JPS61285282A - Composition for connection terminal of optical transmission channel - Google Patents

Abstract

PURPOSE:To provide a composition for the connection terminal of an optical transmission channel, composed of a resin exhibiting anisotropy in molten state and an antistatic agent, having high dimensional accuracy and excellent dimensional stability, giving little loss of light by repeated connection and disconnection, producible in large quantities and suitable as an optical connector. CONSTITUTION:The objective composition for the connection terminal of an optical transmission channel can be produced from (A) a resin exhibiting anisotropy in molten state (preferably a polyester, etc., composed of 70-80mol% unit of formula I and 20-30mol% unit of formula II, (B) an antistatic agent (preferably a nonionic antistatic agent) and, if necessary, (C) a filler (preferably carbon black powder). The amounts of the components B and C are 0.1-0.5wt% and 2-30wt%, respectively based on the whole weight including the resin.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to optical communication systems and other optical application fields when interconnecting optical transfer line main lines, branch lines, subline lines, various devices, and their circuit components, etc. The present invention relates to a transmission line connection terminal (connector) to be used, and in particular provides a composition suitable for an optical connector consisting of a component having a fiber insertion hole called a core type connection terminal (ferrule).

[Conventional technology and its problems]

In an optical communication system, connecting parts for connecting optical transfer paths to each other or to various devices and their circuit components are important parts in the optical communication system, and in particular, there are many connections between optical transfer paths. It is expected that the connection parts will be used not only for their excellent mechanical properties but also for their ease of mass production.

Until now, the methods for connecting optical transmission lines include a method of fusing optical fibers together, a permanent method of connecting one end of the optical fibers using splice parts, and a method of connecting and disconnecting optical fibers using connectors. Possible connection methods have been developed.

In particular, the connection method using detachable connectors is an extremely effective method for connecting the circuits of devices such as light oscillation, amplification, modulation, and light reception with transmission lines, and for connecting complex lines, etc., and is highly effective for dimensional accuracy. If it is possible to manufacture parts with excellent performance, low-loss connections can be achieved using a simple method.

Various optical connector structures have been proposed, but the basic structure consists of a fiber insertion plug and a receptacle that supports it, with a fiber fixed to the fiber insertion plug and one end of the fibers butted against each other.

In particular, a structure with a fiber insertion hole called a ferrule is typical. A fiber with an outer diameter of 125 μm and a core diameter of 50 μm is inserted into the fine hole at the tip of this ferrule and fixed with adhesive. and fixed with a receptacle. Unless the dimensions of the fine holes at the tip of the ferrule are controlled with an accuracy of several μm, it is difficult to suppress the fiber connection loss to 1 dB or less.

The component parts of these connectors are required to have extremely precise dimensional accuracy, and not only the ferrule that directly contacts the fiber, but also the sleeve and ferrule that hold and fix the ferrule are required to have dimensional accuracy within several μm. These component parts with extremely high dimensional accuracy can only function as a connector.

In order to meet this required specification, attempts have been made to fabricate core-type connection terminals from metal and ceramic processing and thermoplastic resins. In this case, if metals or ceramics are used as raw materials, parts with good dimensional accuracy can be provided, but on the other hand, special equipment is required, processing time is long, and mass production processability is inferior. It has the disadvantage of being expensive.

On the other hand, resin parts require regular equipment and short molding time.
Although it has excellent mass production processability, conventional resin compositions have poor dimensional accuracy and stability, and have not been able to realize low-loss connections.

[Means for solving problems]

The present inventors have conducted extensive research in order to obtain a ferrule with good dimensional accuracy without impairing the mass production processability of thermoplastic resin, and have completed the present invention.

. That is, the present invention provides (A) a resin exhibiting anisotropy when melted; (B)
This is an optical transfer path connecting terminal composition comprising an antistatic agent and (C) a filler added if desired, and the composition obtained by the present invention has extremely good dimensional accuracy and excellent dimensional stability against environmental temperature changes, It is possible to realize a connector with extremely low loss due to repeated attachment and detachment, and is also excellent in mass production processability.

The resin used in the present invention, which exhibits anisotropy when melted, is called a thermotropic liquid crystal polymer, and has excellent mechanical properties, especially exhibiting liquid crystallinity when melted, and has extremely low viscosity and moldability using fine molds. It is extremely good, and after solidification,
It was discovered that it maintains orientation from the liquid crystal state and has extremely high dimensional stability because the molecule has a rod-like skeleton, making it ideal for this purpose.

