JPH02263831A - New polysilane compound and production thereof - Google Patents

Abstract

NEW MATERIAL:A compound, expressed by formula I (R1 is 1-2C alkyl; R2 is 3-8C alkyl, cycloalkyl, aryl or aralkyl; R3 is 1-4C alkyl; R4 is 1-4C alkyl; A and A' each are 4-12C alkyl, cycloalkyl, aryl or aralkyl; n and m are molar ratios indicating the ratios of the respective numbers of the monomers based on the total monomers in the polymer; n+m=1; 0<=n<=1; 0<=m<1) and having 6000-200000 weight-average molecular weight. EXAMPLE:A compound expressed by formula II. USE:Useful for manufacturing electronic devices and medical equipment. PREPARATION:Dichlorosilane monomer is brought into contact with a condensation catalyst in a high-purity inert atmosphere to synthesize an intermediate polymer, which is then separated from the unreacted monomer. A halogenated organic reagent is subsequently reacted with the above-mentioned polymer in the presence of a condensation catalyst to condense organic groups with the terminals of the polymer. Thereby, the objective compound is synthesized.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical field to which the invention pertains] The present invention relates to a novel polysilane compound and a method for producing the same.

C Description of Prior Art] Polysilane was reported to be insoluble in solvents, but in recent years [The Journal of the American Chemical Society 125, 2291pp (1924)] it has been reported that polysilanes are soluble in solvents and can be easily formed into films. It was reported that [The Journal of American
Ceramic Society Volume 1 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-60=98431;
9550].

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 8 35 2818pp (1987)). . 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 (Jo
urnal ofAa+erlcan Chemica
l 5ociety 9↓(11) 3806pp(1
972), 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 the ability to form a film 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 Material August 15 issue, page 46 (198B)], 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 is described in [The Journal of Organometallic Chemistry 198p.
p C27 (1980) or The Journal of
Polymer Science, Polymer Chemistry Edisilane Vol, 22159-170p''p (
19B4)). 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 polysilane compounds as photoconductors have also been reported (U, S, P, Th461
8551, U, S, P, magnetic 4772525, JP-A-62
-269964), the influence of unreacted chloro groups and by-products due to side reactions is presumed.

In U, S, P, Magneto 4618551, the above-mentioned polysilane compound is used as an electrophotographic photoreceptor, but an unusually high applied potential of tooov is used, whereas in a general copying machine, the applied potential is only 500 to 800μ. ing. 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 .

Many problems still remain in using polysilane compounds for such electronic materials, and the reality is that no industrially usable polysilane compounds have yet been provided.

[Purpose of the invention]

An object of the present invention is to provide a novel and hitherto unknown polysilane compound having a weight average molecular weight of 6,000 to 200,000, in which all substituents and terminal groups of the polysilane are substituted with specific organic groups, and a method for producing the same.

Another object of the present invention is to provide the above-mentioned novel polysilane compound having good solvent solubility and excellent film-forming ability, and a method for producing the same.

Still another object of the present invention is to provide the novel polysilane compound useful for producing various electronic devices and medical equipment, and a method for producing the same.

[Structure and effects of the invention]

The present invention achieves the above object, and is represented by the following general formula (1) and has a weight average molecular weight of 6000 to 20.
0000, a novel polysilane compound hitherto unknown and a method for producing the same.

RR2 A -ES i product "--÷Si+-r-A'...
(r) Electron Rx Ra (wherein, R1 is an alkyl group having 1 or 2 carbon atoms, R
g is an alkyl group having 3 to 8 carbon atoms, a cycloalkyl group,
Aryl group or aralkyl group, R2 represents an alkyl group having 1 to 4 carbon atoms, R1 represents an alkyl group having 1 to 4 carbon atoms, A and A' each represent an alkyl group having 4 to 12 carbon atoms, a cycloalkyl group , an aryl 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<fi≦1, 0≦mal. ] The novel polysilane compound represented by the general formula (1) and having a weight average molecular weight of 6,000 to 200,000 provided by the present invention has no chlorine groups or side reaction-forming groups, and all Sl groups have oxygen. Substituted with a specific organic group that is not toxic, aromatic solvents such as toluene, benzene, xylene, halogenated solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, and other tetrahydrofuran (THF) It is easily soluble in solvents such as 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, is rich in hardness, and has toughness.
).

