JPH012006A - plastic light transmitting fiber - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a plastic light-transmitting fiber, and more specifically, it is used for optical sensor means and optical fibers installed in high-temperature areas such as the engine room of automobiles and ships. The present invention relates to a plastic light transmitting fiber with excellent heat resistance that can be suitably used as a means of communication.

[Conventional technology and its problems 1] In recent years, plastic optical fibers have become more resistant to bending stress, easier to handle, and cheaper than inorganic glass optical fibers that have been widely used as optical transmission fibers. The development of sexual fibers is progressing and they are being put into practical use.

This plastic light transmitting fiber generally consists of a core made of a polymer with excellent light transparency and a sheath made of a polymer with a lower refractive index than the core and excellent transparency. Polymethyl methacrylate is widely used as the core material.

However, polymethyl methacrylate.

Its glass transition temperature (Tg) is about 100°C.

Due to its low heat resistance, it is not suitable for use in high-temperature environments.

Therefore, for the purpose of improving heat resistance, a plastic light transmitting fiber using a polycarbonate resin with a glass transition temperature (Tg) of 140 to 150°C as a core material has been proposed (Japanese Patent Laid-Open No. 81-210303). Although this product improves heat resistance, it is difficult to use for a long time because the optical transmission loss decreases as the temperature increases, so it is especially suitable for use under conditions of 150°C or higher. The problem is that it cannot be done.

On the other hand, for use in high-temperature environments, for example, a three-layer plastic light transmitting fiber in which a sheath material layer is covered with a protective layer with excellent heat resistance has been proposed. (Refer to Japanese Unexamined Patent Publication No. 80-32QO4) Since the single-layer structure becomes more complicated, the manufacturing process also becomes more complicated, which is a new problem. Currently, the development of fibers is desired.

[Objective of the Invention] The object of the present invention is to solve the above-mentioned problems, to have excellent heat resistance and a simple structure, and to withstand long-term use with small reduction in optical transmission loss even in operating environments of 150°C or higher. An object of the present invention is to provide a novel plastic light transmitting fiber.

[Means for achieving the above object] In order to achieve the above object, the inventor has made extensive studies and has found that when a core material is formed using a specific polycarbonate obtained from bisphenol, heat resistance is improved. The present invention was achieved by discovering that a fiber with excellent optical transmission properties can be obtained with a two-layer structure.

That is, the outline of this invention is that the core material and the sheath material layer are basic structural units, and the core material has the following formula [A1:[A] and the formula [BI R213, 1151 (where XI and X2 are hydrogen atoms, carbon Represents any one of an alkyl group having 1 to 6 carbon atoms, a 7-aryl group having 6 to 8 carbon atoms, and a halogen atom; and a halogen atom, ill, R
2 represents either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; ) has a repeating unit represented by
The present invention is a plastic light transmitting fiber made of a polycarbonate polymer having a polycarbonate polymer having a sheath material layer having a refractive index lower than that of a core material by 0.01 or more.

The polycarbonate polymer has the formula [A1゜[8
It may be a block copolymer of each repeating unit shown in ] or a random copolymer, but a random copolymer is preferable.

Furthermore, the mole fraction of the repeating unit represented by the formula [AI is preferably 5 to 100 mol%, and the mole fraction of the repeating unit represented by [B] is preferably 95 mol% or less,
The mole fraction of the green return unit in [B] may be 0.

This polycarbonate polymer is, for example, 4.4°-
Dihydroxytetraphenylmethane, 2,2-bis(4
-hydroxyphenyl)furopane, 2,2-bis(3-
Methyl-4-hydroxyphenyl)propane, 2.2-
Bis(3-chloro-4-hydroxyphenyl)propane, l-phenyl-1,1-bis(4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)-bis(
4-methylphenyl)methane, bis(4-hydroxyphenyl)-bis(4-n-propylphenyl)methane, bis(4-hydroxyphenyl)-bis(3-methoxyphenyl)methane, bis(3-methyl-4- hydroxyphenyl)-bis(4-methylphenyl)methane,
A polycarbonate oligomer obtained by a phosgenation reaction such as bis(4-methylphenyl)-bis(4-hydroxyphenyl)methane or 2.2-bis(4-hydroxyphenyl)methane and bisphenol are polycondensed by, for example, a solvent method. You can get it.

