JPH0343423A - Polysiloxane and optical element comprising polysiloxane - Google Patents

Abstract

PURPOSE:To obtain a polysiloxane providing an optical material having stable light transmission characteristics in a range from visible light rays to near infrared rays, excellent heat resistance and water-vapor resistance, comprising a polymer having a specific repeating unit. CONSTITUTION:For example, chlorosilane is dissolved in an organic solvent such as toluene, hydrolyzed and polymerized with an alkali such as potassium hydroxide to give a polymer or copolymer having a repeating unit shown by formula I and/or formula II [R1 and R2 are group shown by formula III (Y is deuteron or halogen; (n) is <=5) or group shown by formula IV]. The polysiloxane can be made into plastic optical materials having a low loss from visible light rays to near infrared rays and a only slight influence on OH vibration absorption resulting from moisture absorption, surface treating materials such as water repellent and functional film such as oxygen enriching film.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to halogen-based materials used as optical materials such as optical integrated circuit waveguides and plastic optical fibers, and electronic component materials such as electrical insulating materials. It concerns polysiloxanes containing elements and deuterium.

[Prior Art] Inorganic materials such as quartz glass and multi-component glass are generally used as base materials for optical components and optical fibers because they have low optical transmission loss and a wide transmission IF range. has been done.

On the other hand, optical materials based on plastic have also been developed. These plastic optical materials are attracting attention because they have characteristics such as better processability and easier handling than inorganic materials.

For example, in optical fibers, the core is made of highly transparent plastic such as polymethyl methacrylate (PMM8) or polystyrene, and the cladding is made of PLUSDEC, which has a lower refractive index than the core. Those consisting of concentric core-clad structures are known.

[Problems to be Solved by the Invention] However, these plastic optical fibers have a problem in that the degree of attenuation of light transmitted inside is greater than that of inorganic fibers.

Light is transmitted by total internal reflection of the light incident on one end of an optical circuit or fiber along its length, but when light is transmitted inside plastic, it is absorbed or scattered. Therefore, it is important to minimize factors that increase the attenuation of light.

Optical circuit components use light with a wavelength of 650 to 1600 nm, which is used in current optical fiber communications, so when plastic is used as the material for optical fibers, it is even more urgent to reduce loss in the above wavelength range. It is.

The biggest factor in optical transmission loss in plastics is harmonics of infrared vibration absorption between carbon and hydrogen in the molecules that make up the plastic. In order to reduce the harmonics caused by this carbon-hydrogen bond and shift the wavelength to longer wavelengths, it has been proposed to replace hydrogen atoms in plastic molecules with halogen atoms such as fluorine or deuterium atoms.

For example, as a plastic in which hydrogen is replaced with fluorine, polymethacrylate in which part of the hydrogen in the ester side chain is replaced with fluorine has been shown to have a lower loss than PMMA (for example, "
Toshikuni Kaino, Polymer Papers, Volume 42, 1985, 257
- p. 264, "The Society of Polymer Science and Technology").

However, because carbon-hydrogen bonds remain in the methyl group of the ester side chain or main chain, it is not sufficient to reduce the loss.Replacing all hydrogens in the ester side chain with deuterium or fluorine does not reduce the loss. Considered useful. However, there are synthetic problems such as poor stability of the raw material alcohol, and it has been extremely difficult to obtain a completely substituted monomer as described above.

In addition, although deuterated polymethyl methacrylate-CD2-C(CD3)-0OCD3 used as the core material has lower loss than polymethyl methacrylate, it has harmonic absorption caused by C'-D bonds, although it is small. 1300~1600nn like optical integrated circuits
When using light around +, optical loss cannot be ignored, and it has higher hygroscopicity than polystyrene and the like, with a saturated moisture absorption rate of about 2.

Therefore, in a humid environment, vibrational absorption of 011 of water molecules affects optical loss. The harmonics of 011 vibration absorption reduce optical transmission loss, especially in the near-infrared region (for example, "Toshikuni Kaino, Polymer Preprints.