For these reasons, the polysilane compound provided by the present invention is a polymeric substance that can be used in the production of 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. Examples of the medical devices include artificial organs, artificial blood vessels, blood transfusion bags, and the like.

As mentioned above, the novel polysilane compound represented by the general formula (1) provided by the present invention has a weight average molecular weight of 6,000 to 200,000, but has poor solubility in solvents and film-forming ability. More preferable from this point of view are those having a weight average molecular weight of 8000 to 1200.
00, and the optimal one is a weight average molecular weight of 0.
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 general formula (1) of the present invention is desired to have particularly strong toughness in the film to be formed, the terminal groups A and A' may be an alkyl group having 5 to 12 carbon atoms, a carbon number The most preferred polysilane compound of the present invention is preferably a group selected from the group consisting of 5 to 12 cycloalkyl groups, aryl groups, and aralkyl groups, in which the terminal groups A and A' have 5 to 5 carbon atoms. This is the case when the group is selected from an alkyl group having 1 to 12 carbon atoms and a cycloalkyl group having 5 to 12 carbon atoms.

The above-mentioned novel polysilane compound provided by 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 intermediate polymer is separated from unreacted monomers, and the intermediate polymer is reacted with a predetermined halogenated organic reagent in the presence of a condensation catalyst made of an alkali metal to condense an organic group at the terminal of the intermediate polymer. be synthesized.

In the above synthesis operation, the dichlorosilane monomer as the starting material, the intermediate polymer, the halogenated organic reagent, and the alkali metal interlocking catalyst all have high reactivity with oxygen and moisture, so the presence of these oxygen and moisture is necessary. In such an atmosphere, 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 of the present invention needs to be carried out in an atmosphere in which neither oxygen nor moisture is present.

For this reason, care must be taken regarding the reaction vessel and all reagents used to avoid the presence of either oxygen or moisture in the reaction system. Perform substitution to prevent adsorption of moisture and oxygen into the system. In any case, the argon gas used is dehydrated by passing it through a silica gel column in advance, and then the copper powder is
It is deoxidized by passing it through a column heated to ℃ 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 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 used as a starting material for producing the novel polysilane compound represented by the general formula (1) of the present invention is a silane compound represented by the following formula: R+Rx5IC1z, or a silane compound represented by the formula: R3R4.
A silane compound represented by 1 g of SiC is selectively used.

As the above-mentioned condensation catalyst, an alkali metal is preferably used which initiates the condensation reaction by eliminating halogen, and 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 selected from halogenated alkyl compounds, halogenated cycloalkyl compounds, halogenated aryl compounds, and halogenated aralkyl compounds. A suitable compound selected from the group consisting of - formula: AX and/or - formula FA'-X, where X is C
Z or Br) and suitable compounds in the specific examples described below.

Used selectively.

The dichlorosilane monomer represented by the general formula: Rr Rt Si Cl z or this and the formula: Rs Ra Si Cl g used in synthesizing the above-mentioned intermediate polymer is dissolved in a predetermined solvent to form a reaction system. In this case, a paraffinic non-polar hydrocarbon solvent is preferably used as the solvent. Preferred examples of the solvent include n-hexane, n-octane, n-nonane,
Mention may be made of 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 the desired intermediate is obtained by 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 above-described novel polysilane compound represented by the general formula (1) of the present invention will be described below.

That is, the method for producing the above-mentioned novel polysilane compound according to the present invention comprises (1) producing an intermediate polymer; and (ii)
) introducing substituents A and A' to the terminals of the intermediate polymer.