That is, the resin used in the present invention is a thermoplastic melt-processable polymer composition that exhibits optical anisotropy when melted, and is generally classified as a thermotropic liquid crystal polymer.

Polymers that form such an anisotropic melt phase have a property in which polymer molecular chains are regularly arranged in parallel in a molten state. The state in which the molecules are arranged in this way is often called the liquid crystal state or the nematic phase of liquid crystal materials. Such polymers are generally elongated, oblate, and are made from monomers that are fairly rigid along the long axis of the molecule and have multiple chain extensions, usually in either coaxial or parallel relationships. Manufactured.

The nature of the anisotropic melt phase can be confirmed by conventional polarization testing using crossed polarizers. More specifically, the anisotropic melt phase can be confirmed by using a Leitz polarizing microscope and observing a sample placed on a Leitz hot stage at a magnification of 40 times under a nitrogen atmosphere.

The polymer is optically anisotropic. That is, it transmits light when examined between orthogonal polarizers. If the sample is optically anisotropic, polarized light will pass through it even if it is at rest.

Constituent components of the polymer that forms the anisotropic melt phase as described above include: - Consisting of one or more of aromatic dicarboxylic acids and alicyclic dicarboxylic acids - Aromatic diols, alicyclic diols, and aliphatic diols Consisting of one or more of the following ■ Consisting of one or more aromatic hydroxycarboxylic acids ■ Consisting of one or more aromatic thiol carboxylic acids
.

Consisting of more than one ■ Aromatic dithiol, aromatic thiol phenol
Polyesters consisting of one or more of aromatic hydroxyamines and aromatic diamines, etc. Polyesters that form an anisotropic melt phase include polyesters consisting of ■)■ and ■■) Polyester consisting only of ■ Polyester consisting of ■) ■, ■ and ■ ■) Polythiol ester consisting only of ■ ■) Polythiol ester consisting of ■) ■ Polythiol ester consisting of ■ and ■ ■) ■ and ■ It is composed of a combination of polyesteramide consisting of ■) and ■ and polyesteramide consisting of ■ and ■.

Furthermore, although it is not included in the above range of combinations of ingredients,
Polymers that form an anisotropic melt phase include aromatic polyazomethines, and specific examples of such polymers include poly-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine. ) ; poly
trilo-2-methyl-1,4-phenylenenitrilomethylidine-1,4-phenylenemethylidine); Can be mentioned.

Furthermore, although not included in the above combination of ingredients,
Polyester carbonate is included as a polymer that forms an anisotropic melt phase. It may consist essentially of 4-oxybenzoyl units, dioxyphenyl units, dioxycarbonyl units and terephthaloyl units.

The compounds constituting the above-mentioned components I) to (2) are listed below.

As the aromatic dicarboxylic acid, terephthalic acid, 434"
-diphenyldicarboxylic acid, 4.4'-)diphenyldicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenoxybutane-4 , 4”-dicarboxylic acid, diphenylethane-4,4
'-dicarboxylic acid, isophthalic acid, diphenyl ether-3,3°-dicarboxylic acid, diphenoxyethane-3,
Aromatic dicarboxylic acids such as 3″-dicarboxylic acid, diphenylethane-3,3°-dicarboxylic acid, naphthalene-1,6-dicarboxylic acid, or chloroterephthalic acid, dichloroterephthalic acid, bromoterephthalic acid, methylterephthalic acid, Examples include alkyl, alkoxy or halogen substituted products of the aromatic dicarboxylic acids such as dimethyl terephthalic acid, ethyl terephthalic acid, methoxyterephthalic acid and ethoxyterephthalic acid.

Examples of alicyclic dicarboxylic acids include alicyclic dicarboxylic acids such as trans-1゜4-cyclohexanedicarboxylic acid, cis-1,4-cyclohexanedicarboxylic acid, and 1,3-cyclohexanedicarboxylic acid, or trans-L4- (1
-methyl)cyclohexanedicarboxylic acid, trans-L
4-(1-rol)cyclohexanedicarboxylic acid, etc.
Examples include alkyl, alkoxy, or halogen-substituted products of the above alicyclic dicarboxylic acids.