Japan, Vol. 32, No. 4, 1983, p. 2525.”
reference). That is, there is a problem in that optical transmission loss fluctuates due to changes in humidity in the usage environment.

Further, the glass transition temperature of organic polymers, particularly polymethyl methacrylate polymers, is generally around 100°C.

Therefore, the upper limit of the heat resistance temperature is about 70°C, and it could not be used for practical purposes. In order to solve these heat resistance problems, leading waveguides and optical fibers using rubber-like polysiloxane have been proposed (for example, Japanese Patent Application No. 63-986).
No. 03). Although these exhibit excellent heat resistance and stable transmission characteristics, they have the problem of high optical transmission loss due to the presence of a C-11 bond on the inner side.

The present invention was made in view of the current situation, and
The purpose is to achieve low loss in the visible light to near-infrared light range.
Moreover, the surface IA of plastic optical materials, water repellent materials, etc., which has excellent heat resistance and is less affected by OH vibration absorption due to moisture absorption.
The object of the present invention is to provide a polysiloxane that can be used as a filler and a functional film such as an oxygen enrichment film.

[Means for Solving the Problem] In order to achieve such an object, the present invention provides a formula: RI 5i-0- 2 [wherein R3 and R2 are each CnY2. ,, (Y
are the same or different deuterated or halogenated alkyl groups represented by deuterium or a halogen element, n is a positive integer of 5 or less), or the same or different deuterated or halogenated alkyl groups each represented by CoYs (where Y is deuterium or a halogen element) Hydrogenated or halogenated phenyl group] It is characterized by being a polymer consisting of repeating units represented by the following.

Further, the present invention also provides the formula % formula % [wherein R1 and R2 are each CIIY2o-1(Y
are the same or different deuterated or halogenated alkyl groups represented by deuterium or a halogen element, and n is a positive integer of 5 or less; It is characterized by being a polymer consisting of repeating units represented by different deuterated or halogenated phenyl groups.

Furthermore, the present invention is based on the following formula:
or the same or different deuterated or halogenated alkyl groups represented by C, Y, (Y is deuterium or a halogen element), respectively; Repeating unit ##≠ General formula % Formula % [In the formula, R1 and R2 are C1Y2n and + (
Y is deuterium or a halogen element, n is a positive integer of 5 or less), the same or different deuterated or halogenated alkyl group, or the same or different deuterated or halogenated alkyl groups, each represented by C, Y5 (Y is deuterium or a halogen element) Or characterized by different weights.

Furthermore, the optical element of the present invention is made of a polysiloxane consisting of a repeating unit represented by the following formula (1) or (1) or a polysiloxane containing repeating units of the general formulas (1) and (II). It is characterized by having an optical transmission medium.

12 1 5f-0- R However, in the formula, R and R2 are each cnY2□1〈
Y is the same or different deuterated or halogenated alkyl group represented by deuterium or a halogen element (1h, n is a positive integer of 5 or less), or C6Ys (Y
are the same or different deuterated or halogenated phenyl groups represented by deuterium or halogen element).

[Function] In the present invention, by halogenating or deuterating the hydrogen in the polysiloxane side chain, the harmonic absorption caused by the C-11 bond is reduced and the wavelength is shifted to a longer wavelength, thereby creating a low-loss optical material. can be obtained. Furthermore, since the main chain structure is siloxane, it exhibits high moisture resistance, but due to the halogenation of the temporal region, the hygroscopicity of the polymer is significantly reduced, and the 0-H vibration absorption strength based on moisture absorption becomes extremely small. Since PMMA-based polymers have high hygroscopicity, the absorption intensity based on the 011 group fluctuates greatly due to moisture absorption or dehumidification, making it impossible to obtain stable light guiding properties.In contrast, the present invention has extremely stable optical properties. It has the characteristic of being maintainable.