Examples of the solvent used when polycarbonate oligomer and bisphenol are subjected to condensation polymerization by a solvent method include methylene chloride, chlorobenzene, xylene, and the like.

Examples of the oxygen binder include hydroxides such as sodium hydroxide and potassium hydroxide, and pyridine.

Furthermore, a tertiary amine such as triethylamine or a quaternary salt thereof can be used to promote the polycondensation reaction, and a terminator such as L-butylphenol can be used to adjust the average molecular weight. .

Intrinsic viscosity number [η] of the polycarbonate polymer
(in methylene chloride, 20°C) is usually 0.30 dl/
g or more. If the intrinsic viscosity number [ηJ (in methylene chloride, 20° C.) is less than 0.30 dl/g, optical transmission loss at high temperatures becomes large and desirable characteristics cannot be obtained.

The glass transition temperature (Tg) of the polycarbonate polymer
) is usually 160°C or higher, and the refractive index is usually 1
．． 595 or less. Glass transition temperature (Tg) is 140
If the temperature is below .degree. C., the light transmitting fiber of the present invention may not be sufficient. Furthermore, if the refractive index is less than 1.570, it may be undesirable as a light transmitting fiber.

The sheath material layer has a refractive index lower than that of the core material.
．． It is constructed using a polymer that is smaller than 01 and has excellent transparency.

The difference between the refractive index of the glass material layer and the refractive index of the core material is 0.0.
If it is less than 1, it is impossible to obtain a light transmitting fiber with low light transmission loss.

Specific examples of the polymer constituting the glass material layer include poly-
4-methylpentene-1, polyarylate, alicyclic polycarbonate, aromatic polycarbonate, fluorine-containing polymethyl methacrylate, vinylidene fluoride polymer,
Examples include vinylidene fluoride/hexafluoropropylene copolymers.

The light transmitting fiber of the present invention can be produced by, for example, simultaneously supplying the polymer constituting the core material and the polymer constituting the glass material layer to a spinning head of a composite spinning machine using a screw melt extruder. These are mixed and discharged at a temperature of 220 to 270°C, and after being further cooled and solidified,
It can be carried out by a composite spinning method in which fibers are drawn at a speed of 8 m, or by a combination of the spinning step and the coating step, but from the viewpoint of simplifying the manufacturing process, the composite spinning method is preferable.

An example of the structure of the plastic light transmitting fiber obtained in this way is an outer diameter of about 1000 p, m,
Core material diameter 900~98Gpm, sheath material layer thickness lO~5
It is 0 end m.

The plastic light transmitting fiber of this invention uses a core material made of a polymer with a higher glass transition temperature than conventional plastic light transmitting fibers, so it cannot be used with conventional plastic light transmitting fibers. It can also be suitably used in fields that have not been possible before, such as sensor means and optical communication means installed in high-temperature areas such as the engine rooms of automobiles and ships.

[Effect of the invention] According to this invention.

(1) The core material is made of a specific polycarbonate that has a high glass transition temperature and a small drop in optical transmission loss in high-temperature environments, so it has excellent heat resistance. In addition, there is no need to provide a protective layer for improving heat resistance as the third M other than the core material and sheath material layers, and (3) the manufacturing process does not become complicated.

It is possible to provide a novel plastic light transmitting fiber having various effects such as.

[Example 1] Next, an example of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) 22 g of 4,4°-dihydroxytetraphenylmethane and 2,2-bis(4-
Hydroxyphenyl) propane (42.8 g) was added to 850 m of a 6% by weight sodium hydroxide aqueous solution.
Solution and solvent methylene chloride 300m dissolved in Jl
JL was placed in a reactor equipped with a baffle plate, and while stirring vigorously at room temperature, phosgene gas was blown into it at a rate of 900 mJl/min. When the pH of the reaction system reached 8.0, the phosgene gas injection was stopped. , and separated by standing to obtain a methylene chloride solution of polycarbonate oligomer.

Next, this solution was diluted with methylene chloride, and the whole solution was diluted with methylene chloride.
1.6 g of p-tert-butylphenol and 5.4 g of 4.41-dihydroxytetraphenylmethane as molecular ff1m moderators, and 2.
2-bis(4-hydroxyphenyl)propane 12.5
To the mixture was added a solution prepared by dissolving 1.g in a 2N sodium hydroxide aqueous solution, and while stirring vigorously, a 5% by weight aqueous solution of triethylamine was added as a catalyst, and the reaction was carried out for 1 hour.

