JP4600072B2 - Compact - Google Patents

Description

  The present invention relates to a molded article formed by coating a substrate with a liquid crystal polyester resin composition.

  In recent years, the demand for electric wires and cables for building various communication networks in the information society has increased. In particular, due to the widespread use of cable TV and mobile phones, electric wires and cables having excellent electrical characteristics that exhibit lower loss transmission characteristics in a high frequency range are widely demanded from the market. Widely marketed coating materials include polyethylene and polyvinyl chloride. However, polyethylene, for example, has excellent electrical properties but poor fire resistance, and polyvinyl chloride has excellent fire resistance, but contains halogen elements, so it generates harmful gases during combustion after disposal. It does not satisfy the request sufficiently.

  On the other hand, melt-type liquid crystal (thermotropic liquid crystal) polymers such as liquid crystal polyester show heat resistance, high strength, and impact resistance, but have high orientation in the molecular chain direction and flexibility in the direction perpendicular to the molecular chain. Therefore, there was a problem such as cracking when used as a coating material.

  Under such circumstances, Patent Document 1 discloses that a coating material having excellent wear resistance can be obtained by adding a liquid crystal polymer to an olefin resin. It was necessary to add a metal hydroxide as a flame retardant, and there was a problem in recyclability.

JP 2002-146120 A.

  An object of the present invention is to supply electricity to a molded body and a substrate having a coating material and a substrate that are excellent in flame retardancy without adding a flame retardant, have a low dielectric constant and dielectric loss tangent, and excellent in flexibility. Sometimes, it is to provide a molded body with a small transmission loss, particularly an electric wire or cable.

  The present invention comprises (1) (A) a liquid crystal polyester as a continuous phase, and (B) a liquid crystal polyester resin composition having a copolymer having a functional group having reactivity with the liquid crystal polyester as a dispersed phase. And (2) a molded body having a coating layer made of the liquid crystal polyester resin composition, and (3) an electric wire or cable coated with the resin composition.

  According to the present invention, it is not essential to include a halogen-based flame retardant or a phosphorus-based flame retardant, and a molded body having a coating material that has excellent flame retardancy, low dielectric constant, low dielectric loss, and excellent flexibility. Provided is a molded product with less transmission loss when the substrate is energized.

Next, the present invention will be described in more detail.
The liquid crystal polyester of the component (A) of the liquid crystal polyester resin composition in the present invention is a polyester called a thermotropic liquid crystal polymer.

In particular,
(1) A combination of an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid.
(2) A combination of different kinds of aromatic hydroxycarboxylic acids.
(3) A combination of an aromatic dicarboxylic acid and a nucleus-substituted aromatic diol.
(4) Those obtained by reacting an aromatic hydroxycarboxylic acid with a polyester such as polyethylene terephthalate.
The anisotropic melt is formed at a temperature of 400 ° C. or lower. In addition, these ester-forming derivatives may be used in place of these aromatic dicarboxylic acids, aromatic diols and aromatic hydroxycarboxylic acids.

  As the repeating structural unit of the liquid crystal polyester, the following (d) a repeating structural unit derived from an aromatic dicarboxylic acid, (e) a repeating structural unit derived from an aromatic diol, and (f) derived from an aromatic hydroxycarboxylic acid. Although a repeating structural unit can be illustrated, it is not limited to these.

(d) Repeating structural unit derived from aromatic dicarboxylic acid:

(e) Repeating structural unit derived from aromatic diol:

(f) Repeating structural unit derived from aromatic hydroxycarboxylic acid:

なる繰り返し構造単位を含むものであり、さらに好ましくはかかる繰り返し構造単位を少なくとも全体の３０モル％以上含むものである。具体的には繰り返し構造単位の組み合わせが下記（Ｉ）〜（VI）のいずれかのものが好ましい。 A particularly preferred liquid crystal polyester is a balance of heat resistance, mechanical properties and processability.

The repeating structural unit is more preferably contained at least 30 mol% or more of the repeating structural unit. Specifically, the combination of repeating structural units is preferably any of the following (I) to (VI).