Aromatic diols include hydroquinone, resorcinol, 4.4°-dihydroxydiphenyl, 4.4'-dihydroxytriphenyl, 2.6-naphthalenediol,
4,4'-dihydroxydiphenyl ether, bis(4
-hydroxyphenoxy)ethane, 3,3'-dihydroxydiphenyl, 3,3'-dihydroxydiphenyl ether, ■, 6-naphthalenediol, 2,2-bis(
4-hydroxyphenyl)propane, 2,2-bis(4
Aromatic diols such as -hydroxyphenyl)methane, chlorohydroquinone, methylhydroquinone, 1
-Butylhydroquinone, phenylhydroquinone, methoxyhydroquinone, phenoxyhydroquinone=
Examples include alkyl, alkoxy or halogen substituted products of the above aromatic diols such as 4-chlorresorcin and 4-methylresorcin.

Examples of alicyclic diols include trans-1,4-cyclohexanediol, cis-1,4-cyclohexanediol, trans-1,4-cyclohexane dimetatool,
Alicyclic diols such as cis-1,4-cyclohexane dimetatool, trans-1,3-cyclohexanediol, cis-1,2-cyclohexanediol, trans-1,3-cyclohexane dimetatool, or trans-1 , 4-, (1-methyl) cyclohexane diol, trans-1,4-(1-chloro) cyclohexane diol, and other alkyl, alkoxy or halogen substituted alicyclic diols.

Aliphatic diols include ethylene glycol, 1,3
-Light chain or branched aliphatic diols such as propanediol, 1,4-butanediol, neopentyl glycol and the like can be mentioned.

Examples of aromatic hydroxycarboxylic acids include 4-hydroxybenzoic acid, 3-hydroxybenzoic acid, and 6-hydroxybenzoic acid.
Aromatic hydroxycarboxylic acids such as 2-naphthoic acid and 6-hydroxy-1-naphthoic acid, or 3-methyl-4-
Hydroxybenzoic acid, 3,5-dimethyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid
Froic acid, 3-methoxy-4-hydroxybenzoic acid, 3.5
-dimethoxy-4-hydroxybenzoic acid, 6-hydroxy-5-methyl-2-naphthoic acid, 6-hydroxy-5
-methoxy-2-naphthoic acid, 3-chloro-4-hydroxybenzoic acid, 2-chloro-4-hydroxybenzoic acid,
2,3-dichloro-4-hydroxybenzoic acid, 3,5-
Dichloro-4-hydroxybenzoic acid, 2.5-dichloro-4-hydroxybenzoic acid, 3-bromo-4-hydroxybenzoic acid, 6-hydroxy-5-chloro-2-naphthoic acid, 6-hydroxy-7=chloro -2-naphthoic acid,
Examples include alkyl, alkoxy or halogen substituted aromatic hydroxycarboxylic acids such as 6-hydroxy-5,7-dichloro-2-naphthoic acid.

Examples of aromatic mercaptocarboxylic acids include 4-mercaptobenzoic acid, 3-mercaptobenzoic acid, 6-mercapto-2-naphthoic acid, and 7-mercapto-2-naphthoic acid.

Examples of the aromatic dithiol include benzene-1,4-dithiol, benzene-1,3-dithiol, 2,6-naphthalene-dithiol, and 2,7-naphthalene-dithiol.

Examples of aromatic mercaptophenol include 4-mercaptophenol, 3-mercaptophenol, 6-mercaptophenol, and 7-mercaptophenol.

Aromatic hydroxyamine, aromatic diamine is 4-
Aminephenol, N-methyl-4-aminophenol, lI4-phenylenediamine, N-methyl-1,4-
Phenyldiamine, N, N'-dimethyl-1,4-
Phenylene diamine, 3-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-7minophenol, 4-amino-1-naphthol, 4-amino-
4′-hydroxydiphenyl, 4-amino-4′-hydroxydiphenyl ether, 4-amino-4′-hydroxydiphenylmethane, 4-amino-4′-hydroxydiphenyl sulfide, 4.4”-diaminophenyl sulfide (thiodianiline), 4.4'-diaminodiphenylsulfone, 2.5-diaminotoluene, 4,
4′-ethylene dianiline, 4,4°-diaminodiphenoxyethane, 4.4”-diaminodiphenylmethane (
methylene dianiline), 4,4'-diaminodiphenyl ether (oxydianiline), and the like.

The above-mentioned polymers I) to ① consisting of each of the above components may or may not form an anisotropic melt phase depending on the constituent components, the composition ratio in the polymer, and the sea fence distribution, but they may or may not form an anisotropic melt phase. The polymers that can be used are limited to those that form an anisotropic melt phase among the above-mentioned polymers.