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 condense 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 reaction formula (i) below, the chloro group of the dichlorosilane monomer and the catalyst cause a desalting reaction, and the 31 groups repeat condensation to form a polymer, producing an intermediate polymer. do.

R, RyuCl -eS i-+-7-(-31-)-r-CI
-(i) R mushroom 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 evaporating the sampling liquid and determining whether a film can be formed.

As the condensation 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 monomer is separated from the reaction system by decantation to obtain an intermediate polymer.

Next, the step (above) is carried out, that is, the terminal chloro groups of the obtained intermediate polymer are subjected to desalting condensation using a halogenated organic agent and a condensation catalyst (alkali gold), and the polymer terminal groups are converted to a predetermined concentration. Substitution with an organic group.The reaction at this time is shown in the following reaction formula (11) as follows:
Rs A -ESi-T----÷Si-t1-A'
... (ii) Rχ R4 Specifically, an aromatic solvent is added to the intermediate polymer obtained by condensation of dichlorosilane monomer, a condensation catalyst (alkali metal) is added, and the mixture is heated at room temperature. Add the halogenated organic agent dropwise. 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 amount. 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.The polysilane compound produced in the next stage is extracted with toluene and purified using a silica gel column. Thus, the desired new polysilane compound of the present invention is obtained.

R, R1SiC1@ and RiR* StCl g Note): Among the following compounds, a-2~! 6.18.20,2
1°23.24 is R, l? , used for SiC1,
a-1゜2.11.1? , I9, 22.23.25 is R
3R4SiC1! used for.

(CH3) xs+c 1.

((Qls) zcH) JiCj! z((CH3)
30□SjC et A-X and A'-X body (CI+3)! 01101. CjI CII+(Oft)nlJ aIs (CIIJ sC1 a-NG013 (CHi) + oc j!) C1h(C1l□) 5Br CHs(Oft)+oBr The catalyst is preferably an alkali metal.

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.

CH3 O13(Oh) 5-5t ←, (Ob) 5(113
01(CH,) I CI(Gls)t 01! h Cll.

l1ff ll3 (CHz) x Note): In the above structural formula, both X and Y represent monomer polymerized units, and n represents X/ (X+y), and m represents Y/ (x+Y). Each is calculated using a calculation formula.

〔Example〕

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

In addition, in the above-mentioned production examples and comparative production examples, first of all, CI! Check the presence or absence of Ct
For those in which the presence of groups is recognized, we quantify them.
Its abundance was expressed in millimole equivalents per 1000 grams of product.

In addition, regarding the obtained product, the long chain structure of 5L-3L
Whether or not it was a polysilane compound having a main chain consisting of bonds was confirmed by FT-IR and/or UV spectra. Furthermore, in conjunction with this, the presence or absence of bonding of substituents in the side chains was confirmed by examining by FT-IR and/or by examining protons in the substituents by FT-NMH.

The structure of the synthesized product was determined from the results obtained above.

As mentioned above, confirmation of the absence of CJ groups in the product can be done using fluorescent X&
I analyzer (fully automatic fluorescent X-ray analyzer system 3080
: manufactured by Rigaku Denki Kogyo Co., Ltd.). At that time, trimethylchlorosilane (manufactured by Chisso Co., Ltd.) was prepared as a standard sample, and 1.5.10.50,10
Standard solutions were prepared by diluting each of them 0 times, and each standard solution was subjected to the fluorescence X-ray analysis and folding device to measure the amounts of C and Z groups, and a calibration curve was determined based on the obtained results. . On the other hand, regarding the product to be tested, 1 gram of the product was dissolved in dehydrated toluene to make a total volume of 10 milliliter to prepare a test sample, which was measured using the fluorescent X-ray analyzer, and the measurement results were reported as described above. The amount of CZ group was determined by comparing with a calibration curve.

For measurement by FT-I H, a KBr berent of the test sample is prepared, and this is coated with N1coet FT-I R750.
(manufactured by Nikolay Japan) and measured.

