JPH11199674A - Organosilicon-based polymer composition and cross-linking method thereof - Google Patents

Abstract

(A) (A) (Amended) (A) 100 parts by weight of an organosilicon-based polymer substance having a Si—Si bond and at least two or more Si—H in one molecule (B) One molecule Compounds containing a multiple bond selected from two or more alkenyl groups or alkynyl groups 1 to 20
0 parts by weight (C) an azo radical generator 1 represented by the formula (1)
An organosilicon-based polymer composition characterized by containing 〜50 parts by weight. [R ¹ , R ² , R ⁴ , and R ⁵ represent a hydrocarbon group, and R ³ and R ⁶ represent —R ¹¹ _a COOR ¹² or —R ²¹ _a OOCR ²² (R ¹¹ , R ²¹
Is a divalent hydrocarbon group, R ¹² and R ²² are monovalent hydrocarbon groups, and a is 0 or 1). [Effect] The composition is crosslinked by heating in an inert gas stream, so that the solubility in a solvent is improved. It gives a low, strong and transparent film, and the Si-Si skeleton does not participate in this crosslinking reaction and maintains almost the same optical and chemical properties as before the crosslinking.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic silicon-based polymer containing an organic silicon-based polymer material containing a Si--Si bond, such as polysilane, which is useful as a conductive material, a photoconductive material, and a nonlinear optical material. The present invention relates to a molecular composition and a method for cross-linking the same, and more particularly to a method for obtaining a cross-linked product while a product after cross-linking optically or chemically retains properties specific to Si—Si bonds.

[0002]

2. Description of the Related Art Conventionally, organic silicon-based polymer materials containing Si—Si bonds, such as polysilane, have been attracting attention for their unique chemical and optical properties. Although it is expected as a substance, a photoconductive substance, a non-linear optical substance, etc., it has not been able to obtain a sufficient development due to a problem of insufficient physical strength and compatibility with other substances. Since the Si—Si bond has photodegradability, its application as a radical initiator has been studied, but it has not been possible to obtain a sensitivity sufficient for practical use.

As a method for improving the strength of a silicon-based polymer material containing a Si—Si bond, a method has been proposed in which ≡Si—H and a compound containing two or more multiple bonds are crosslinked by an addition reaction. In this case, as the catalyst, a method using a Group VIII compound such as a platinum compound frequently used in polysiloxane or a method using a radical generator such as an organic peroxide or an azo compound such as AIBN is proposed. Have been.

However, when a heavy metal such as a platinum compound is used, there is a risk of migration or the like even in a trace amount when applied to a coating agent or the like used directly on a semiconductor surface such as an LSI, and the use thereof is not preferable.

On the other hand, the cross-linking reaction using an organic radical initiator requires a large amount of a radical generator because these reactions are not a radical chain but a sequential reaction.
It is a preferred catalyst for applications that do not contain metals and in which contamination with metallic impurities is a problem. However, in the case of a peroxide-based radical generator, the formation of siloxane due to the oxidation reaction of the Si-Si skeleton cannot be ignored, and there is a problem in obtaining a crosslinked product while maintaining the properties unique to the Si-Si skeleton. .

In particular, a nitrile group-containing radical generator such as AIBN as an azo-based radical initiator contains a large amount of Si-Si bonds such as polysilane, although there is a concern about the safety of decomposition products. Poor compatibility with silicon-based polymer substances, it is relatively difficult to obtain a composition in which the cross-linked film has dissolved therein an effective amount necessary to show solvent insolubility. No suitable cross-linking method has yet been found.

Accordingly, the present invention relates to an organosilicon-based polymer which can be crosslinked without contamination while retaining the properties specific to the Si-Si bond of the organosilicon-based polymer material containing a Si-Si bond. It is an object to provide a composition and a method for crosslinking the composition.

[0008]

Means for Solving the Problems and Embodiments of the Invention The present inventors have attained the above-mentioned object and have achieved the object of the present invention by using Si-S
As a result of diligent studies to obtain a method for improving the physical strength by cross-linking the organosilicon polymer material containing i-bonds without impairing the optical and chemical properties, an organosilicon polymer such as polysilane was obtained. The radical initiator consisting of a specific non-nitrile azo compound having an ester group instead of the azo compound containing a nitrile group proposed in the prior art relating to the crosslinking of a substance is an organosilicon containing a normal Si-Si bond The present inventors have found that they show good compatibility with a system polymer substance, and have accomplished the present invention.