The polyesters (I), n), and III) and the polyesteramide (ii), which are polymers that form an anisotropic melt phase suitable for use in the present invention, contain functional groups that form the required repeating units by condensation. It can be produced by various ester formation methods that allow the organic monomer compounds that are present to react with each other. For example, the functional groups of these organic monomer compounds may be carboxylic acid groups, hydroxyl groups, ester groups, acyloxy groups, acid halides, amine groups, and the like. The organic supercompounds described above can be reacted without the presence of a heat exchange fluid by a melt acidolysis method. In this method, the monomers are first heated together to form a molten solution of the reactants. As the reaction continues, solid polymer particles become suspended in the liquid. Vacuum may be applied to facilitate removal of by-product volatiles (eg acetic acid or water) during the final stage of condensation.

Slurry polymerization techniques can also be employed to form fully aromatic polyesters suitable for use in the present invention. In this process, a solid product is obtained in suspension in a heat exchange medium.

Regardless of whether the above-mentioned melt acidolysis method or slurry polymerization method is employed, the organic monomer reactant for inducing the fully aromatic polyester is in a modified form (i.e., lower (as an acyl ester). The lower acyl group preferably has about 2 to 4 carbon atoms. Preferably, an acetate ester of such an organic monomer reactant is subjected to the reaction.

Furthermore, representative examples of catalysts that can optionally be used in either the melt acidolysis method or the slurry method include dialkyltin oxides (e.g., dibutyltin oxide), diaryltin oxides, titanium dioxide, antimony dioxide, alkoxytitanium silicates, titanium alkoxides, Alkali and alkaline earth metal salts of carboxylic acids (e.g. zinc acetate), Lewis (e.g. BF3), hydrogen halides (e.g.
Examples include gaseous acid catalysts such as 1fcl). The amount of catalyst used is generally about o, based on the total weight of monomer.
ooi to 1% by weight, especially about 0.01 to 0.2% by weight.

Fully aromatic polymers suitable for use in the present invention tend to be substantially insoluble in common solvents and are therefore unsuitable for solution processing.

However, as previously mentioned, these polymers can be readily processed using conventional melt processing methods. Particularly preferred fully aromatic polymers are somewhat soluble in pentafluorophenol.

Fully aromatic polyesters suitable for use in the present invention generally have a weight average molecular weight of about 2.000 to 200.000.
, preferably about 10,000 to 50,000, particularly preferably about 20,000 to 25,000. On the other hand, suitable fully aromatic polyesteramides generally have a molecular weight of about 5.000 to 50,000, preferably about 10,000.
~30,000. For example, 15,000-17,000. Such molecular weight measurements can be carried out by gel permeation chromatography as well as other standard methods of measuring polymers that do not involve solution formation, such as quantification of end groups by infrared spectroscopy on compression molded films. Alternatively, the molecular weight can be measured using a light scattering method using a pentafluorophenol solution.

The fully aromatic polyesters and polyesteramides described above also yield 0.1% of pentafluorophenol at 60°C.
When dissolved at a weight percent concentration of at least about 2.0 d
! /g, for example about 2.0 to 10.0d17g.

Particularly preferred anisotropic melt phase forming polyesters for use in the present invention include repeat units containing naphthalene moieties such as 6-hydroxy-2-naphthoyl, 2,6-hydroxynaphthalene and 2,6-dicarboxynaphthalene. It contains about 10 mol% or more. Preferred polyesteramides are those containing repeating units of the naphthalene moiety described above and a moiety consisting of 4-aminophenol or 1,4-phenylenediamine. Specifically, the details are as follows.

(1) A polyester consisting essentially of the following repeating units I and ■.

This polyester contains about 10 to 90 mol% of unit ■ and about 1
Contains 0 to 90 mol % of units (■). In ILi-like, the unit (■) is about 65 to 85 mol%, preferably about 70 to 80
present in an amount up to mol % (eg, about 75 mol %). In another embodiment, the unit ■ is present in much lower concentrations of about 15-35 mole %, preferably about 20-30 mole %. In addition, at least some of the hydrogen atoms bonded to the ring are
Optionally, an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
may be substituted with a substituent selected from the group consisting of an alkoxy group, halogen, phenyl, substituted phenyl, and combinations thereof.

(2) A polyester consisting essentially of the following repeating units ■, ■, and ■.

This polyester contains about 30 to 70 mole percent of units. The polyester preferably has about 40 to 60
Contains mol % of units I, about 20-30 mol % of units (), and about 20-30 mol % of units -. In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally consist of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, or a combination thereof. It may be substituted with a substituent selected from the group.