In addition, for measurement by FT-NMR, the test sample is CD Cj
The measurement was carried out by dissolving the sample in s and setting it in FT-NMRFX-90 (manufactured by JEOL Ltd.).

In addition, in the UV spectrum, if the polysilane compound is a low-molecular one, the spectrum will be on the short wavelength side, and if it is a polymer, the spectrum will be on the long wavelength side. Chemistry (Pure & Applied Chemistry)
try) 5 4. F&i5. p p, 1 0 4
1-1050 (1982).

A three-way flask was prepared in a blow 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 tri-Solo flask, and heated to 100°C with stirring.0-order dichlorosilane monomer (Tisso ■1?) (a-7) 0.1 Mol was dissolved in 30 grams of dehydrated dodecane, and the prepared solution was slowly dropped into the reaction system.

After the dropwise addition, a white solid was precipitated by condensation polymerization at 100° C. for 1 hour. Thereafter, the mixture was cooled, the dodecane was decanized, 100 grams of dehydrated toluene was added to dissolve the white solid, and 0.01 mol of sodium metal was added.

Next, n-hexyl chloride (manufactured by Tokyo Kasei) (b-3
A solution prepared by dissolving 0.01 mol of ) in 10 ml of toluene was slowly added dropwise to the reaction system with stirring, and heated at 100° C. for 1 hour. Thereafter, the mixture was cooled, and 50 liters 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 purified by developing with a silica gel column and chromatography.
The product was obtained in a yield of . For this product, the C
When the content of jl groups was measured by a quantitative determination method, no Cl groups were found (ie, 0.00 mmole equivalent in 1000 grams of sample).

When the weight average molecular weight of the product was measured by GPC method by THF development, it was found to be 75.000 (
polystyrene as standard).

The product is then converted into KBr of the product as described above.
Create a pellet and N1coet F T -I R7
The FT-r R was measured using a FT-NMRFX-90Q (Cole Japan), and then a sample of the product was dissolved in CDCls as described above and FT-NMRFX-90Q
(manufactured by JEOL Ltd.) was used for FT-NMR measurement. As a result, it was found that the product was a polysilane compound having the above-mentioned structure C-1, which had all 5L-C1 bonds, 5i-0-3L bonds, and 5i-0-R bonds.

The above results are shown in Table 4.

1 Pilgrimage ■1 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.

In this Mitsuro flask, 100 grams of dehydrated dodecane and 1
0.3 mol of metallic lithium of square fi was charged and heated to 100°C with stirring.0-order dichlorosilane monomer (
Chisso special) (a-7) 0.1 mol dehydrated dodecane 30
A solution prepared by dissolving the solution in grams was slowly added dropwise to the reaction system, followed by condensation polymerization at 100° C. for 2 hours to precipitate a white solid. 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 0.02 mole of metallic lithium was added.

Next, chlorobenzene (manufactured by Tokyo Kasei) (b-5) 0.0
A solution prepared by dissolving 2 moles in 10 mj of toluene was slowly added dropwise to the reaction system with stirring, and 100 mj of toluene was added.
Heated at ℃ for 1 hour. Thereafter, the mixture was cooled, and methanol 50-1 was slowly added dropwise to remove excess metal lithium. This produced a suspended layer and a toluene layer.

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 Arashi 2 (structural formula: C-3). Yield is 7
2%, and the weight average molecular weight was 92.000.

The identification results are shown in Table 4.

1 stop■↓ Prepare a three-solo flask in a blow box that has been vacuum suctioned and replaced with argon, attach a reflux condenser, thermometer, and dropping funnel to it, and pass argon gas through the bypass pipe of the dropping funnel. .

