JP2576312B2 - Polysilane film composition and crosslinked polysilane film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a polysilane film having excellent solvent resistance and excellent properties such as abrasion resistance and impact resistance. It relates to a polysilane film.

[0002]

2. Description of the Related Art A polysilane polymer is a compound useful as a material for preceramics, conductive materials, semiconductors, etc. because of its properties such as photoreactivity and thermochromic properties. In particular, polysilane has attracted much attention in recent years because polysilane is soluble in an organic solvent and can be dissolved in a solvent and applied in a solution state on various substrates to form a film. This is because a very wide range of applications can be expected. Therefore, research on polysilanes has been dominant in one-dimensional structures, but recently research has expanded to polysilanes with two-dimensional and three-dimensional structures, such as ladder-polysilane and silacuban, which can further improve the characteristics of semiconductors. Have been.

However, polysilanes having a two-dimensional or three-dimensional structure have disadvantages in that their solubility in organic solvents is lower than those having a one-dimensional structure, and gel insolubles are formed, resulting in a poor reaction yield. For this reason, application in a wide range was difficult.

[0004] Further, as a method of forming a film of a polysilane solution on a substrate to fix and insolubilize it, (1) a method of crosslinking using a titanium compound, and (2) a polysilane having a vinyl group and SiH generated by thermal rearrangement of the polysilane. A method of crosslinking using a reaction with a group is known. However, the crosslinking groups in these methods are SiOTiOSi groups or SiCH ₂ CH ₂ Si groups, and charge delocalization does not occur. Therefore, when the polysilane solution is immobilized and insolubilized by these methods and applied to a semiconductor, its characteristics It was difficult to expect improvement.

[0005] The present invention has been made in view of the above circumstances,
Highly soluble in organic solvents, used in a solution state to form a film on a substrate, insoluble in the solvent by crosslinking this,
Another object of the present invention is to provide a polysilane polymer composition which gives a crosslinked polysilane film capable of satisfactorily improving its properties when applied to a semiconductor or the like, and a crosslinked polysilane film obtained therefrom.

[0006]

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a polysilane containing a SiH group represented by the following general formula (1), polyethynylbenzene, When a cross-linking catalyst such as α, α'-azobisisobutyronitrile or a platinum catalyst and an organic solvent are blended, the polysilane can be easily dissolved in the organic solvent to form a solution, and the polysilane solution is added to the substrate. It has been found that a polysilane film composition which is insoluble in a solvent and which gives a crosslinked polysilane film having excellent properties, when coated on a film, crosslinked by film formation, is obtained.

[0007]

Embedded image (Where R ¹ , R ² and R ³ each have 1 to 8 carbon atoms)
R ⁴ is the same group as R ¹ or a hydrogen atom, an OH group or an OR ¹ group, and m and n are each (m / m + n) × 100 = 0.1 to 50 mol% Is the number )

That is, the polysilane of the above formula (1) is different from a conventional cross-linking group-based polysilane in that a group represented by the following formula (2) in which electrons can be delocalized using a π-electron system is used as a cross-linking group. By doing so, the electrons are delocalized on both the main chain Si-Si and the cross-linking group, and when cross-linked, the polysilane film becomes insoluble in the solvent without any decrease in semiconductor properties, and the strength is also improved. Abrasion resistance, knowing that the so-called durability such as impact resistance is improved, for example, finding that it can be suitably applied as a charge transfer body for a copying drum,
The present invention has been made.

[0009]

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Accordingly, the present invention provides a polysilane film comprising (1) a polysilane containing a SiH group represented by the above general formula (1), (2) polyethynylbenzene, (3) a crosslinking catalyst, and (4) an organic solvent. Provided are a composition and a crosslinked polysilane film obtained by forming the polysilane film composition into a film and crosslinking the composition.

Hereinafter, the present invention will be described in more detail. The first essential component of the polysilane film composition of the present invention is a polysilane containing a SiH group represented by the following general formula (1).