  Regarding the production methods of the liquid crystalline polyesters (I) to (VI), for example, Japanese Patent Publication No. 47-47870, Japanese Patent Publication No. 63-3888, Japanese Patent Publication No. 63-3891, Japanese Patent Publication No. 56-18016, No. 2-51523. Among these, a combination of (I), (II) and (IV) is preferable, and a combination of (I) and (II) is more preferable.

  In the present invention, in the field where high heat resistance is required, the liquid crystal polyester of component (A) has the following repeating unit (a ′) of 30 to 80 mol% and repeating unit (b ′) of 0 to 10 mol%. A liquid crystal polyester having a repeating unit (c ′) of 10 to 25 mol% and a repeating unit (d ′) of 10 to 35 mol% is preferably used.

（式中、Ａｒは２価の芳香族基である。）

(In the formula, Ar is a divalent aromatic group.)

  In the molded body of the present invention, in the field where easiness of disposal such as incineration after use is required from the viewpoint of environmental problems, carbon, hydrogen, among the preferred combinations of the fields required so far, A liquid crystal polyester comprising a combination consisting of only oxygen elements is particularly preferably used.

The component (B) used in the layer comprising the liquid crystal polyester resin composition in the present invention is a copolymer having a functional group having reactivity with the liquid crystal polyester. The functional group having reactivity with the liquid crystal polyester may be anything as long as it has reactivity with the liquid crystal polyester, and specific examples include an oxazolyl group, an epoxy group, and an amino group. Preferably, it is an epoxy group.
Epoxy groups and the like may exist as part of other functional groups, and examples of such groups include glycidyl groups.

  In the copolymer (B), the method for introducing such a functional group into the copolymer is not particularly limited, and can be performed by a known method. For example, at the copolymer synthesis stage, it is possible to introduce a monomer having the functional group by copolymerization, or to graft copolymerize the monomer having the functional group to the copolymer. It is.

  Unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether are preferably used as the monomer having a functional group reactive with the liquid crystal polyester, particularly the monomer containing a glycidyl group.

（Ｒは、エチレン系不飽和結合を有する炭素数２〜１３の炭化水素基である。）
で表される化合物であり、また不飽和グリシジルエーテルは、好ましくは一般式

（Ｒは、エチレン系不飽和結合を有する炭素数２〜１８の炭化水素基であり、Ｘは、−ＣＨ₂−Ｏ−または

である。）
で表される化合物である。 The unsaturated carboxylic acid glycidyl ester is preferably of the general formula

(R is a C2-C13 hydrocarbon group having an ethylenically unsaturated bond.)
The unsaturated glycidyl ether is preferably a compound represented by the general formula

(R is a hydrocarbon group having 2 to 18 carbon atoms which has an ethylenically unsaturated bond, X is -CH ₂ -O- or

It is. )
It is a compound represented by these.

Specifically, examples of the unsaturated carboxylic acid glycidyl ester include glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, and p-styrene carboxylic acid glycidyl ester.
Examples of the unsaturated glycidyl ether include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, methacryl glycidyl ether, and styrene-p-glycidyl ether.

  The copolymer (B) having a functional group having reactivity with the liquid crystal polyester is preferably a copolymer containing 0.1 to 30% by weight of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. A polymer, more preferably a copolymer containing 1.0 to 25% by weight.

  Further, the copolymer (B) having a functional group having reactivity with the liquid crystal polyester may be a thermoplastic resin or rubber, or a mixture of a thermoplastic resin and rubber. . Rubber is more preferred because of its excellent thermal stability and flexibility.

More preferably, the copolymer (B) having a functional group reactive with the liquid crystal polyester is preferably a copolymer having a crystal heat of fusion of less than 3 J / g.
Further, the copolymer (B) preferably has a Mooney viscosity of 3 to 70, more preferably 3 to 30, and particularly preferably 4 to 25.
The Mooney viscosity here refers to a value measured using a 100 ° C. large rotor according to JIS K6300.