That is, the present invention relates to the following: [I] (A) 100 parts by weight of an organosilicon polymer having at least two Si—H bonds and one Si—H in one molecule; 1 to 200 parts by weight of a compound containing a multiple bond selected from two or more alkenyl groups or alkynyl groups, and (C) 1 to 50 parts by weight of an azo radical generator represented by the following formula (1). An organosilicon-based polymer composition, and [II] a method for crosslinking an organosilicon-based polymer composition, comprising heating the composition at a temperature of 100 ° C or higher.

[0010]

Embedded image [Wherein, R ¹ , R ² , R ⁴ , and R ⁵ represent an unsubstituted or substituted monovalent hydrocarbon group, and R ³ and R ⁶ represent —R ¹¹ _a COOR ¹² or —R
²¹ _a OOCR ²² (R ¹¹ and R ²¹ are unsubstituted or substituted divalent hydrocarbon groups, R ¹² and R ²² are unsubstituted or substituted monovalent hydrocarbon groups,
a is 0 or 1). ]

Hereinafter, the present invention will be described in more detail.

The component (A) of the organosilicon polymer composition of the present invention is an organosilicon polymer material having a Si—Si bond and two or more SiH groups in one molecule.

Here, as this organosilicon-based polymer substance, a linear or branched polysilane or polycarbosilane having a weight average molecular weight of 500 to 500,000 can be used. The ones shown can be used.

[(R ³¹ _x R ³² _y Si) _n (HR ³³ _z Si) _m (Q) _q ] _p (2) where R ³¹ is a hydrogen atom, a halogen atom such as a chlorine atom,
An alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group, or an unsubstituted or substituted monovalent hydrocarbon group;
Examples of the valent hydrocarbon group include C 1-20, especially 1-10
Are preferred, specifically, a methyl group, an ethyl group,
Saturated hydrocarbon groups such as alkyl groups such as propyl group, isopropyl group, butyl group, tert-butyl group and hexyl group, cycloalkyl groups such as cyclohexyl group, and aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group An aromatic hydrocarbon group such as an aralkyl group such as a benzyl group or a phenylethyl group; an unsaturated hydrocarbon group such as an alkenyl group such as a vinyl group, an allyl group, a propenyl group, an isopropenyl group or a butenyl group; Examples thereof include a halogen-substituted hydrocarbon group such as a 3-trifluoropropyl group, and a cyano-substituted hydrocarbon group. R ³² and R ³³ are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group as described above.

Further, x is 0 to 1, y is 1 to 2, x + y =
Is a number satisfying 1 to 3, z is 0 to 1, and n is 2
The above integer m is a number satisfying that two or more SiH groups are contained in one molecule.

Q is a divalent organic group, and those having 1 to 20, particularly 2 to 20, carbon atoms can be used. Q is 0 to 1. Examples of Q include the following.

[0017]

Embedded image

The above Q is interposed between Si-Si bonds, and can form the following structure, for example.

[0019]

Embedded image

In the above formula (2), q is from 0 to 3
Is the number of p is a weight average molecular weight of 500 to 500,0.
This is a number that satisfies 00.

As the polymer substance of the above formula (2), particularly in applications utilizing optical characteristics in the ultraviolet region,
Units containing an aryl group are preferred.

The polymer used in the present invention is not particularly limited as long as it satisfies the above conditions.
In applications utilizing the optical or electronic properties due to σ conjugation specific to polymers having i-Si bonds, it is preferable that there be at least two or more Si-chains, and the weight average molecular weight is 500 to 500,000. It is desirable. If the molecular weight is less than 500, the chain unit length is small, the crosslinking efficiency is reduced, and characteristics such as solvent resistance are hardly obtained. On the other hand, when the molecular weight exceeds 500,000, the viscosity increases when dissolved in an organic solvent, and it becomes difficult to ensure uniformity of the applied thickness.