100 g of dehydrated n-hexane and 0.3 mol of monometallic sodium were charged into this three-ring flask, and heated to 80°C with stirring.0. A solution prepared by dissolving 1 mol in dehydrated n-hexane was slowly dropped into the reaction system. After 0 drops, condensation polymerization was carried out at 80 ° C. for 3 hours.
A white solid precipitated out. After cooling, n-hexane was decanized and 100 grams of dehydrated toluene was added to dissolve the white solid, and 0.01 mol of sodium metal was added to the solution, followed by benzyl chloride (manufactured by Tokyo Kasei). (b-12) 0.01 mol toluene 1
A solution prepared by dissolving the solution in 0 ml was slowly added dropwise to the reaction system while stirring, and heated at 80° C. for 1 hour.

After this, it is cooled and the excess metal sodium is disposed of.
50 sl of methanol 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 development using a silica gel column and chromatography to obtain polysilane compound 11h3 (structural formula: C-4). The yield was 61%t, and the weight average molecular weight was 47,000. The identification results are shown in Table 4.

Note that in this polysilane compound, unreacted s t
-cIl, by-product Si -0-3L, 5i-O-
There was no IRQ yield attributed to H.

Otoshi ■ Reciprocal parallel development Synthesis was carried out in the same manner as in Example 3 using the dichlorosilane monomer and end group treatment agent shown in Table 1, and polysilane compound dynamics 4 (structural formula: C-6) and polysilane compound Na
5 (Structural formula: C-2), 60% and 62%, respectively
It was obtained in a yield of .

Note that in this polysilane compound, unreacted S 1
-Cjl, by-products 5i-0-3i, and 5t-O-R were not present at all.

The identification results are summarized in Table 4.

Synthesis was carried out in the same manner as in Example 3, except that dichlorosilane monomer (manufactured by Chisso ■) (a-7) was condensed in the same manner as in Example 3, and the end groups of the polymer were not treated. A polysilane compound NaD-1 having the structural formula shown in was obtained. The yield was 60% and the weight average molecular weight was 46,000. The identification results are shown in Table 4.

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

Polymerization was carried out in the same manner as in Example 3 using the dichlorosilane monomers shown in Table 2 and changing the reaction times as shown in Table 2. Further, a synthetic product using the compounds shown in Table 2 as the end group treatment agent was purified in the same manner as in Example 3. (The polysilane compound light 6 to 1 shown in Table 4)
I got 0.

Yield, weight average molecular weight, and weight average molecular weight of each polysilane compound obtained
The results of FT-IR and FT-NMR were as shown in Table 4.

In addition, in any polysilane compound, unreacted 3
iCl % by-product 5i-o-sl.

Attributed to 5i-0-R! There was no R absorption at all.

Stop comparison inhibition main example 6. Synthesis was carried out in exactly the same manner as in Example 6 except that the reaction time of the dichlorosilane monomer was changed to 10 minutes to obtain polysilane compound Arashi D-2 shown in Table 4.

Yield, weight average molecular weight of the obtained polysilane compound,
Conclusions by FT-IR and FT-NMR.

The results were as shown in Table 4.

In addition, regarding the obtained polysilane compound, unreacted (7) Si-CI and by-product (F) Sl-0-3t.

There was no TR absorption assigned to S l-0-R.

Table 2 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 to obtain polysilane compound dynamics 11 to &14 shown in Table 4. Ta. Yield, weight average molecular weight, F of each polysilane compound obtained
The results of T-IR and FT-NMR were as shown in Table 4.

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

A three-way flask was prepared in a blow box that had been used for main vacuum suction and argon replacement, and a reflux condenser, temperature needle, 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 wire-shaped sodium metal were placed in this three-ring flask, and heated to 100°C with stirring. 0.1 mol of 0-order dichlorosilane monomer (manufactured by Chinso) was added to 30 grams of dehydrated dodecane. The prepared solution was slowly added dropwise to the reaction system. After 0 drops, the solution was polycondensed at 100°C for 1 hour.
A white solid precipitated out. Thereafter, the mixture was cooled, and 50 tsl of methanol was slowly added dropwise to remove excess metal sodium.

