these electrodes to obtain a desired polysilane composition.

The electrolyte solution is prepared by dissolving the norogen compound as an electrolyte in a Ja-containing solvent, and specific examples of the Ja-containing solvent include acetonitrile, propylene carbonate, T-butyrolactone, and chlorobenzene. The electrolyte concentration at this time is preferably 5xlO
-6g/6 to 5xlO2g/7! , more preferably 5
x10-'g/l to 5X10'' g/6. Optimally t
It is preferable that x io−'g7t; to 1×lO”g/n.

Moreover, specifically, as the metal electrode, PtAu
, Ag, Cu, Pd, etc.

In the present invention, an acceptor level is formed by using the polysilane molded product as an anode.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these in any way.

In this example, the above-mentioned doping treatment method (1)
A polysilane composition of the present invention was prepared.

First, put it in a Mitsuro flask that has been thoroughly dried and replaced with nitrogen.
Polysilane compound (Nal) synthesized in Synthesis Example 1
10 g was taken, and while stirring in a nitrogen stream, 100 m6 of tetrahydrofuran that had been dried by double distillation was added dropwise to dissolve it, thereby preparing a polysilane solution.

Next, liquid 5bFSO002μ as a dopant agent
1 was added dropwise to the polysilane solution in the Mitsuro flask using a microsyringe in a nitrogen stream, and stirring was continued for 30 minutes at room temperature.

After stirring, this polysilane solution was transferred to a spin coating device installed in a glove box filled with nitrogen, and #7059 glass (1 inch x 3 inches) manufactured by Corning was used as a substrate. 1.
A film of the polysilane composition was formed with a thickness of 0 μm.

Furthermore, the film was subjected to vacuum drying treatment to obtain sample seed 1.

The amount of the dopant solution dropped is 0.5μL 5μ150
0,clj! , 3m115rr+J was used to prepare film sample NQ2 of polysilane composition using the same operation and method.
~6 was produced.

Next, each sample was set in a vacuum evaporation device, and I
At a vacuum level of about 0-5 Torr, P was used as the vapor-deposited metal for gear electrode formation, and by electron beam evaporation method, a gap of I50 μm and a length of 3 was formed in the gap for measuring electrical conductivity.
cm comb-shaped electrode and 10 cm in the gap for thermoelectromotive force measurement
100 parallel gap electrodes each with a length of 0 μm and a length of 5
It was formed with a film thickness of 0. The sample was not particularly heated during vapor deposition.

After taking it out, the dark current was measured using a microammeter HP4140B at an applied voltage of 30 V, and the dark electrical conductivity σa
(S/01m) was determined, and conduction type ρ was further determined using a thermoelectromotive force measuring device. The measurement and evaluation results are shown in Table 5.

From these results, it was found that all samples except Samples 1 ml and 6 exhibited good electrical characteristics.

Furthermore, a piece of commercially available cellophane tape was cut to a width of 5u and a length of 1c11 and applied to a film of the polysilane composition.After 5 minutes, the cellotape was peeled off and an adhesion test of the formed film to the substrate was conducted, all of which were found to be good. It showed good adhesion.

Further, when a scratch test was conducted using a diamond needle, no scratches were observed up to a needle pressure of 2 g.

In Example 1, the polysilane compound synthesized in Synthesis Example 13 (1m13) was used instead of the polysilane compound (Hiro 1).
) were used to prepare six types of polysilane composition film samples with different amounts of doping using the same procedures and methods. It is shown in Table 5.

The amount of dopant liquid dropped is 0.02μi and 5mj! It was found that film samples other than those prepared as shown in Table 1 showed good electrical properties.

Furthermore, the adhesion and scratch resistance inertia were as good as the results obtained in Example 1.

In Example 1, a polysilane compound (F&L l )
The polysilane compound synthesized in Synthesis Example 9 (9) was used instead of SbF, and 1000 m7 of dry benzene was used instead of SbF as a dopant agent. 6 with different doping amount using the same operation and method except that a dopant solution containing 0.5 g of 5bC1 as a dopant agent was used.
Various kinds of IJ silane film samples were prepared. Note that the amount of dopant solution dropped is 5 μL 10. c+L
100 μl.

It was set as 1mC10m6.50m1.

Each of the obtained samples was measured and evaluated in the same manner as in Example 1, and the results are shown in Table 5.

It was found that film samples other than those prepared with the dopant solution dropped in an amount of 5 μl and 50 m6 exhibited good electrical characteristics.

Furthermore, the adhesion and scratch resistance inertia were as good as the results obtained in Example 1.

