JPH0565351A - Polyethylene film containing organosilicon polymer and preparation thereof - Google Patents

Abstract

PURPOSE:To provide the subject film which contains an organopolysilane easily handled yet retaining characteristics inherent in an organopolysilane. CONSTITUTION:The objective film contg. 0.1-10wt.% polymethylphenylsilane and having a thickness of 10-1,000mum is prepd. by pouring a soln. of polyethylene contg. polymethylphenylsilane in an amt. of 0.1-10wt.% of polyethylene into a poor solvent to give a powdered precipitate, thermally melt molding the precipitate into a film, and, if necessary, stretching the film. Polymethylphenylsilane having an average mol.wt. of 1,000-1,000,000 and polyethylene having an average mol.wt. of 1,000-150,000 are used. The film is useful as an optical waveguide material, a nonlinear optical material, and a light- emitting material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a soluble organic polysilane polymer which is a new type of functional material which is not present in conventional polymer materials having a carbon skeleton as an optical waveguide material, a non-linear optical material and a light emitting material. And a method for producing the same.

[0002]

2. Description of the Related Art Recently, soluble organic polysilane, which is a polymer having silicon as a skeleton, has a new type of function as an optical waveguide material, a non-linear optical material, and a light emitting material, which is not present in conventional polymer materials having a carbon skeleton. Has attracted a lot of attention as a functional polymer material. However, the organic polysilane alone is not sufficient in film forming ability. This is because if you try to control the near-ultraviolet absorbance range, which is characteristic of polysilane, to about 0.5 to 4 which is practical for application, the film thickness will be on the order of submicron, which is very thin. It is completely impossible to form a single film of organic polysilane without the presence of a metal. On the other hand, it is necessary to control the molecular weight of the organic polysilane in order to carry out the melt molding process, but at present the method is not known and impossible. Therefore, there is usually only a method of immobilizing such an ultrathin film on a supporting substrate by an operation of applying a solution of organic polysilane dissolved in an appropriate organic solvent on the supporting substrate. Therefore, the handling of organic polysilane has been extremely inconvenient from the viewpoints of optical waveguide materials, nonlinear optical materials, and light emitting materials. On the other hand, since the near-ultraviolet absorption band of organic polysilane extends in the polymer main chain direction, uniaxial orientation is desirable in order to further improve the properties of organic polysilane as an optical waveguide material, a nonlinear optical material, and a light emitting material. However, until now, there has been no example of successful orientation with organic polysilane alone, but there is only an example of rubbing orientation of dihexylpolysilane having a very low melting point of 40 ° C. on a glass substrate.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide organic polysilanes expected as optical waveguide materials, nonlinear optical materials, and light emitting materials in a form that is easy to handle while retaining the properties of organic polysilanes. Therefore, it is an object of the present invention to provide a polymer film containing an organic polysilane and a method for producing the same. Another object of the present invention is to provide a polymer film containing an organic polysilane having an organic polysilane main chain oriented by stretching the polymer film containing the organic polysilane, and a method for producing the same.

[0004]

SUMMARY OF THE INVENTION The present invention will be outlined. The first invention of the present invention relates to a polyethylene film containing an organic silicon polymer, wherein polymethylphenylsilane is added to polyethylene in an amount of 0.1 to 10%. It is characterized by containing by weight and having a thickness of 10 to 1000 μm. The second invention of the present invention relates to a method for producing a polyethylene film containing an organic silicon polymer, wherein polymethylphenylsilane is contained in an amount of 0.1 to 10% by weight based on polyethylene.
The mixed solution is reprecipitated in a poor solvent, and the obtained organosilicon polymer-containing polyethylene powder is further melt-heated and molded to form a film having a thickness of 10 to 1000 μm. And the third invention of the present invention is an invention relating to another method for producing a polyethylene film containing an organic silicon polymer, wherein a solution prepared by mixing polymethylphenylsilane in an amount of 0.1 to 10% by weight with respect to polyethylene is used. After reprecipitation in a solvent, the obtained organosilicon polymer-containing polyethylene powder is further melt-heat molded and further stretched to have a thickness of 1
It is characterized in that the film has a thickness of 0 to 1000 μm.