  The term “rubber” as used herein corresponds to a polymer material having rubber elasticity at room temperature according to the new edition of the Dictionary of Polymers (edited by the Society of Polymer Science, published in 1988, Asakura Shoten). Specific examples thereof include natural rubber. , Butadiene polymer, butadiene-styrene copolymer (including random copolymer, block copolymer (including SEBS rubber or SBS rubber), graft copolymer, etc.) or its hydrogenated product, isoprene polymer , Chlorobutadiene polymer, butadiene-acrylonitrile copolymer, isobutylene polymer, isobutylene-butadiene copolymer rubber, isobutylene-isoprene copolymer, acrylate-ethylene copolymer rubber, ethylene-propylene copolymer rubber , Ethylene-butene copolymer rubber, ethylene-propylene-styrene copolymer Rubber, styrene-isoprene copolymer rubber, styrene-butylene copolymer, styrene-ethylene-propylene copolymer rubber, perfluoro rubber, fluorine rubber, chloroprene rubber, butyl rubber, silicone rubber, ethylene-propylene-nonconjugated diene copolymer Examples thereof include polymer rubber, thiol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (for example, polypropylene oxide), epichlorohydrin rubber, polyester elastomer, polyamide elastomer, and the like. Among them, an acrylate-ethylene copolymer is preferably used, and a (meth) acrylate-ethylene copolymer rubber is more preferable.

  These rubber-like substances may be produced by any production method (for example, emulsion polymerization method, solution polymerization method, etc.) and any catalyst (for example, peroxide, trialkylaluminum, lithium halide, nickel-based catalyst, etc.). .

In the present invention, the rubber as the copolymer (B) is a rubber having a functional group reactive with the liquid crystal polyester in the rubber as described above.
In such a rubber, a method for introducing a functional group having reactivity with liquid crystal polyester into the rubber is not particularly limited, and can be performed by a known method. For example, at the rubber synthesis stage, the monomer having the functional group can be introduced by copolymerization, or the monomer having the functional group can be graft-copolymerized on the rubber.

  As a specific example of the copolymer (B) having a functional group having reactivity with the liquid crystal polyester, as the rubber having an epoxy group, (meth) acrylate-ethylene- (unsaturated carboxylic acid glycidyl ester and / or Saturated glycidyl ether) copolymer rubber.

  Here, the (meth) acrylic acid ester is an ester obtained from acrylic acid or methacrylic acid and an alcohol. As the alcohol, an alcohol having 1 to 8 carbon atoms is preferable. Specific examples of (meth) acrylic acid esters include methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate and the like. be able to. In addition, as (meth) acrylic acid ester, the 1 type may be used independently or 2 or more types may be used together.

  Preferably, (meth) acrylic acid ester units are 40-96.9% by weight, more preferably 45-70% by weight, ethylene units are 3-50% by weight, more preferably 10-49% by weight, unsaturated carboxylic acid The glycidyl ether unit and / or unsaturated glycidyl ether unit is 0.1 to 30% by weight, more preferably 0.5 to 20% by weight.

When the (meth) acrylic acid ester unit of such copolymer rubber is 40% by weight or more, the rubber elasticity is increased and the effect of improving the impact resistance of the composition is increased. Further, it is preferable that the (meth) acrylic acid ester unit is 96.9% by weight or less because the brittle point of the copolymer rubber is lowered and the mechanical properties at low temperature of the composition are improved.
Further, when the unsaturated carboxylic acid glycidyl ester unit and / or unsaturated glycidyl ether unit is 0.1% by weight or more, the impact resistance of the composition is improved, and when it is 30% by weight or less, the rigidity of the composition is increased. It is preferable because it goes up.

The copolymer rubber can be produced by a usual method, for example, bulk polymerization using a free radical initiator, emulsion polymerization, solution polymerization or the like. Representative polymerization methods include those described in JP-B-46-45085, JP-B-61-127709, and the like, in the presence of a polymerization initiator that generates free radicals, a pressure of 500 kg / cm ² or more, It can be manufactured under conditions of a temperature of 40 to 300 ° C.

  Other rubbers that can be used in the copolymer (B) of the present invention include acrylic rubbers having functional groups reactive with liquid crystalline polyesters, and vinyl aromatic hydrocarbon compounds having functional groups reactive with liquid crystalline polyesters. -A conjugated diene compound block copolymer rubber can also be illustrated.