The polymer of the present invention is a homopolymerized or copolymerized silanol or cyclic polysiloxane obtained by hydrolysis of a chlorosilane represented by the general formula (Ill), (IV) or (V) R3 CI Cl-5t-C1 (rV) CI CI. A deuterated or halogenated alkyl compound, which can be obtained by polymerization [wherein R1+R2 are the same or different, CI, Y2°, (Y is deuterium or a halogen element, and n is a positive integer of 5 or less] or a deuterium or halogenated phenyl group represented by C, Y, (Y is deuterium or a halogen element), or - formula (III),
Polymers can also be obtained by polymerization of various alkoxysilanes obtained by reacting chlorosilanes represented by (IV) or (V) with alcohols, or by condensation polymerization of halogenosilanes and alkoxysilanes.

Note that if n is 6 or more, the glass transition temperature of the polymer will be low, causing problems in handling, so n is preferably 5 or less.

The method for producing the polymer in the present invention is similar to the general method for producing bosslochitin, in which chlorosilane is dissolved in organic 691 such as toluene or xylene, and hydrolyzed and polymerized with an alkali such as KOll or preferably KOD. It is something.

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

■ 244 g of 05iC1°, t4og of C6D6, and BCl3 as a catalyst were placed in a stainless steel autoclave at a temperature of 270°C and a maximum pressure of 6.
The reaction was carried out at 5 kg/cm2 for 10 hours. After cooling, 340
g of product solution was obtained.

This product liquid was distilled under normal pressure to obtain 13130 g of C6DsSiC as a fraction of 200 to 201 t.

■ 37.4 g of 5rC1a dissolved in 200 ml of hebutane was placed in a 500 ml flask. Next, from the dropping funnel, phenymagnesium chloride d-5
A solution of tetrahydrofuran was added dropwise at a rate of 500 rnl/h, and the temperature was maintained at 40-50° C. with stirring.

After the dropwise addition, the mixture was refluxed for 2 hours, and then the precipitate was filtered. The filtrate was distilled and C6D of the 200-201'C fraction was distilled at atmospheric pressure.
20g of 5SiCI+ was obtained.

Si powder 45 was added to the IL stainless steel autoclave.
g, Cu(:l ag and ZnCl20.25g
were mixed well and filled. This mixture was mixed in a nitrogen stream for 4 hours.
It was heated to 30°C to reduce CuH. After cooling, 540 g of monochlorobenzene d-d was added and reacted at 430° C. for 15 hours to obtain about 20 g of chlorosilane. This chlorosilane is distilled in a distillation column, and the vapor pressure is 30n+m! Ig
13 g of diphenyldichlorosilane d-10, a fraction of 184 to 186° C., was obtained.

45 g of Si powder was placed in a quartz reaction tube in a tubular electric furnace.

18 g of CuC and 20.25 g of ZnCl were mixed well and filled. This mixture was heated to 300°C in a nitrogen stream.
The temperature was further increased to 32°C to reduce CuC1.
By keeping the temperature at 0°C and flowing chloromethane d-3 into the reaction tube at a rate of 0.81/hr, about 20 g of chlorosilane was obtained in 15 hours of reaction. This chlorosilane was rectified in a rectification column to obtain 12 g of dimethyldichlorosilane d-6, a fraction of 69 to 70°C.

Si powder 458°Cu was placed in a quartz reaction tube in a tubular electric furnace.
18 g of C and 20.25 g of ZnCl were thoroughly mixed and charged. This mixture was heated to 300° C. in a nitrogen stream to reduce CuCl. Furthermore, when the temperature was maintained at 320° C. and chloromethane d-3 was flowed into the reaction tube at a rate of 0.41/hr, about 20 g of chlorosilane was obtained in 15 hours of reaction. This chlorosilane is rectified in a rectification column, and the 64-65°C fraction is methyltrichlorosilane d-
14g of 3 was obtained.

