JPH0413720A - Polycarbonate - Google Patents

Abstract

PURPOSE:To obtain the title polycarbonate composed of specific recurring units, having light-transmitting characteristics extremely excellent in visible light to near-infrared light area, remarkably reduced in increase in loss even when exposed under high-temperature and high humidity conditions and useful as a light signal transmitting medium. CONSTITUTION:The aimed carbonate consisting of recurring units expressed by the formula (X and Y are heavy hydrogen or halogen element). Furthermore, the aimed carbonate is preferably obtained by dissolving bisphenol in an organic solvent such as pyridine or an aqueous solution of dichloromethane-sodium hydroxide, introducing phosgene into the solution and carrying out condensation polymerization.

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 polycarbonates containing elements and deuterium.

C.Y.

However, in the formula, X and Y are the same or different and are deuterium or a halogen element.

(Left below) [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 band. 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 an optical fiber, the core is a highly transparent plastic such as polymethyl methacrylate (PMMA) or polystyrene, and the sheath (cladding) is a plastic with a lower refractive index than the core. Those consisting of a core-clad structure 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. It is important to minimize factors that may 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 -CH, -C(CH,)-COO(CHI), (CF2) in which some of the hydrogens in the ester side chains are substituted with fluorine. It has been shown that cFs has a lower loss than PMMA (for example, see "Toshikuni Kaino, Kobunshi Saishuu, Vol. 42, pp. 257-264, 1985, 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. It is considered useful for However, deuterium substitution tends to cause hydrogen exchange reactions, and fluorine substitution has synthetic problems such as poor stability of the raw alcohol, making it extremely difficult to obtain completely substituted monomers as described above. there were.

Deuterated polymethyl methacrylate-CDx-C(CDs)-COOCD is also used as a core material.

Although it can achieve lower loss than polymethyl methacrylate, it has harmonic absorption due to CD bond, although it is small, and when using light around 1300 to 1600 nm as in optical integrated circuits, optical loss can be ignored. Furthermore, it has higher hygroscopicity than polystyrene, etc., and has a saturated moisture absorption rate of about 2%.

Therefore, in a humid environment, vibrational absorption of OH in water molecules affects optical loss. The optical transmission loss, especially in the near-infrared region, decreases due to the harmonics of OH vibration absorption (see, for example, "Toshikuni Kaino, Proceedings of the Society of Polymer Science and Technology, Vol. 32, No. 4, 1983, p. 2525"), that is, the humidity of the usage environment conditions. There was a problem in that optical transmission loss fluctuated due to changes.

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, optical waveguides and optical fibers using polycarbonate have been proposed (for example, ``Nichi et al., Fujitsu, 39
roll.

No. 1, page 65). Although these exhibit excellent heat resistance and stable transmission characteristics, they have the problem of high optical transmission loss due to the presence of C--H bonds in their side chains.

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, it is an object of the present invention to provide a polycarbonate which has excellent heat resistance and can be used as a surface treatment agent such as a plastic optical material, a water repellent material, etc., and a functional film such as an oxygen enrichment film, which is less affected by OH vibration absorption due to moisture absorption.

[Means for Solving the Problems] In order to achieve such an object, the present invention is characterized by comprising a repeating unit represented by the following formula (1).

However, in the formula, X and Y are the same or different and are deuterium or a heliogen element.

[Function] In the present invention, by halogenating or deuterating the hydrogen of polycarbonate, the harmonic absorption caused by the C-H bond is reduced and the wavelength is shifted to a longer wavelength, thereby obtaining a low-loss optical material. I can do it. Furthermore, due to the halogenation of the side chains, the hygroscopicity of the polymer decreases significantly, and the 0-H vibration absorption strength becomes extremely small (P
Because MMA-based polymers have high hygroscopicity, they absorb or dehumidify, resulting in OH groups (absorption strength fluctuates greatly,
Compared to the case where stable light guiding characteristics were not obtained, the present invention is characterized in that extremely stable optical characteristics can be maintained.

The method for producing the polymer in the present invention is similar to the general method for producing polycarbonate, in which bisphenol is dissolved in an organic solvent such as pyridine or a dichloromethane-sodium hydroxide aqueous solution, phosgene is introduced, and condensation polymerization is performed. .

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

20g of deuterodiphenyolpropane d-14 and 140ml of pyridine were placed in a 100m1 three-bottle flask. After dissolution, phosgene was passed through the solution at a rate of about 1+g/ml with stirring. The temperature was kept at 25-30°C.