（式中、Ｒ¹は、炭素原子数１〜１８のアルキル基またはシアノアルキル基を示す。）、
一般式（２）

（式中、Ｒ²は、炭素原子数１〜１２のアルキレン基、Ｒ³は炭素原子数１〜１２のアルキル基を示す。）および
一般式（３）

（式中、Ｒ⁴は、水素原子またはメチル基、Ｒ⁵は、炭素原子数３〜３０のアルキレン基、Ｒ⁶は、炭素原子数１〜２０のアルキル基またはその誘導体、ｎは１〜２０の整数を示す。）で表される化合物から選ばれる少なくとも１種の単量体を主成分とするものである。 The acrylic rubber here is preferably a general formula (1)

(Wherein R ¹ represents an alkyl group having 1 to 18 carbon atoms or a cyanoalkyl group),
General formula (2)

(Wherein R ² represents an alkylene group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 12 carbon atoms) and the general formula (3)

Wherein R ⁴ is a hydrogen atom or a methyl group, R ⁵ is an alkylene group having 3 to 30 carbon atoms, R ⁶ is an alkyl group having 1 to 20 carbon atoms or a derivative thereof, and n is 1 to 20 The main component is at least one monomer selected from the compounds represented by:

  Specific examples of the alkyl acrylate ester represented by the general formula (1) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, actyl acrylate, 2-ethylhexyl acrylate, and nonyl acrylate. Decyl acrylate, dodecyl acrylate, cyanoethyl acrylate and the like.

  Examples of the acrylic acid alkoxyalkyl ester represented by the general formula (2) include methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, and ethoxypropyl acrylate. One or more of these can be used as the main component of the acrylic rubber.

As an acrylic rubber constituent, an unsaturated monomer copolymerizable with at least one monomer selected from the compounds represented by the general formulas (1) to (3) is used as necessary. Can do.
Examples of such unsaturated monomers include styrene, α-methylstyrene, acrylonitrile, halogenated styrene, methacrylonitrile, acrylamide, methacrylamide, vinylnaphthalene, N-methylolacrylamide, vinyl acetate, vinyl chloride, chloride. Examples include vinylidene, benzyl acrylate, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.

A preferred component ratio of the acrylic rubber having a functional group having reactivity with the liquid crystal polyester is at least one monomer selected from the compounds represented by the general formulas (1) to (3) 40.0 to 99. .9% by weight, unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether 0.1-30.0% by weight, at least one selected from the compounds represented by the above general formulas (1) to (3) 0 to 30.0% by weight of an unsaturated monomer copolymerizable with the monomer.
The unsaturated monomer is an optional component and may not be included.
It is preferable that the component ratio of the acrylic rubber is within the above range because the composition has good heat resistance, impact resistance and molding processability.

  The method for producing the acrylic rubber is not particularly limited, and is described, for example, in JP 59-1113010, JP 62-64809, JP 3-160008, or WO 95/04764. Such a known polymerization method can be used, and it can be produced by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization in the presence of a radical initiator.

  The vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber having a functional group reactive with the liquid crystalline polyester is preferably (i) a sequence mainly composed of a vinyl aromatic hydrocarbon compound; and (ii) Examples thereof include a rubber obtained by epoxidizing a block copolymer having a sequence mainly composed of a conjugated diene compound, or a rubber obtained by epoxidizing a hydrogenated product of the block copolymer.

  A vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer or a hydrogenated product thereof can be produced by a known method. For example, this method is disclosed in Japanese Patent Publication No. 40-23798 and Japanese Patent Laid-Open No. 59-133203. It is described in the gazette.

Examples of the vinyl aromatic hydrocarbon compound include styrene, vinyl toluene, divinyl benzene, α-methyl styrene, p-methyl styrene, vinyl naphthalene, and among them, styrene is preferable.
Examples of the conjugated diene compound include butadiene, isoprene, pyrylene, 1,3-pentadiene, 3-butyl-1,3-octadiene, and butadiene or isoprene is preferable.