By using chloropentane d-11 instead of chloromethane d-3 in Monomer Production Example 4, the boiling point! 66
10 of pentyltrichlorosilane d-11 at ~188°C
I got g.

5 (equipped with reflux condenser, thermometer and gas injection tube)
A 100W water-cooled high-pressure mercury lamp was installed in the center of the fourth 10ml flask, and freshly distilled (CD3) DS
86 g of iCh and 2136 g of CaO were charged.

After stirring the charge with a magnetic stirrer and replacing the inside of the reflux vessel with nitrogen gas, a high-pressure mercury lamp was turned on, and chlorine gas was blown at a rate of 70 g/hr at room temperature for 7 hours to cause a reaction. By distilling 220 g of the reaction liquid under reduced pressure, 58 g of phenylmethyldichlorosilane d-8 having a temperature of 203 to 205°C was obtained.

2 equipped with calcium chloride tube, thermometer and dropping funnel
In a 00ml flask, 100ml of carbon tetrachloride, phenyltrichlorosilane d-5 obtained in Monomer Production Example 1
20g of iron catalyst and 0.2g of iron catalyst were added, and 5.3g of bromine was added dropwise while cooling in a cold bath.The reaction was allowed to proceed for 10 hours, and the resulting reaction solution was distilled to give a vapor pressure of 1! ~
15 g of a fraction at 125°C was obtained.

2 with calcium chloride tube, thermometer and dropping funnel
In a 00ml flask, 100ml of carbon tetrachloride, phenyltrichlorosilane d-5 obtained in Sentsuma Production Example 1
20g, ferric chloride 01g and iodine 0.1g,
The resulting reaction solution into which 50 g of chlorine gas was blown was distilled to obtain 18 g of a fraction with a vapor pressure of 7 mm, 11 g, and a temperature of 87 to 88°C.

In step (3) of Monomer Production Example 1, fluorophenylmagnesium chloride d-4 was used instead of phenylmagnesium chloride d-5, and under the same conditions,
Fluorophenyltrichlorosilane d-4 was obtained as a fraction of 194-196°C at a vapor pressure of 6 mm)Ig.

2 with calcium chloride tube, thermometer and dropping funnel
Into a 00ml flask, add 100ml of carbon tetrachloride. Dimethyldichlorosilane d-620 obtained in Monomer Production Example 1
g, 0.3 g of ferric chloride, and 0.1 g of iodine were added, and 50 g of chlorine gas was blown into the flask. The obtained reaction solution was distilled,
12g of chloromethylmethyldichlorosilane d-5 was obtained.

2 with calcium chloride tube, thermometer and dropping funnel
00ml flask, carbon tetrachloride 100n+1. Diphenyldichlorosilane d-1 obtained in Monomer Production Example 2
030 g of ferric chloride, 0.3 g of ferric chloride, and 0.1 g of iodine were added, and 50 g of chlorine gas was blown into the reactor.The resulting reaction solution was distilled to obtain 13 g of a distillate having a temperature of 175 to 179°C at a vapor pressure of 7 nuel/g.

Polymer Production Example 1 510 g of phenyltrichlorosilane d-obtained in Monomer Production Example 1 and KOD were placed in a flask with a volume of approximately 50 m1.
100 mg was added and mixed with 15rAl of toluene.

This mixture was then refluxed for 16 hours. After the reaction was completed, the mixture was cooled, a small amount of precipitate was filtered, and the solution was poured into methanol to perform reprecipitation.

The molecular weight of the obtained polyphenylsilsesquioxane is M
w-15000, Mw/Mn·2.1. The infrared absorption spectrum shows that silsesquioxane has 5
A double peak due to i-0 was observed at 104104O' and 1160 cm-'. This polymer also showed high heat resistance, and no change was observed even after heat treatment at 300° C. for 1 hour.