In the large construction site example, the above-mentioned doping treatment method (2)
A polysilane composition of the present invention was prepared.

First, put it in a Mitsuro flask that has been thoroughly dried and replaced with nitrogen.
Polysilane compound (m2) 1 synthesized in Synthesis Example 2
0 g was taken, and while stirring in a nitrogen stream, 100 ml of toluene that had been dried by double distillation was added dropwise to dissolve it to prepare a polysilane melt.

Next, this polysilane solution was transferred to a spin coating apparatus installed in a glove box filled with nitrogen, and using Corning #7059 glass (1 inch x 3 inches) as a substrate, a coating film was coated on the glass substrate. .0μm
A polysilane film was formed to a thickness of .

Further, the polysilane film was set in a film holder installed in a vacuum processing apparatus, and vacuum-dried while heating the film holder to 40°C.

Subsequently, the pressure in the vacuum processing apparatus is set to 500 Torr.
A doping treatment was performed by introducing gaseous AsF5 until the temperature reached , and exposing the polysilane film to an ASFS atmosphere for 2 hours while maintaining the above pressure.

Hereinafter, the pressure inside the vacuum processing apparatus was set to 300 Torr.

100Torr, 50Torr, 10Torr
Doping treatment was performed in the same manner except that rr was used.

The film samples of each polysilane composition produced in this way were subjected to the same measurements and evaluations as in Example 1, and the results are shown in Table 6.

It was found that film samples other than those produced with the pressure in the vacuum processing apparatus set at 10 Torr exhibited good electrical characteristics.

Furthermore, the adhesion and scratch resistance inertia were as good as the results obtained in Example 1.

Forfeiture 1 In Example 4, the polysilane compound (6) synthesized in Synthesis Example 6 was used instead of the polysilane compound (M2), and AsF was used as the dopant agent.

Six types of polysilane composition film samples having different doping amounts were prepared using the same operation and method except that PF was used instead of PF.

Each of the obtained samples was measured and evaluated in the same manner as in Example 1, and the results are shown in Table 6.

It was found that film samples other than those produced with the pressure in the vacuum processing apparatus set to 10 Torr exhibited good electrical characteristics.

In addition, the adhesion and scratch resistance were as good as the results obtained in Example 1.

In this example, the above-mentioned doping treatment method (3)
A polysilane composition of the present invention was prepared.

First, put it in a Mitsuro flask that has been thoroughly dried and replaced with nitrogen.
Polysilane compound synthesized in Synthesis Example 11 (lkl
1) 10 g was taken, and while stirring in a nitrogen stream, 100 ml of twice-distilled and dried toluene was added dropwise to dissolve it to prepare a polysilane solution.

Next, this polysilane solution was transferred to a bar coating device installed in a glove box filled with nitrogen, and #7059 glass manufactured by Corning (1 inch x 3 inches) was used as a substrate. A polysilane film was formed with a thickness of .0 μm.

Further, the film was thoroughly dried under a nitrogen stream while being heated to 30° C., and then set in a vacuum evaporation apparatus, and an A1 dot/7 dot electrode of φ3n was deposited by a resistance heating evaporation method. After all the Pt wires were connected to the A1 dot electrode using a wire bong, this was connected to the (+) voltage side of a constant voltage voltage device using a conductive wire to form a polysilane electrode.

On the other hand, in 1ffi of propylene carbonate, 5bFs
Prepare an electrolyte solution in which 5 g of PTT electrode (20 mm x 5 Q m While applying a constant voltage of 0.5 V between both electrodes, doping treatment was performed for 2 hours.

After the doping treatment, the polysilane electrode was taken out and vacuum dried to produce a polysilane IJ1 film sample.

Further, doping treatment was performed in the same manner except that the applied voltages were changed to IV, 5V, IOV, and 50V to prepare polysilane composition film samples.

Each of the obtained samples was measured and evaluated in the same manner as in Example 1, and the results are shown in Table 7.

It was found that film samples other than those produced with applied voltages of 0.5 V and 50 V exhibited good electrical characteristics.

In addition, the adhesion and scratch resistance were as good as the results obtained in Example 1.

In Example 6, the polysilane compound synthesized in Synthesis Example 3 (layer 3) was used instead of the polysilane compound (NIl, 1).
) and using AsBr3 instead of 5bFS as the dopant agent, five types of polysilane composition film samples with different doping amounts were prepared using the same operation and method.

Each of the obtained samples was measured and evaluated in the same manner as in Example 1, and the results are shown in Table 7.