  The rubber used as the copolymer (B) is preferably a (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber.

The rubber used as the copolymer (B) can be vulcanized as necessary and used as a vulcanized rubber.
Vulcanization of the above (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is a polyfunctional organic acid, polyfunctional amine compound, imidazole compound, etc. However, the present invention is not limited to these.

Moreover, as a specific example of the copolymer (B) having a functional group having reactivity with the liquid crystal polyester, the thermoplastic resin having an epoxy group includes (a) 50 to 99% by weight of ethylene units, and (b) unsaturated. The carboxylic acid glycidyl ester unit and / or the unsaturated glycidyl ether unit is 0.1 to 30% by weight, preferably 0.5 to 20% by weight, and (c) the ethylenically unsaturated ester compound unit is 0 to 50% by weight. An epoxy group-containing ethylene copolymer can be mentioned.
(C) The ethylenically unsaturated ester compound unit is an optional component and may not be contained.

  Examples of the ethylenically unsaturated ester compound (c) include vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and other carboxylic acid vinyl esters, α , Β-unsaturated carboxylic acid alkyl ester and the like. In particular, vinyl acetate, methyl acrylate, and ethyl acrylate are preferable.

  Specific examples of the epoxy group-containing ethylene copolymer include, for example, a copolymer composed of ethylene units and glycidyl methacrylate units, a copolymer composed of ethylene units, glycidyl methacrylate units and methyl acrylate units, ethylene units and glycidyl methacrylate units. And a copolymer composed of ethyl acrylate units, a copolymer composed of ethylene units, glycidyl methacrylate units and vinyl acetate units.

  The melt index (hereinafter sometimes referred to as MFR. JIS K6760, 190 ° C., 2.16 kg load) of the epoxy group-containing ethylene copolymer is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 50 g. / 10 minutes. The melt index may be outside this range, but if the melt index exceeds 100 g / 10 minutes, it is not preferable in terms of mechanical properties when it is made into a composition, and if it is less than 0.5 g / 10 minutes, the component (A) The compatibility with the liquid crystal polyester is inferior.

Further, the epoxy group-containing ethylene copolymer is preferably in the range stiffness modulus of 10~1300kg / cm ^2, further preferably from 20~1100kg / cm ^2.
If the bending rigidity is outside this range, the molding processability and mechanical properties of the composition may be insufficient, which is not preferable.

  The epoxy group-containing ethylene copolymer is usually an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a high pressure radical polymerization method for copolymerization. It can also be made by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt graft copolymerized in an extruder.

The liquid crystal polyester resin composition in the present invention is a resin composition containing the above liquid crystal polyester, and comprises a copolymer having a functional group having (A) a liquid crystal polyester as a continuous phase and (B) a reactivity with the liquid crystal polyester. It is a resin composition used as a dispersed phase.
When the liquid crystal polyester is not a continuous phase, the electrical properties, heat resistance, etc. of the molded article formed by coating the liquid crystal polyester resin composition are remarkably lowered, which is not preferable.

  In the resin composition of such a copolymer having a functional group and a liquid crystal polyester, although the details of the mechanism are unknown, a reaction occurs between the component (A) and the component (B) of the composition. However, it is considered that the component (A) forms a continuous phase and the component (B) is finely dispersed, which improves the moldability of the composition.

One embodiment of the liquid crystal polyester resin composition in the present invention is (A) liquid crystal polyester 56.0-99.9% by weight, preferably 65.0-99.9% by weight, more preferably 70-98% by weight, And (B) a copolymer having a functional group having reactivity with the liquid crystalline polyester 44.0 to 0.1% by weight, preferably 35.0 to 0.1% by weight, more preferably 30 to 2% by weight It is a resin composition.
When the component (A) is 56.0% by weight or more, the flame retardancy of the molded article coated with the composition is further improved, and the dielectric constant and dielectric loss are reduced, which is preferable. Further, when the component (A) is 99.9% by weight or less, the orientation of the coating material becomes smaller, and it is difficult to cause breakage when the clothing body is bent, and flexibility is maintained, which is preferable.