Nira ± Nidando Kita 1 Diphenyldichlorosilane d obtained in Monomer Production Example 2
30 g of diphenylsilanediol obtained by reacting -10 with heavy water was added to 500 ml of chloroform.
The mixture was dissolved and reacted at 5° C. for 20 hours using CF, SO, and H as catalysts. The reaction wave was poured into methanol to obtain a white solid polymer. The molecular weight of this polymer is Mw-100
00.Mw/Mn-1.6.

E4 Salmon 1 Dimethyldichlorosilane d- obtained in Nanatsuma Production Example 3
100 mg of Koji was added to 810 g and mixed with 15 ml of toluene. Thereafter, the same treatment as in Polymer Production Example 1 was performed to obtain a polymer. The molecular weight of the obtained polymer is M
w"18 (100, MW/Mr+-2.5.

310 g of methyltrichlorosilane d-obtained in Sentsuma Production Example 4 and KO were placed in a flask with a volume of about 50 ffil.
100 mg of D was added and mixed with 15 mJ of toluene.

This mixture was then refluxed for 16 hours. After the reaction was completed, the mixture was cooled and a small amount of precipitate was filtered, followed by reprecipitation by pouring the solution into methanol. The molecular weight of the obtained polymethylsilsesquioxane is M+y-20000
, Mw/Mn-3.1.

Polymer Production Example 5 KOD I (JQmg was added to Feyulmethyldikuaosilane d-81 (Ig) obtained in Monomer Production Example 6, and 1
Mixed with 5ml of toluene. Thereafter, the same treatment as in Polymer Production Example 1 was performed to obtain a polymer. The molecular weight of the obtained polymer was Mw-53000, Mw/Mn-2,81'.

Polymer Production Example 6 Phenyltrichlorosilane d obtained in Monomer Production Example 1
IcKOD 10
0B was added and mixed with 15ml toluene. This mixed solution was refluxed for 16 hours, and after the zero reaction was completed, it was cooled.
After filtering a small amount of precipitate, reprecipitation was performed by pouring the solution into methanol. The molecular weight of the obtained polymer was MW-21000.

Phenyltrichlorosilane d obtained in Production Example 1
-510 g and dimethyldichloride obtained in Monomer Production Example 3 silane d-623 KOD 100 o+g
'r was added and mixed with 15 ml of toluene. and,
This mixture was refluxed for 16 hours. After the reaction was completed, the mixture was cooled and a small amount of precipitate was filtered, followed by reprecipitation by pouring the solution into methanol. The molecular weight of the obtained polymer was My-18,000.

Polymer production examples have been described above, and in addition to those produced in the above-mentioned production examples, polymers could also be obtained by a similar method using the monomers listed in the monomer production examples.

Optical components manufactured using the manufactured polymer will be described below.

The polymer obtained in Ainairiyu Polymer Production Example 1 was processed into a plate shape, both sides of the plate-shaped polymer were optically polished, and absorption in the near infrared to visible light range was measured using a spectrometer. As a result, the wavelength is 660,850
．． The optical density (OD) at 1300 and 155 Onm was 0.007, 0.003°0.002 and 0.023 (ca-'), respectively, indicating extremely high light transmittance. Absorption was similarly measured for other polymers. Table 1 summarizes the results.

Table 1 Light transmission of the produced polymer Structure 1; 1 (2) Example 2 Producing a guiding waveguide using the polymer obtained in Polymer Production Example 1 as the core component and the polymer obtained in Polymer Production Example 4 as the cladding component did.

The above two types of polymers were dissolved in methyl isobutyl ketone to form a solution. First, a cladding component polymer was applied onto a silicon substrate to a thickness of about 20 μm.

After firing and drying, the core component polymer was coated onto the cladding component polymer to a thickness of about 8 μm. Next, the core component polymer was processed into a linear rectangular pattern with a length of 50 mm, a width of 8 μm, and a height of 8 μm by photolithography and dry etching. After processing, the cladding component was applied onto the core component polymer to obtain a leading waveguide.