(3) Polyester consisting essentially of the following repeating units ■, ■, ■ and ■: (wherein R means methyl, chloro, bromo or a combination thereof, and is a substituent for the hydrogen atom on the aromatic ring. ), and about 20 to 60 mol% of the unit ■,
It contains about 5 to 18 mol % of units 1, about 5 to 35 mol % of units m, and about 20 to 40 mol % of units . The polyester preferably comprises about 35 to 45 mole percent units, about 10 to 15 mole percent units, and about 15 to 2 mole percent units.
5 mol% unit■, and approximately 25-35 mol% unit■
Contains. However, the total molar concentration of units ■ and ■ is substantially equal to the molar concentration of unit ■.

In addition, at least some of the hydrogen atoms bonded to the ring are
Optionally, an alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
may be substituted with a substituent selected from the group consisting of an alkoxy group, halogen, phenyl, substituted phenyl, and combinations thereof. This fully aromatic polyester was converted into pentafluorophenol by 0.3w at 60°C.
When dissolved at /vχ concentration, the amount is 2.0 dl/
g For example 2.0-10. Logarithmic viscosity in Oj/g is generally indicated.

(4) Polyester consisting essentially of the following repeating units I, ■, ■ and ■: ■ General formula -EO-Ar-0) (wherein Ar means a divalent group containing at least one aromatic ring) ), containing at least one aromatic ring, 2
20 to 40 mol% of units I and more than 10 mol% and up to about 50 mol% of units 1. Contains the unit (2) in an amount of more than 5 mol% but not more than about 30 mol%, and contains the unit (2) in an amount of more than 5 mol% and not more than about 30 mol%. The polyester preferably contains about 20 to 30 mole percent (e.g. about 2
5 mol%) unit ■, about 25 to 40 mol% (e.g. about 35 mol%)
mol%) unit ■, about 15 to 25 mol% (e.g., about 20 mol%) unit ■, and about 15 to 25 mol% (e.g., about 2
0 mol %) of the unit ■. In addition, at least some of the hydrogen atoms bonded to the ring may have a carbon number of 1
It may be substituted with a substituent selected from the group consisting of ~4 alkyl groups, C1-4 alkoxy groups, halogens, phenyls, substituted phenyls, and combinations thereof.

Units ■ and ■ have a symmetrical arrangement on one or more aromatic rings in which the divalent bonds connecting these units to other units on either side within the polymer backbone (e.g., on a naphthalene ring) When present, they are preferably symmetrical in the sense that they are arranged para to each other or on a diagonal ring. However, asymmetric units such as those derived from resorcinol and isophthalic acid can also be used.

The preferred dioxyaryl unit ■ is and the preferred dicarboxyaryl unit ■ is It is.

(5) Polyester consisting essentially of the following repeating units ■, ■ and ■: ■ General formula -EO-Ar-0) (wherein Ar means a divalent group containing at least one aromatic ring) It consists of a dioxyaryl unit as shown, a small number (both mean a divalent group containing one aromatic ring) of a dicarboxyaryl unit, and about 10 to 90 mol% of the unit (■) and 5 of the unit (■). -45 mol%, and contains units (2) in an amount of 5 to 45 mol%. The polyester preferably contains about 20 to 80 mole percent units I, about 10 to 40 mole percent units {circle around (2)}, and about 10 to 40 mole percent units ■. More preferably, the polyester contains about 60 to 80 mole % units of
It contains about 10 to 20 mol % of units (2) and about 10 to 20 mol % of units (2). In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, or a combination thereof. may be substituted with a substituent selected from.

The preferred dioxyaryl unit ■ is and the preferred dicarboxyaryl unit ■ is It is.

(6) Polyesteramide consisting essentially of the following repeating units I, ■, ■, and ■: a divalent group containing at least one aromatic ring or a divalent trans-
cyclohexane group), ■ General formula (Y-Ar
-23- (wherein Ar is a divalent group containing at least one aromatic ring, Y is 0, NH or NR, Z is NH or NR
respectively, and R is an alkyl group having 1 to 6 carbon atoms,
or aryl group), ■ General formula I0-Ar
'-0) (in the formula, total means a divalent group containing at least one aromatic ring), and contains about 10 to 90 mol% of unit I and about 5 to 45 mol% of unit U , about 5 to 45 mol % of the unit (■), and about 0 to 40 mol % of the unit (2). In addition, at least a portion of the hydrogen atoms bonded to the ring may optionally be a group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, halogen, phenyl, substituted phenyl, or a combination thereof. may be substituted with a substituent selected from.