The reason why polymethylphenylsilane is selected as the organic polysilane and polyethylene is selected as the matrix polymer is shown below.

Among various organic polysilanes known so far, dialkyl polysilanes having the thermal characteristics that the glass transition point is considerably lower than room temperature and the melting point is slightly higher than room temperature are used as optical waveguide materials and nonlinear materials. From a practical point of view such as an optical material and a light emitting material, organic polysilanes having a glass transition point sufficiently higher than room temperature are preferable because it is difficult to obtain stable characteristics. Polymethylphenylsilane is
Among the organic polysilanes known so far, the glass transition point is about 100 ° C., which is sufficiently higher than room temperature, and it can be processed by heat molding. Therefore, it can be used in practical applications such as optical waveguide materials, nonlinear optical materials, and light emitting materials. It is the most desirable organic polysilane from the viewpoint.

On the other hand, as the matrix polymer, polyethylene is most preferable among various engineering plastics in consideration of flexibility, raw material cost, transparency in the UV-visible range, melt-molding processability, moisture resistance and the like. ..
Here, the weight average molecular weight range of polymethylphenylsilane is 1,000 to 1,000,000 (evaluated using gel permeation chromatography, standard polystyrene).
Can be used. Polyethylene having a high-density linear type and a low-density branched type and having a weight (number) average molecular weight range of 1,000 to 150,000 can be used.

In addition to isopropyl alcohol, alcohols such as methanol and ethanol, aliphatic hydrocarbon solvents such as hexane and isooctane, and acetone can be used as the poor solvent for reprecipitation.

[0009]

EXAMPLES The present invention will be described in more detail below with reference to examples and application examples, but the present invention is not limited to these examples.

Example 1 Polymethylphenylsilane-containing polyethylene film and method for producing the same A polymethylphenylsilane-containing polyethylene film can be produced as follows. A hot xylene solution is prepared by mixing 2% by weight of polymethylphenylsilane (weight average molecular weight: 8,000) with low density polyethylene. This homogeneous mixed solution is reprecipitated in isopropyl alcohol to obtain polyethylene powder containing polymethylphenylsilane. This powder is further sandwiched between two glasses and melt-molded by heating. Adjust the heating temperature and time until the appropriate thickness is achieved. By this method, the thickness can be controlled in the range of 10 to 1000 μm. Further, the content of polymethylphenylsilane can be controlled by this method in the range of 0.1 to 10% by weight.
Fig. 1 shows the obtained polymethylphenylsilane-containing polyethylene film (polymethylphenylsilane content 2%, thickness 1
The UV-visible absorption spectrum of (00 μm) is shown by the relationship between the absorbance (vertical axis) and the wavelength (nm, horizontal axis). The absorption around 340 nm and 270 nm, which is characteristic of polymethylphenylsilane, is clearly observed.

Example 2 Oriented Polymethylphenylsilane-Containing Polyethylene Film and Method for Producing the Same The oriented polymethylphenylsilane-containing polyethylene film can be produced as follows. A polyethylene film containing polymethylphenylsilane (polymethylphenylsilane content 2%, thickness 100 μm) is stretched in one direction while heating at 100 to 150 ° C. FIG. 2 shows the polarization dependence of the ultraviolet-visible absorption spectrum of the obtained oriented polymethylphenylsilane-containing polyethylene film (stretching ratio 5). That is, FIG. 2 shows the polarization dependence of the absorbance (vertical axis).
Is a diagram showing the relationship between the wavelength and the wavelength (nm, abscissa), where is the case where the knitting direction is parallel to the stretching direction, and is the case where the polarization direction is perpendicular to the stretching direction. The polarization absorption dependence around 340 nm and 270 nm, which is characteristic of polymethylphenylsilane, is clearly recognized. In addition, due to the anisotropic orientation of polymethylphenylsilane in polyethylene over 400 to 800 nm, polarization dependency is also recognized for the baseline based on the anisotropy of refractive index. 340
For nm absorption, the dichroic ratio is estimated to be 1.2. Utilizing these properties, it has been shown that it can be used as a polarizing filter in the near ultraviolet to visible range.