[0012]

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Here, R ¹ , R ² , R ³ in the above equation (1)
Is a monovalent hydrocarbon group having 1 to 8, preferably 1 to 7 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group and a cyclohexyl group, and an aryl group such as a phenyl group and a tolyl group. Is exemplified. R ⁴ is R ¹
Or a hydrogen atom, an OH group or an OR ¹ group. Further, m and n are (m / m + n) × 100 =
It is a number that can be 0.1 to 50 mol%, preferably 1 to 10 mol%.

Specific examples of the polysilane of the formula (1) include compounds having the following structures (in the following formula, Me is a methyl group and Ph is a phenyl group).

[0015]

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The polysilane of the above formula (1) is, for example, a compound represented by the following formula (3) and a compound represented by the following formula (4):
It can be easily obtained by polycondensing the compound represented by the formula with sodium metal. [R. We
st, JACS 103, 7352, (1981)]

[0017]

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In this case, in the above reaction, the amount of SiH groups in the polysilane obtained by the mixing ratio of both compounds, that is, the values of m and n can be controlled, and the value of m (Si
If the amount of the H group is less than the above range, the strength of the crosslinked film will be insufficient, and if it is more than the above range, the molecular weight of the obtained polysilane will decrease.

The second essential component, polyethynylbenzene, is an acetylene compound in which at least two or more ethynyl groups are directly bonded to a benzene ring, and bisethynylbenzene or triethynylbenzene is particularly preferably used. You.

The amount of polyethynylbenzene is 0.01 to 1 with respect to 10 parts of the polysilane of the formula (1).
0 parts (parts by weight, hereinafter the same), particularly preferably 0.1 to 5 parts. If the amount is less than 0.01 part, sufficient crosslinking strength may not be obtained. If the amount of the polysilane of the formula (1) is larger than the above, yellowing may be caused by a decrease in heat resistance.

The above polyethynylbenzene can be easily prepared by reacting the corresponding polybromobenzene with trimethylsilylacetylene in the presence of a palladium catalyst as shown in the following reaction formula and then hydrolyzing to remove the silyl group. (N. Hagihar)
a, Synthesis, 627, 1980).

[0022]

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Further, in the present invention, a catalyst for promoting a cross-linking reaction between the SiH group of the polysilane of the above formula (1) and the HC≡C- group of the polyethynylbenzene is blended as the third essential component. As the catalyst, the radical generators α and α ′
-Azobisisobutyronitrile (hereinafter abbreviated as AIBN) or a platinum catalyst used as a general hydrosilylation catalyst can be blended.

Here, as the platinum catalyst, for example, chloride white
Auric acid, PtCl_Two(COD) (where COD is 1,5-
An olefin complex such as cyclooctadiene), Pt
Cl_Two(CH_ThreeCN )_TwoNitrogen-containing complex such as Pt (PPh_Three)
_FourAnd the like.

The amount of the above catalyst can be a catalytic amount, but AIBN is added to 10 parts of the polysilane of the formula (1).
Is preferably 0.001 to 5 parts, particularly 0.1 to 3 parts, and the platinum catalyst is preferably 0.0001 to 1 part, particularly 0.01 to 0.1 part.

When AIBN is used, it is preferable to heat the mixture to 60 to 180 ° C. to promote the crosslinking reaction so that radicals can be easily generated by thermal decomposition. When a platinum catalyst is used, the reaction proceeds if the composition is left for a long time even at room temperature.
It is desirable to heat to about 120 ° C. If the amount of the catalyst or the reaction temperature is less than the above range, the crosslinking reaction may not proceed sufficiently.
In some cases, the characteristics may be deteriorated due to the breaking of the Si bond.

The composition of the present invention contains an organic solvent as a fourth essential component. In this case, as the organic solvent,
Any one can be used as long as it can dissolve the polysilane of the formula (1) and polyethynylbenzene. Examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, and ethers such as tetrahydrofuran (THF). And one or more of these are preferably used.

The amount of the organic solvent is from 10 to 10,000 parts, especially from 90 to 10 parts, per 10 parts of the polysilane of the formula (1).
If the amount is less than 10 parts, the polysilane film may not be formed properly.
If it exceeds 000 parts, the composition may be too diluted to form a good film.