It was found that film samples other than those produced with applied voltages of 0.5 V and 50 V exhibited good electrical characteristics.

Also, the adhesion and scratch resistance were good, similar to the results obtained in Example I.

In Example 6, the polysilane compound (lbll) synthesized in Synthesis Example 7 was used instead of the polysilane compound (lbll).
Five types of polysilane & III parabolic film samples with different doping amounts were prepared using the same operation and method except that .

Each of the obtained samples was measured and evaluated in the same manner as in Example 1, and the results are shown in Table 7.

It was found that film samples other than those produced with applied voltages of 0.5 V and 50 V exhibited good electrical characteristics.

In addition, the adhesion and scratch resistance were as good as the results obtained in Example 1.

In the actual combustion example 3, the polysilane compound (Hiroshi 4) synthesized in Synthesis Example 4 was used instead of the polysilane compound (9), and P was used instead of 5bC1s as a dopant agent.
The same operation was performed, except that a dopant solution using CI was used, and a stainless steel substrate (5 inches thick, 5 inches thick, In) with 1 μm of Ag deposited was used instead of Corning #7059 glass. A polysilane composition film sample was prepared by the method. Note that the amount of the dopant solution dropped was 500 μl.

Subsequently, on the polysilane composition film, A of φ5n was applied.
The u thin film was deposited by 100 people using the electron beam evaporation method. Further, a conductive wire for taking out current was bonded to the Au thin film using a wire bonder, and diode characteristics were evaluated using a microammeter HP4140B.

As a result, the diode factor was n-1,40±0.05, indicating good diode characteristics.

In Example 4, the polysilane compound (11 kL) synthesized in Synthesis Example 14 was used instead of the polysilane compound (Ko 2).
A polysilane composition film sample was prepared in the same manner as in Example 9, except that a stainless steel substrate treated in the same manner as in Example 9 was used. The pressure inside the vacuum processing equipment is 100 Torr.
It was set as r.

Subsequently, a Pt thin film having a diameter of 5 mm was deposited by 100 people on the polysilane & fl bottom film of each sample using the electron beam evaporation method. Further, a conductive wire for taking out current was bonded to the PT thin film using a wire bonder, and diode characteristics were evaluated using a microammeter HP4140B.

As a result, the diode factor was n-1,35±0.05, indicating good diode characteristics.

As a general rule, in Example 6, the polysilane compound (llthll) synthesized in Synthesis Example 8 was used instead of the polysilane compound (llthll).
A polysilane composition film sample was prepared using the same procedure and method, except that a stainless steel substrate treated in the same manner as in Example 9 was used. Note that the applied voltage was IOV.

Subsequently, a Ptl film of φ5fi was deposited on the polysilane composition film of each sample by electron beam evaporation.
00 people were deposited. Further, a conductive wire for taking out current was bonded to the PT thin film using a wire bonder, and diode characteristics were evaluated using a microammeter HP4140B.

As a result, the diode factor was n-1,40±0.05, indicating good diode characteristics.

Table 1 Table 1 [Summary of Effects of the Invention] As explained above, the polysilane composition of the present invention is subjected to condensation polymerization by eliminating halogen from a dichlorosilane monomer, and then converting the end groups of the polysilane into halogens. Good electrical properties (acceptor level) can be achieved by adding a specific amount of a halogen compound to the polysilane compound, which has been stabilized by desalination condensation with an organic group or an alcohol-substituted organic group in the presence of an alkali metal. can be produced.

Furthermore, this polysilane composition has excellent solubility in solvents and film-forming ability, as well as excellent adhesion and film strength.

Claims (4)

[Claims] (1) Represented by general formula (I) and has a weight average molecular weight of 600
0 to 200,000, and the polysilane compound 1 as an acceptor rank forming substance.
00 parts by weight, the general formula MXa (where M is an element belonging to group VA of the periodic table, X is a halogen element, and a is a positive integer determined according to the valence of the element M, respectively. ) 1×10^-^4 to 1
A polysilane composition characterized in that it contains 0 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, R_1 is an alkyl group with 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 ratio of the number of each monomer to the total monomers in the polymer, and n
+m=1, 0<n≦1, 0≦m<1. ) (2) The polysilane composition according to claim (1), wherein in the polysilane compound represented by general formula (I), A and A' are an alkyl group having 5 to 12 carbon atoms or a cycloalkyl group. (3) The polysilane composition according to claim 1, wherein the elements belonging to the VA group are N, P, As, and Sb. (4) The polysilane composition according to claim 1, wherein the halogen element is F, Cl, Br, or I.