The loss of the waveguide was calculated by irradiating light with a wavelength of 1300 nm from one end of the waveguide and measuring the amount of light coming out from the other end. The loss of this waveguide is 0.1 d [17 cm, which is considered to be sufficient for use in various optical circuits.

An optical fiber was produced using the polymer obtained in Polymer Production Example 4 as a core component and the polymer obtained in Polymer Production Example 3 as a cladding component.

The core component polymer was heated and made into a fiber using an extruder, and the fiber was passed through a melted cladding component polymer to perform coating.

Through this process, the core diameter is 0.75mm and the cladding film thickness is 0.75mm.
An optical fiber of 0.05 mm was obtained. This fiber has a wavelength as
70dB/km at onm, 40d[l at wavelength 850nm
A low loss window of +n or less was detected in /.

This plastic optical fiber was heated at a temperature of 60°C and a humidity of 90°C.
After standing for two days and nights under kRH conditions, it was taken out and its optical transmission characteristics were measured. Loss increase due to moisture absorption at wavelength 850nm
It was less than 50d[l/km. Under the same conditions, the increase in loss due to moisture absorption of bardeuteropolymethyl methacrylate was 300 d8/km, and the optical loss was significantly improved.

[Effect of the invention] As explained above, the polysiloxane according to the present invention has the following properties:
Compared to conventional plastic optical materials, it has extremely excellent optical transmission properties in the visible to near-infrared light range, and exhibits significantly less increase in loss even when exposed to high temperature and humidity conditions. Therefore, it has the advantage that it can be stably used as an optical signal transmission medium over a distance of several hundred meters using a material for optical integrated circuits in the near-infrared light region and a light source for the visible light region or near-infrared light region.

In addition, 850~
Since it has low loss in the wavelength range of 1800 nm, it can be used in connection with multi-component glass and quartz optical fibers without optical/electrical conversion or electrical/optical conversion. In other words, it is possible to construct economical optical signal transmission systems such as local area networks using optical components made using these optical materials.
” There is a point.

Claims (1)

[Claims] 1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are each C_nY_2_n
The same or different deuterated or halogenated alkyl groups represented by ___+_1 (Y is deuterium or a halogen element, n is a positive integer of 5 or less), or each C_
The same or different deuterated or halogenated phenyl groups represented by 6Y_5 (Y is deuterium or a halogen element)] A polysiloxane characterized by being a polymer consisting of repeating units represented by the following formula. 2) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are each C_nY_2_n
The same or different deuterated or halogenated alkyl groups represented by ___+_1 (Y is deuterium or a halogen element, n is a positive integer of 5 or less), or each C_
The same or different deuterated or halogenated phenyl groups represented by 6Y_5 (Y is deuterium or a halogen element)] A polysiloxane characterized by being a polymer consisting of repeating units represented by the following formula. 3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are each C_nY_2_n
The same or different deuterated or halogenated alkyl groups represented by ___+_1 (Y is deuterium or a halogen element, n is a positive integer of 5 or less), or each C_
Repeating units represented by 6Y_5 (Y is deuterium or halogen element), identical or different deuterated or halogenated phenyl groups] and general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are respectively C_nY_2_
n_+_1 (Y is deuterium or halogen element, n is 5
the same or different deuterated or halogenated alkyl groups represented by the following positive integers), or each C
A polysiloxane characterized by being a copolymer of repeating units represented by the same or different deuterated or halogenated phenyl groups represented by _6Y_3 (Y is deuterium or a halogen element). 4) Polysiloxane consisting of repeating units represented by the following general formula (I) or (II) or general formula (I
) and (II); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲Mathematical formulas, chemical formulas, There are tables, etc.▼...(II) However, in the formula, R_1 and R_2 are each C_nY_
2_n_+_1 (Y is deuterium or halogen element, n
are the same or different deuterated or halogenated alkyl groups represented by C_6Y_5 (Y is deuterium or a halogen element), respectively (Y is a positive integer of 5 or less); be.