In the compound containing an aliphatic multiple bond selected from two or more alkenyl groups or alkynyl groups in one molecule of the component (B), the alkenyl group and the alkynyl group include a vinyl group, a (meth) acryl group, Examples of these compounds include vinyl group-containing siloxane, vinyl group-containing polysilane, 1,4-butanediol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Acrylates of polyhydric alcohols such as, further, allyl ether compounds such as triallyl formal, triallyl isocyanurate and triallyl cyanurate;
Diethynylbenzene, 1,3-diethynylbenzene,
Acetylene derivatives such as 1,1′-diethynylbiphenyl can be exemplified.

Of these, those having two or more (meth) acryloxy groups in one molecule are preferred.

The compounding amount of the compound containing the multiple bond of the component (B) is 1 to 200 parts, preferably 5 to 5 parts, per 100 parts (parts by weight, hereinafter the same) of the polymer substance of the component (A).
It is preferably 0 parts, more preferably 5 to 30 parts.

The component (C) of the composition of the present invention is an azo radical generator containing an ester group represented by the following formula (1).

[0027]

Embedded image [Wherein, R ¹ , R ² , R ⁴ , and R ⁵ represent an unsubstituted or substituted monovalent hydrocarbon group, and R ³ and R ⁶ represent —R ¹¹ _a COOR ¹² or —R
²¹ _a OOCR ²² (R ¹¹ and R ²¹ are unsubstituted or substituted divalent hydrocarbon groups, R ¹² and R ²² are unsubstituted or substituted monovalent hydrocarbon groups,
a is 0 or 1). ]

Here, R ¹ , R ² , R ⁴ , R ⁵ , R ¹² , R ²²
Examples of the monovalent hydrocarbon group include the same as those exemplified for R ³² and R ³³ . In addition, R ¹¹ and R ²¹
Preferred are those having 1 to 8 carbon atoms, particularly 1 to 6 carbon atoms, and examples thereof include an arylene group such as an alkylene group and a phenylene group. Incidentally, the like can be exemplified OOCCH _3, COOCH ₃ as the group R ^3, R ⁶ of formula (1) is to form an ester.

Among these, 1,1′-azobis (1
-Acetoxy-1-phenylethane) [trade name OTaz
o-15, manufactured by Otsuka Chemical], dimethyl-2,2'-azobis (2-methylpropionate) [trade name: V-601,
Manufactured by Wako Pure Chemical Industries, Ltd.] can be preferably used.

According to the present invention, by using the radical generator of the above formula (1), the compatibility with the component (A) is good, and a strong film is obtained by crosslinking.

[0031]

Embedded image

The amount of the radical generator (C) is 1 to 50 parts, preferably 1 to 20 parts, more preferably 3 to 10 parts, per 100 parts of the component (A).

The organosilicon polymer composition of the present invention is preferably used in the form of a solution in which the above components are dissolved in an organic solvent. In this case, as the organic solvent, the above (A)
Any component capable of dissolving the components (C) to (C) may be used. For example, toluene, xylene, anisole, PGMEA and the like can be used. The solid content varies depending on the method of forming the coating film and the desired thickness, but is 3 to 40% by weight, particularly 5 to 40% by weight.
It is preferably 20% by weight.

The composition of the present invention may contain, if necessary, appropriate components within a range not to impair the object of the present invention.

The composition of the present invention is applied on a substrate by an appropriate method such as a spin coating method and crosslinked to be used.
In this case, the crosslinking involves bringing the composition above 100 ° C., preferably 1 ° C.
It can be carried out by heating to 00 to 250 ° C, more preferably 120 to 200 ° C. Further, the atmosphere for heating is preferably a non-oxidizing atmosphere having an oxygen concentration of 0.1% by volume or less.

[0036]

According to the present invention, Si-Si bond and Si-
A transparent composition comprising a silicon-based polymer such as H-containing polysilane, a compound having two or more multiple bonds in one molecule, and an azo radical initiator containing an ester group can be obtained. This composition is crosslinked by heating in an inert gas stream to give a strong and transparent film with low solubility in a solvent, and the Si-Si skeleton does not participate in this crosslinking reaction and is almost equivalent to that before crosslinking. Maintain the optical and chemical properties of

[0037]

EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, in the following examples, a part shows a weight part.