Preferred dicarboxyaryl units (2) are, preferred units (2) are, and preferred dioxyaryl units (2) are.

Furthermore, the polymer forming the anisotropic melt phase of the present invention includes:
A part of one polymer chain is composed of polymer segments that form an anisotropic melt phase as explained above, and the remaining part is composed of thermoplastic resin segments that do not form an anisotropic melt phase. Also includes polymers.

The antistatic agent used in the present invention has a remarkable effect in preventing the adhesion of dust in the air due to repeated attachment and detachment, and the addition of the antistatic agent enables low-loss connections. The purpose of the antistatic agent used can be achieved by either a coating type or a kneading type, but the kneading type is preferable in consideration of mass production processability.

In addition, antistatic agents can be classified into cationic, anionic, nonionic, and amphoteric types, and anionic antistatic agents include phosphate ester type M=, Na or (Cd5.0), and lHM. = to +Na or (C2H3O), H sulfonic acid type 1? Examples include s03M ROS03M M=K or Na sulfate ester type RO (C2H40)flS03M. ' As for the cation type, quaternary ammonium salt type imidacillin type amide amine type X-=NO+-, CHzCOO-, R(C2H4,0H
)Z-, CI(, +5O4-, etc.).

Nonionic types include alkyl ether, ester type RO (CZH,,0) secondary RCOO (CJ40). H Polyoxyethylene sorbitan ester type CHt
CHCOOR Alkylamine type, alkylamide type, etc. are mentioned.

As a bisexual type betaine type R' RN”-CHzCOO- R' Alanine type RNHCHzCOONa etc.

These antistatic agents are used in the same way as for normal thermoplastic resins, but considering thermal stability etc.
Anionic, nonionic and amphoteric antistatic agents are preferred, and nonionic antistatic agents are particularly preferred.

The antistatic agent is used in an amount of 0.1% to 5% by weight of the total weight including the resin.

In addition to the usual antistatic agent, it is also possible to use usual methods for preventing damage caused by static electricity, such as applying a conductive paint or incorporating a conductive filler, but the latter is preferred. Conductive fillers include metal powders and their flakes such as iron powder, brass powder, copper powder, aluminum powder, and nickel powder, carbon powders such as carbon black and acetylene plaque, graphite and carbon microballoons, nickel, granite, copper, etc. metal-coated glass flakes, metal oxides such as iron oxide, tin oxide, etc. are possible, but carbon powder is particularly preferred.

These conductive fillers account for 0.5 of the total weight including resin etc.
Used from 2 to 50% by weight, preferably from 2 to 30% by weight
It is. Further, these compounds having antistatic ability are selected from at least one kind or a combination of two or more kinds from among the above.

Further, the filler used if desired includes fibers and inorganic powders as reinforcing agents normally used for resins. These are effective in preventing protrusion of the core during polishing of the connection end surface, and also improve dimensional accuracy.

The following fibers can be used.

Metal fibers include fibers of mild steel, stainless steel, copper and its alloys, brass, aluminum and its alloys, lead, etc. Carbon fibers include PA made from polyacrylonitrile.
Pitch-based fibers made from N-based pitch are used.

In addition to regular glass fibers, can we use glass fibers coated with nickel or copper rings, silane fibers, aluminosilicate glass fibers, hollow glass fibers, non-hollow fibers, etc.? can be,
Inorganic fibers include various fibers such as rock wool, zirconia, alumina-silica, potassium titanate, barium titanate, silicon carbide, alumina, silica, and blast furnace slag, and whiskers include silicon nitride whiskers and oxynitride. Iridium whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, silicon carbide whiskers, boron whiskers, etc. are used.

As the synthetic fiber, aramid fiber which is a completely aromatic polyamide, kynol which is a phenolic resin fiber, etc. are used.

As the mineral fiber, asbestos, wollastonite, etc. are used, and as the natural fiber, cellulose fiber, hemp thread, etc. are used.

These fibers are used in an amount of 2 to 70% by weight, preferably 10 to 50% by weight of the total weight including resin.

Examples of inorganic powders include the following.