The polysilane film composition of the present invention can be formed into a film by thoroughly mixing the above-mentioned first to fourth essential components, dispersing them in a solvent, applying the mixture on a substrate, and air-drying. .

In this case, various substrates can be used, for example, quartz, glass plate, silicon plate, aluminum foil,
Stainless steel foil, copper plate, etc. can be used. Further, it is desirable that the coating thickness on the substrate is 0.1 to 100 μm.

Further, after air-drying, it is preferable to put it in an oven at 60 to 180 ° C., particularly 80 to 150 ° C. and heat it for 1 to 30 minutes, whereby a strong thin film insoluble in an organic solvent is formed on the substrate. Can be formed.

[0032]

As described above, the polysilane film composition of the present invention comprises:
A polysilane film having excellent solvent resistance and excellent properties such as abrasion resistance and impact resistance is provided, and is suitable as a material for semiconductors, charge transfer bodies for copying drums, and the like.

[0033]

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. All parts in each example are parts by weight.

Examples and Comparative Examples (1) Synthesis of polysilane containing 3.0 mol% of SiH group West, JACS, 103, 7352, 1981
A mixture of 97 mol% of phenylmethyldichlorosilane and 3 mol% of methyldichlorosilane was dropped into sodium metal dispersed in toluene, and a polysilane containing 3.0 mol% of a SiH group represented by the following formula was prepared according to the method described in (1). Hereinafter, abbreviated as HPS) was synthesized.

[0035]

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Similarly, methyl dichlorosilane 0 mo
1% of polysilane (hereinafter abbreviated as PS) was also synthesized. (2) Synthesis of diethynylbenzene Hagihara, Sythesis, 627,
According to the method described in 1980, diethynylbenzene represented by the following formula (hereinafter abbreviated as DEB) was synthesized.

[0037]

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The polysilane obtained by the above method, DAB,
α, α'-azobisisobutyronitrile (hereinafter referred to as AIB
N), PtCl ₂ (1,5-cyclooctadiene) (hereinafter abbreviated as PtCl ₂ (COD)), and toluene in the mixing ratio shown in Table 1 and sufficiently dissolved with a shaker to obtain a polysilane film. A solution of the composition was obtained.

This solution was applied on a quartz plate and heated at 25 ° C. for 1 hour.
It was air-dried for 5 minutes to form a polysilane thin film of 2-3 μm. Next, this polysilane thin film was heated in an oven at 120 ° C. for 15 minutes for cross-linking to obtain a sample film.

The external appearance after coating on a quartz plate and air-drying at 25 ° C. for 15 minutes and the external appearance after heating and crosslinking at 120 ° C. for 15 minutes were observed, and the residual ratio of the sample film to wetness with toluene was evaluated by the following method. The results are also shown in Table 1. Toluene wet residual ratio: The polysilane film on the glass plate was put into toluene and wetted, pulled up after one hour, and the residual ratio of the polysilane area remaining on the glass plate after the solvent was wiped off was determined as the toluene wet residual ratio.

[0041]

[Table 1]

From the results shown in Table 1, it was confirmed that the polysilane film composition of the present invention (Examples 1 to 3) gave a polysilane film having excellent solvent resistance. Further, the composition of the present invention had high strength and was excellent in so-called durability such as abrasion resistance and impact resistance.

Claims (2)

(57) [Claims] (1) Si represented by the following general formula (1)
Polysilane containing H groups. Embedded image (Where R ¹ , R ² and R ³ each have 1 to 8 carbon atoms)
R ⁴ is the same group as R ¹ or a hydrogen atom, an OH group or an OR ¹ group, and m and n are each (m / m + n) × 100 = 0.1 to 50 mol% Is the number A polysilane film composition comprising (2) polyethynylbenzene (3) a crosslinking catalyst (4) an organic solvent. 2. A crosslinked polysilane film obtained by forming the polysilane film composition according to claim 1 into a film and crosslinking the film.