After completion of the reaction, the product was diluted by adding methylene chloride, and then added with 1.5 J of water and 0.5 J of a normal concentration sodium hydroxide aqueous solution. Water 0.51.0.01 Normal concentration of salt @0.51. Washing was performed using 0.5 ounces of water in this order.

Thereafter, the organic layer was separated, poured into 5J1 methanol, and purified by reprecipitation to obtain a white product.

The obtained product had an intrinsic viscosity [η1 (in methylene chloride, 20° C.) of 0, 51 djL/g. Also,
As a result of nuclear magnetic resonance (+8-NMR) spectrum analysis of this product, it was found that this product consists of repeating units [Al1 and [Bl] shown by the following formula, and is a repeating unit. [It was confirmed that the copolymer had an Al1 content of 22 mol%.

Using the polycarbonate polymer obtained in step (1) above as the material for the core material and polymethylpentene-1 as the material for the sheath material layer, they were simultaneously processed into a composite spinning machine using a screw melt extruder set at a temperature of 280"0. was supplied to the spinning head.

Next, the polycarbonate-based polymer and polymethylpentene-1 were simultaneously discharged at a temperature of 2130°C using this composite spinning machine, cooled and solidified, and then withdrawn at a speed of 4.5 m/min to reduce the outer diameter. A plastic optically transmitting fiber having a target of 1000 JLo, a core material diameter of 94 G pm, and an IF material layer thickness of 307 tm was obtained.

Thereafter, two types of samples were prepared by leaving some of the obtained light transmitting fibers at room temperature and others at a temperature of 150° C. for 3,000 hours.

Optical transmission loss at a wavelength of 77 QBm was measured for each sample.

The results are shown in Table 1.

(Example 2.3) In (1) of Example 1, the usage ratio of 4,4°-dihydroxytetraphenylmethane and 2,2-bis(4-hydroxyphenyl)propane was changed to 44g of the former and 21g of the latter.
．． [1 g (Example 2), and the repeating unit [AI 1] and the repeating unit [BI] were prepared in the same manner as in Example 1, except that the former was 63.2 g and the latter was 4.58 g (Example 3). A polycarbonate-based polymer having a molar fraction of . a! II was evaluated for thermal properties and optical transmission loss.

The results are shown in Table 1.

(Example 4) The repeating unit [consisting only of Al1] was prepared in the same manner as in Example 1 except that 2,2-bis(4-hydroxyphenyl)propane was not used in A polycarbonate polymer was prepared, and the thermal properties and optical transmission loss of a light transmitting fiber using this polycarbonate polymer as a core material were evaluated.

The results are shown in Table 1.

(Example 5) In Example 1, except that 2.2-bis(3-methyl-4-hydroxyphenyl)propane was used instead of 2.2-bis(4-hydroxyphenyl)propane, In the same manner as in Example 1, the repeating unit [A
A polycarbonate-based polymer having I 1 and an eel repeat unit [B11] represented by the following formula was prepared.

[B11 using the obtained polycarbonate polymer.

A plastic light transmitting fiber was prepared in the same manner as in Example 1, and the thermal properties and light transmission loss of this light transmitting fiber were evaluated.

The results are shown in Table 1.

(Example 6) Substitute 2,2-bis(4-hydroxyphenyl)propane for (1) in Example 1 above? 2. The repeating unit [A
A polycarbonate-based polymer having l 1 and a repeating unit [B31] represented by the following formula: 31! I did it.

[B11 Using the obtained polycarbonate polymer, a plastic light transmitting fiber was prepared in the same manner as in Example 1,
Thermal properties and optical transmission loss of this optically transmitting fiber were evaluated.

The results are shown in Table 1.

(Example 7) In (1) of Example 1, l-phenyl-1,1 was used instead of 2,2-bis(4-hydroxyphenyl)propane.
- Bis(4-hydroxyphenyl)ethane was used in the same manner as in Example 1, but the spelling unit [A
A polycarbonate polymer having 11 and an edge turning unit [B11] represented by the following formula was prepared.

[84] Using the obtained polycarbonate polymer, a plastic light transmitting fiber was prepared in the same manner as in Example 1, and this light transmitting fiber was evaluated for thermal properties and light transmission loss. Ta.