Next, the white solid was collected by filtration, washed repeatedly with n-hexane and methanol, and the polysilane compound magnetodynamic D-
I got 3.

This polysilane compound contains toluene, chloroform, TH
Since F and the like are insoluble in organic solvents, identification was performed by FT-IR. The results were as shown in Table 4.

A three-ring flask was prepared in a blow box that had undergone vacuum suction and argon substitution, a reflux condenser, a thermometer, and a dropping funnel were attached to it, and argon gas was passed through each tube of the dropping funnel.

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

Next, diphenyldichlorosilane monomer (manufactured by Chisso ■)
A solution prepared by dissolving 0.1 mole of in 30 grams of dehydrated dodecane was slowly added dropwise to the reaction system.
A white solid was precipitated by condensation polymerization at 0° C. for 1 hour.

After this, it is cooled and the excess metal sodium is disposed of.
50-J of methanol was slowly added dropwise.

Next, the white solid was collected by filtration and washed repeatedly with n-hexane and methanol to form a polysilane compound shown in Table 4.
I got 4.

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

Table 1, LfLL An example of using the polysilane compound of the present invention as a resist material is shown below.

Phenolborac resin (AZ-
B50J manufactured by Nijitsu Brei Co., Ltd.) was formed to a thickness of 2 μm by spin coating and heated at 150°C for 30 minutes.
Next, 5 parts by weight of polysilane 1 obtained in Example 1,
Dissolve 0.5 parts by weight of p-hydroquinone in toluene,
A polysilane layer with a thickness of 0.3 μm was formed by spin coating, and a composite resist layer was prepared by beta-coating at 90° C. for 30 minutes.

This was irradiated with ultraviolet light for 30 seconds using a 500 W xenon-mercury lamp through a quartz mask with a width of 0.2 μm and 0.5 μm. After immersing in a mixed solvent of toluene and isopropyl alcohol (weight ratio 1:5) for 30 seconds and developing, rinse with isopropyl alcohol to obtain 0.2μm and 0°5μm.
A positive resist pattern with m line width was obtained. Next, oxygen plasma etching is performed, and the lower organic layer is dry etched to give an asbestos ratio of 0.2 pmv or more of 2.
A resist pattern with an A width and a line width of 0.5 μm could be formed.

The film-forming ability and resist pattern developability of this polysilane compound were evaluated and shown in Table 5.

In addition, the polysilane compound was dissolved in dichloromethane, and the ultraviolet absorption spectrum was measured using a spectrophotometer (U-'34 (10, manufactured by Hitachi Seisakusho), and the obtained maximum absorption wavelength (λwax) is shown in Table 5. .

The value of the polysilane compound used in Usage Example 1 is Na2~1
Resist patterns were formed and evaluated in exactly the same manner except that resist patterns No. 4 and D-1-D-4 were replaced. The results are shown in Table 5.

(Summary of the Effects of the Invention) As explained above, the polysilane compound of the present invention is produced by condensation polymerization by removing halogen from a dichlorosilane monomer, and further converting the terminal group of the polysilane into a halogenated organic group and in the presence of an alkali metal. It is a novel polysilane compound synthesized by desalting condensation and has excellent solubility and film-forming ability.

Claims (3)

[Claims] (1) Represented by general formula (I) and has a weight average molecular weight of 600
A new and previously unknown polysilane compound having a molecular weight of 0 to 200,000. ▲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 proportion of the number of each monomer to the total monomers in the polymer, and n
+m=1, 0<n≦1, 0≦m<1. ] (2) In general formula (I), A and A' have 5 carbon atoms
The polysilane compound according to claim 1, which is represented by 1 to 12 alkyl groups or cycloalkyl groups. (3) 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. Synthesis is carried out by separating the polymer from unreacted monomers, reacting the polymer with a predetermined halogenated organic reagent in the presence of a condensation catalyst made of an alkali metal, and condensing an organic group at the end of the polymer. The general formula according to claim 1, characterized in that (
A method for producing a novel polysilane compound represented by I).