Kaolin, fired clay, Tano L;-2, Canadian mica,
Mica, vermiculite, calcium silicate, feldspar powder, acid clay, waxite clay, sericite, sillimanite, bentonite, glass flakes, glass powder, glass peas, slate powder, silicates such as silane, calcium carbonate, whitewash, carbonic acid Barium, magnesium carbonate, carbonates such as dolomite, pallite powder, Planfix, precipitated calcium sulfate, sulfates such as calcined gypsum, hydroxides such as hydrated alumina, alumina, antimony oxide, magnesia,
These include titanium oxide, zinc white, amorphous silica, flint quartz, silica sand, white carbon, diatom oxides, and sulfides such as molybdenum disulfide.

In addition to inorganic compounds, it is also possible to add wood flours such as wood flour, coconut flour, walnut flour, and pulp flour.

These inorganic powders are used in an amount of 2 to 60% by weight, preferably 10 to 50% by weight of the total weight including the resin.

These fillers are selected from at least one type or a combination of more than the above.

The melt-processable polymer composition that forms an anisotropic melt phase used in the present invention includes: (1) other polymers that form an anisotropic melt phase, (2) thermoplastic resins that do not form an anisotropic melt phase, (2) It may contain one or more of the following: a thermosetting resin, and (1) a low-molecular organic compound. Here, the polymer forming the anisotropic melt phase and the remaining portion in the composition may or may not be thermodynamically compatible.

Examples of the above thermoplastic resin (■) include polyethylene,
Polypropylene, polybutylene, polybutadiene, polyisoprene, polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylic resin, ABS
Resin, AS resin, BS resin, polyurethane, silicone resin, polyacetal, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, aromatic polyester, polyamide, polyacrylonitrile,
Included are polyvinyl alcohol, polyvinyl ether, polyetherimide, polyamideimide, polyetheretherimide, polyetheretherketone, polyethersulfone, polysulfone, polyphenylene sulfide, polyphenylene oxide, and the like.

Examples of the thermosetting resin (2) include phenol resins, epoxy resins, melamine resins, urea resins, unsaturated polyester resins, and alkyd resins.

Examples of the low-molecular-weight organic compounds mentioned in (1) above include substances added to general thermoplastic resins and thermosetting resins, such as stabilizers such as plasticizers, antioxidants, and ultraviolet absorbers;
Low molecules used as flame retardants, colorants such as dyes and pigments, blowing agents, crosslinking agents such as divinyl compounds, peroxides and vulcanizing agents, and lubricants to improve fluidity and mold release properties. Contains organic compounds.

〔Effect of the invention〕

The composition according to the present invention has high dimensional accuracy, an extremely small coefficient of linear expansion, and excellent dimensional stability against changes in environmental temperature. Furthermore, it is possible to mold a connecting terminal (connector) with little optical loss due to repeated attachment and detachment, and mass production is possible using ordinary thermoplastic resin equipment.

〔Example〕

The present invention will be explained below with reference to Examples.

Example 1 A test piece was prepared using a Nissey injection molding machine FS-75Nn using 100 parts of a resin A to be described later and 0.4 parts of a nonionic antistatic agent (Electro Stripper TS-5 manufactured by Kao Soap Co., Ltd.). Its shape is as shown in FIG. 1, and the dimensions of the mold are φ-=0.127 mm and φ=2.511 mm. However, the shape of this figure does not limit the scope of the present invention. Molding conditions are cylinder part 300℃, nozzle 30
0″C1 mold temperature 120℃, injection pressure 400kg/cm
The molded test piece was left in a constant temperature room at 23°C and 50 parts humidity for 48 hours, and the outer diameter was measured for dimensional accuracy using a Sankai Seisakusho dimension measuring device.The eccentricity of the hole was measured using a Tokyo Seimitsu Measurement was performed using a Roncom roundness measuring device.The number of measurement points is the average value of 40 points.The coefficient of linear expansion was calculated by measuring the outer diameter dimension between 25°C and 80°C.

Thereafter, test pieces were prepared using the compositions of Examples 2 to 12 in the same manner, and various measurements were performed. The same applies to Comparative Examples 1 to 5. The results are shown in Tables 1 to 3.

Polymer A forming an anisotropic melt phase was used.

B, C, and D have the following structural units.

=60/20/10/10 =60/20/20 =70/30 =70/15/15 The specific manufacturing methods of the resins A, B, C, and D are described below.