The results are shown in Table 1.

(Example 8) In Example 1 (1), bis(4-human waxyphenyl) was used instead of 4,4'-dihydroxytetraphenylmethane and 2,2-bis(4-hydroxyphenyl)propane. )-Bis(4-methylphenyl)methane was used, but in the same manner as in Example 1, a repeating unit [A? ] A polycarbonate-based polymer was prepared.

Using the obtained polycarbonate polymer, a plastic light transmitting fiber was prepared in the same manner as in Example 1,
Thermal properties and optical transmission loss of this optically transmitting fiber were evaluated.

The results are shown in Table 1.

(Example 9) In Example 8, bis(4-hydroxyphenyl)-bis(4-methylphenyl)methane was replaced with bis(4-hydroxyphenyl)-bis(4-methylphenyl)methane.
A polycarbonate polymer having an edge-turning unit [A3] represented by a linear formula was prepared in the same manner as in Example 8 except that 4-hydroxyphenyl)-bis(4-n-propylphenyl)methane was used. did.

Using the obtained polycarbonate polymer, a plastic light transmitting fiber was prepared in the same manner as in Example 8,
The optical transmission fiber was evaluated for M-3 properties and optical transmission loss.

The results are shown in Table 1.

(Example 10) In Example 8, bis(4-hydroxyphenyl)-bis(4-methylphenyl)methane was replaced with bis(4-hydroxyphenyl)-bis(4-methylphenyl)methane.
A polycarbonate polymer having a repeating unit [A4] represented by the following formula was prepared in the same manner as in Example 8 except that 4-hydroxyphenyl)-bis(3-methoxy5diphenyl)methane was used.

Using the obtained polycarbonate polymer, PLASTI-2 optically transmitting fibers were prepared in the same manner as in Example 8, and the obtained plastic optically transmitting fine fibers were evaluated for thermal properties and optical transmission loss. I did this.

The results are shown in Table 1.

(Example 11) In Example 8, bis(4-hydroxyphenyl)-bis(4-methylphenyl)methane was replaced with bis(4-hydroxyphenyl)-bis(4-methylphenyl)methane.
A polycarbonate polymer having a repeating unit [A5] represented by the following formula was prepared in the same manner as in Example 8 except that 3-methyl-4-hydroxyphenyl)-bis(4-methylphenyl)methane was used. Prepared.

(Hereafter, margin) using the obtained polycarbonate polymer.

A plastic optically transmitting fiber was prepared in the same manner as in Example 1, and about the obtained plastic optically transmitting fiber,
Thermal properties and optical transmission loss were evaluated.

The results are shown in Table 1.

(Example 12) In (1) of Example 1, instead of 4,4'-dihydroxytetraphenylmethane and 2,2-bis (4-hydroxyphenyl) propane, bis (4-methylphenyl)-bis -Hydroxyphenyl)methane and 2,2-bis(4-hydroxyphenyl)propane were used in the same manner as in Example 1. A combination was prepared.

Using the obtained polycarbonate polymer, a plastic light transmitting fiber was prepared in the same manner as in Example 1,
Thermal properties and optical transmission loss of this optically transmitting fiber were evaluated.

The results are shown in Table 1.

(Example 13) In (1) of Example 1, 4.4°-dihydroxytetraphenylmethane and 3 .3-bis(4-hydroxyphenyl)pentane was used, but in the same manner as in Example 1, a polycarbonate polymer having the repeating unit [AI 1 and the repeating unit [B11] represented by the following formula was prepared. Prepared.

Using the obtained polycarbonate polymer, the thermal properties and optical transmission loss of the plastic optical fiber obtained in the same manner as in Example 1 were evaluated.

The results are shown in Table 1.

(Hereafter, margin)

Claims (1)

[Claims] (1) The core material and the sheath material layer are the basic structural units, and the core material has the following formula [A]; ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [A] and formulas [B] ▲ Mathematical formulas, chemical formulas, tables, etc. ▼[B] (However, X^1, Y^2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and R^1, R
^2 represents either a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and X^3 and X^4 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
represents an alkyl group, an aryl group having 6 to 8 carbon atoms, or a halogen atom. ) is made of a polycarbonate polymer having a repeating unit represented by A plastic light transmitting fiber characterized by having a refractive index smaller than that of the material by 0.01 or more.