Example 3 Application Example of Polymethylphenylsilane-Containing Polyethylene Film As an application of the polymethylphenylsilane-containing polyethylene film, it is shown below that an optical circuit can be formed.
Figure 3 shows a polyethylene film containing polymethylphenylsilane (polymethylphenylsilane content 2%, thickness 100μ
The change with time when m) is irradiated with ultraviolet rays of 254 nm and 6 W is shown by the relationship between absorbance (vertical axis) and wavelength (nm, horizontal axis) for t = 0 minutes, 5 minutes, and 30 minutes. The characteristic of polymethylphenylsilane is 34 with UV irradiation.
Absorption near 0 nm and 270 nm and 400 to 800 n
The baseline becomes smaller toward m. 340nm, 270n with ultraviolet irradiation (254nm, 6W)
The absorption around m disappears and the baseline of 400 to 800 nm becomes smaller, but the speed is almost the same between the polymethylphenylsilane alone and the polyethylene film containing polymethylphenylsilane. This means that the photolysis of polymethylphenylsilane by UV irradiation occurs in the polymer itself and does not depend on the state near the polymer chain. By using this property, it is shown that an optical circuit can be formed by irradiating the polymethylphenylsilane-containing polyethylene film with light of 400 nm or less through a mask. That is, the polymethylphenylsilane-containing portion corresponds to the core portion, and the light irradiation portion corresponds to the clad portion.

[0013]

As described above in detail, polymethylphenylsilane is added to polyethylene in an amount of 0.1-10.
A polyethylene film containing an organic silicon polymer and its alignment film, which contain 10 wt.
Polymethylphenylsilane was added to polyethylene at 0.
It can be produced by re-precipitating a solution mixed with 1 to 10% by weight in a poor solvent to obtain an organosilicon polymer-containing polyethylene powder, which is further subjected to melt heat molding and stretching treatment. Polymethylphenylsilane-containing polyethylene film is easy to handle even if it is difficult to handle with organic polysilane alone, by using a suitable organic polymer, for example, a polymer such as polyethylene, as a matrix, for example, optical Applications in a wide range of fields are expected as waveguide materials, nonlinear optical materials, and light emitting materials.

[Brief description of drawings]

FIG. 1 is a diagram showing an ultraviolet-visible absorption spectrum of a polymethylphenylsilane-containing polyethylene film produced in Example 1.

FIG. 2 is a diagram showing polarization dependence of an ultraviolet-visible absorption spectrum of an oriented polymethylphenylsilane-containing polyethylene film (stretching ratio 5) produced in Example 2.

FIG. 3 is a diagram showing the ultraviolet (6W, 254 nm) irradiation time dependence of the ultraviolet-visible absorption spectrum of the polymethylphenylsilane-containing polyethylene film synthesized in Example 1.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area C08L 23:04

Claims (3)

[Claims] 1. Polyethylene containing polymethylphenylsilane in an amount of 0.1 to 10% by weight and having a thickness of 10 to 100.
An organosilicon polymer-containing polyethylene film having a thickness of 0 μm. 2. A solution obtained by mixing polymethylphenylsilane in an amount of 0.1 to 10% by weight with respect to polyethylene is reprecipitated in a poor solvent, and the resulting organosilicon polymer-containing polyethylene powder is further melt-heat molded. , Thickness 10-100
A process for producing an organosilicon polymer-containing polyethylene film, which comprises forming a film having a thickness of 0 μm. 3. A solution obtained by mixing polymethylphenylsilane in an amount of 0.1 to 10% by weight with respect to polyethylene is reprecipitated in a poor solvent, and the obtained organosilicon polymer-containing polyethylene powder is further melt-heat molded, Further stretching,
A method for producing a polyethylene film containing an organic silicon polymer, wherein the film has a thickness of 10 to 1000 μm.