<Resin A> 1081 parts by weight of 4-acetoxybenzoic acid, 460 parts by weight of 6-acetoxy-2-naphthoic acid, 166 parts by weight of isophthalic acid
194 parts by weight of 1,4-diacyoxybenzene were charged into a reactor equipped with a stirrer, a nitrogen inlet tube and a distillation tube, and the mixture was heated to 260° C. under a nitrogen stream. The mixture was vigorously stirred at 260°C for 2.5 hours and then at 280''C for 3 hours while distilling acetic acid from the reactor.

Furthermore, after raising the temperature to 320°C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced to 0.5 minutes after 15 minutes.
The temperature was lowered to 1 mmHg, and the mixture was stirred at this temperature and pressure for 1 hour.

The resulting polymer had an intrinsic viscosity of 5.0, measured in pentafluorophenol at a concentration of 0.1% by weight at 60°C.

Resin B> 4-acetoxybenzoic acid 1081! i parts by weight, 489 parts by weight of 2.6-cyacydoxynaphthalene, 33 parts by weight of terephthalic acid
Two parts by weight were charged into a reactor equipped with a stirrer, a nitrogen inlet tube and a distillation tube, and the mixture was heated to 250° C. under a nitrogen stream. While distilling acetic acid out of the reactor, the mixture was vigorously stirred at 250°C for 2 hours and then at 280°C for 2.5 hours.

Furthermore, after raising the temperature to 320°C and stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced to 0.30 minutes later.
The temperature was lowered to 2 mmHg, and the mixture was stirred at this temperature and pressure for 1.5 hours.

The resulting polymer had an intrinsic viscosity of 2.5, measured in pentafluorophenol at 60° C. and a concentration of 0.1% by weight.

Resin C> 1261 parts by weight of 4-acetoxybenzoic acid and 691 parts by weight of 6-acetoxy-2-naphthoic acid were charged into a reactor equipped with a stirrer, a nitrogen introduction pipe and a distillation pipe, and the mixture was heated under a nitrogen stream. was heated to 250°C. At 250°C for 3 hours, then at 280°C for 2 hours while distilling acetic acid from the reactor.
Stir vigorously for an hour. Further, the temperature was raised to 320"C, and after stopping the introduction of nitrogen, the pressure in the reactor was gradually reduced, and after 20 minutes, the pressure was lowered to (1.1 mm) Ig, and the mixture was stirred at this temperature and pressure for 1 hour. .

The resulting polymer had an intrinsic viscosity of 5.4 as measured in pentafluorophenol at 60'C at a concentration of 0.1% by weight.

<Resin D> 1612 parts by weight of 6-acetoxy-2-naphthoic acid, 4-
290 parts by weight of acetoxyacetanilide, 249 parts by weight of terephthalic acid, and 0.4 parts by weight of sodium acetate in a stirrer,
The mixture was charged into a reactor equipped with a nitrogen inlet tube and a distillation tube, and the mixture was heated to 250° C. under a nitrogen stream. 1 hour at 250"C, then 3 hours while distilling acetic acid from the reactor.
The mixture was stirred vigorously at 00°C for 3 hours. Furthermore, the temperature was increased to 340℃
After stopping the introduction of nitrogen, the pressure inside the reactor was gradually reduced to 0.2 mmHg after 30 minutes.
The mixture was stirred at this temperature and pressure for 30 minutes.

The resulting polymer had an intrinsic viscosity of 3.9 as measured in pentafluorophenol at 60° C. and a 061 degree of gravity.

Also, the connection loss in the table is calculated when the light source is an LED with a wavelength of 0.85 μm.
A 1 km GI type quartz fiber with an outer diameter of 125 μm and a core diameter of 50 μm was used as a dummy fiber.

Cyanoacrylate instant adhesive was used as the connecting agent, and the butted ends were diamond polished.

The loss after repetition was measured in the same manner after attaching and detaching 1000 times.

The antistatic agents, fillers, resins, etc. used are as follows.

Nonionic surfactant; manufactured by Kao Soap Co., Ltd., Electro Stripper TS-5 Anionic surfactant; manufactured by Kao Soap Company, Electro Stripper PC Wollastonite; Interpace Corp.
Manufactured carbon fiber; C6-N glass fiber manufactured by Toho Bethlon ■;
Made by Asahi fiber glass ■847 silica; Made by Toshiba ceramics ■

[Brief explanation of drawings]

FIG. 1 is a schematic diagram of an optical transfer path connection terminal model used in the experiment.

Claims (1)

[Claims] (A) Resin exhibiting anisotropy when melted, (B) Antistatic agent, (
C) Optical transmission line connecting terminal composition comprising a filler added as desired.