Example 1 Average composition formula [Ph H_0.9S
i]_nHaving a weight average molecular weight of 3,200
80 parts of trimethylolpropane triacrylate
(A-TMPT) 20 parts and S as a radical initiator
Table 1 shows terazo-containing OTazo-15 (manufactured by Otsuka Chemical).
The composition was prepared by adding the composition as shown. This composition
Into a 10% solution in xylene and put on a glass slide.
A final film was prepared and air-dried for 30 minutes under nitrogen flow for 12 minutes.
Perform thermal crosslinking at 0 ° C for 5 minutes to form a 0.8 µm thick film.
did. After air drying, after thermal crosslinking, and after thermal crosslinking,
Recall methoxy ether acetate (PGMEA) and
And ethyl lactate (EL) for 1 minute each
After the immersion, the state of the film at each stage was observed.
As a result, the appearance of the film is transparent at any stage,
I got it.

A similar film was formed on quartz glass and a silicon wafer for optical characteristics, and the UV spectrum, IR
The spectrum was measured, and the absorption intensity decreased due to Si—Si showing decomposition of polysilane before and after the heat treatment, and S
No increase in absorption due to i-O-Si was observed.

[0040]

[Table 1] ：: No change in appearance after washing with water at all △: Slight discoloration in appearance after washing with water ×: Discoloration in appearance after washing with water

Comparative Example 1 As in Example 1, a cast film was prepared from a xylene solution using AIBN as a radical initiator. As a result, as shown in Table 2, A-TM
Even when the amounts of PT and AIBN were changed, crystals were precipitated by air drying, and a good film could not be obtained. Table 2 shows the results.

[0042]

[Table 2]

Example 2, Comparative Example 2 The average composition formula is [(Ph ₂ Si) ₄ (MeHSi) ₂ (Me ₂ SiC ₆ H ₄ S)
The same test as in Example 1 and Comparative Example 1 was performed except that a silicon-based polymer material having a weight average molecular weight of 18,000 comprising iMe ₂ ) ₂ ] was used. The results are shown in Table 3. The numbers in Table 3 represent the ratio (parts) of the compounding ratio.

From the results in Table 3, it is clear that A in the xylene solution
Although IBN was dissolved, the homogeneity was lost as the solvent disappeared.

[0045]

[Table 3]

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Eiichi Tabei 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (7)

[Claims] (A) 100 parts by weight of an organosilicon polymer having at least two Si—H bonds in one molecule and (B) two or more alkenyl groups or Compound containing multiple bonds selected from alkynyl groups 1 to 200 parts by weight (C) 1 to 50 parts by weight of an azo radical generator represented by the following formula (1) [Wherein, R ¹ , R ² , R ⁴ , and R ⁵ represent an unsubstituted or substituted monovalent hydrocarbon group, and R ³ and R ⁶ represent —R ¹¹ _a COOR ¹² or —R
²¹ _a OOCR ²² (R ¹¹ and R ²¹ are unsubstituted or substituted divalent hydrocarbon groups, R ¹² and R ²² are unsubstituted or substituted monovalent hydrocarbon groups,
a is 0 or 1). ] An organosilicon-based polymer composition comprising: 2. The composition according to claim 1, wherein the components (A), (B) and (C) are in the form of a solution dissolved in an organic solvent. 3. The composition according to claim 1, wherein the organosilicon polymer is a polysilane or polycarbosilane having a weight average molecular weight of 500 to 500,000. 4. The compound having a multiple bond is a compound having two or more allyloxy groups in one molecule.
Or the composition according to 3. 5. An azo radical generator comprising 1,1′-
The composition according to any one of claims 1 to 4, which is azobis (1-acetoxy-1-phenylethane) or dimethyl-2,2'-azobis (2-methylpropionate). 6. A method for crosslinking an organosilicon-based polymer composition, comprising heating the organosilicon-based polymer composition according to claim 1 at a temperature of 100 ° C. or higher. 7. The method for crosslinking an organosilicon polymer composition according to claim 6, wherein the atmosphere to be heated has an oxygen concentration of 0.1% by volume or less.