When pyridine salt precipitated and the reaction solution turned yellow-red, the addition of phosgene was stopped. The reaction mixture was poured into 600 ml of water to separate the polymer.

The polymer was filtered, washed with water and dried. The molecular weight of the obtained polymer was 54,000. The chemical structure is shown in Table 1.

In a 300 ml flask were placed 20 g of deuterodiphenylohexafluorobroban d-8, 6 g of sodium hydroxide, 1 g of benzyltrimethylammonium chloride, 100 ml of distilled water, and 50+ ol of dichloromethane. . Stir the mixture rapidly and cool with water at 20°C.
Phosgene was passed through at a ratio of Ig/win while maintaining the temperature.

After the reaction was completed, dichloromethane was distilled off, and the crude polymer was washed with water and dried. The molecular weight of the obtained polymer is 75,000
Met. The chemical structure is shown in Table 1.

Polymer 3-8 Polymers shown in Table 1 were produced in the same manner as Production Examples 1 and 2.

Table 1 Chemical structure of the produced polymer Y3 11Ran 1 Both ends of the rod-shaped polymer obtained in Polymer Production Example 1 were optically polished,
Absorption in the near infrared to visible light range was measured using a spectrometer. As a result, the optical density (OD) at 660.850.1300 and 1550 nm is 0.0, respectively.
12.0.005.0.005 and 0.120 (c
m-') and exhibited extremely high translucency. Absorption was similarly measured for other polymers. Table 2 summarizes the results.

Table 2: Transparent chemical structure of the produced polymer (lambda) An optical waveguide was produced using the polymer obtained in Polymer Production Example 1 as a core component and the polymer obtained in Polymer Production Example 2 as a cladding component.

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 15 μm.

After firing and drying, the core component polymer was coated onto the cladding component polymer to a thickness of approximately 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 an optical 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 0.12dB/cI11
Therefore, it is considered that it can be sufficiently applied to various optical circuits.

An optical fiber was produced using the polymer obtained in Polymer Production Example 1 as the core component and the polymer obtained in Polymer Production Example 2 as the cladding component.

The core component polymer was formed into a fiber using an extruder while being heated, and the fiber was passed through the solvated cladding component polymer to perform coating. Through this process, an optical fiber having a core diameter of 0.75 mm and a cladding film thickness of 0.05 mm was obtained. This fiber is 100dB/k at wavelength 650
m, a low loss window of 60 dB/km or less was observed at a wavelength of 850 nm.

This plastic optical fiber was heated at a temperature of 60°C and a humidity of 90°C.
It was left standing for two days and nights under conditions of %RH, and then taken out and its optical transmission characteristics were measured. The increase in loss due to moisture absorption was 50 dB/km or less at a wavelength of 850 or less. Under the same conditions, the increase in loss due to moisture absorption of bardeuteropolymethyl methacrylate was more than 300 dB/km, and the optical loss was significantly improved.

Large 11 Adhesive A This example is an example in which a polymer is used as the sealing insulating material.

The impact strength of the polymer obtained in Polymer Production Example 4 was 410 kg.
cm/cm" (and the glass transition temperature was 160°C and the heat distortion temperature was 140°C, indicating excellent heat resistance. It also had excellent processability, and was made of 30% polymer and 70% solvent. It was possible to encapsulate a semiconductor in a mixture made of silica and heat mold it.When the resin encapsulated product was subjected to an accelerated moisture resistance test (121"C, 100% relative humidity),
No defects occurred even after 1500 hours.

[Effects of the Invention] As explained above, the polycarbonate according to the present invention has extremely superior optical transmission characteristics in the visible to near-infrared light range compared to conventional plastic optical materials, and is resistant to exposure to high temperature and high humidity conditions. However, the increase in losses is extremely small. 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, 650~
Since it has low loss in the wavelength range of 1600 r+m, it can be used in connection with multi-component glass and quartz optical fibers without optical/electrical conversion or electrical/optical conversion. That is, there is an advantage that optical components manufactured using these optical materials can be used to construct optical signal transmission systems such as local area networks that are highly economical.

Furthermore, it has the advantage that it can be used not only as an optical material but also in a wide range of applications.

Claims (1)

[Claims] 1) A polycarbonate characterized by consisting of repeating units represented by the following general formula (1); ▲There are numerical formulas, chemical formulas, tables, etc.▼...(1) However, in the formula, Y is the same or different and is deuterium or a halogen element.