As a method for producing the liquid crystal polyester resin composition in the present invention, a known method can be used. For example, a method of mixing each component in a solution state and evaporating the solvent or precipitating in the solvent can be mentioned. From an industrial point of view, a method of kneading each component in a molten state is preferable. For the melt-kneading, generally used kneading apparatuses such as a single-screw or twin-screw extruder and various kneaders can be used. A biaxial high kneader is particularly preferable.
In the melt-kneading, the cylinder setting temperature of the kneading apparatus is preferably in the range of 200 to 360 ° C, more preferably 230 to 350 ° C.

  At the time of kneading, each component may be mixed uniformly in advance with a device such as a tumbler or a Henschel mixer, or if necessary, a method of omitting the mixing and separately supplying each of the components separately to the kneading device is also used. be able to.

  In the liquid crystal polyester resin composition used in the present invention, an inorganic filler is used as desired. Such inorganic fillers include calcium carbonate, talc, clay, silica, magnesium carbonate, barium sulfate, titanium oxide, alumina, gypsum, glass flakes, glass fibers, carbon fibers, alumina fibers, silica alumina fibers, aluminum borate. Examples include whiskers and potassium titanate fibers.

  If necessary, the liquid crystalline polyester resin composition used in the present invention may further include an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a flame retardant, a lubricant, an antistatic agent, an inorganic or organic colorant. Add various additives such as rust preventives, crosslinking agents, foaming agents, fluorescent agents, surface smoothing agents, surface gloss improvers, mold release improvers such as fluororesins during the manufacturing process or in subsequent processing steps. Can do.

The molded body of the present invention is obtained by coating a substrate with a liquid crystal polyester resin composition having (A) a liquid crystal polyester as a continuous phase and (B) a copolymer having a functional group having reactivity with the liquid crystal polyester as a dispersed phase. It will be. The molded product of the present invention has a liquid crystal polyester resin composition in which (A) a liquid crystal polyester is a continuous phase and (B) a copolymer having a functional group reactive with the liquid crystal polyester is a dispersed phase around the substrate. It has the coating layer which consists of a thing.
The manufacturing method of the multilayer molded body of the present invention is not particularly limited, and can be performed by a known method. For example, the resin is melted from a tubing type extruder, extruded into an annular die having a circular flow path, and the base material is simultaneously coated from the center of the annular die, and the resin is dissolved in a solvent capable of dissolving the resin. , A method of removing the solvent after immersing the substrate in the solution, and a method of coating the resin by powdering and then spraying the substrate and melting it by heating, etc., but extrusion molding is preferably used .

The resin composition in the present invention is a so-called self-extinguishing resin that does not spread even if a flame retardant is not added, but a halogen-based flame retardant or phosphorus-based flame retardant that is a commonly used flame retardant. Can be used.
Examples of the substrate in the present invention include a light or electric conductor. When the base material is an electrical conductor, the conductor is not particularly limited as long as it is a material to be energized, but from the viewpoint of energization performance, a single metal such as iron, aluminum, gold, silver, copper, or these metals An alloy containing 50% by weight or more is preferably used.

  When the substrate is a light conductor, the conductor preferably has a multilayer structure of two transparent materials having different refractive indexes. Examples of the material of the conductor include glass made of silicon dioxide, silica, etc., or plastic made of acrylic resin, fluorine resin, etc., a combination of two kinds of glass, a combination of two kinds of plastic, or a combination of glass and plastic. Is preferred. These are preferably used as optical fibers.

  With respect to the molded body of the present invention, the conductor can be subjected to a surface treatment for the purpose of improving the adhesion between the base material and the covering material. Specifically, techniques such as primer treatment, surface grinding, ultraviolet irradiation treatment, corona discharge treatment, and plasma treatment are preferably used.

The thickness of the coating resin can be arbitrarily adjusted in the range of 0.01 to 10 mm as long as the characteristics of the coating material can be maintained. The coating is preferably performed in the range of 0.03 to 5 mm, more preferably 0.1 to 2 mm. If the thickness is less than 0.01 mm, the insulation becomes insufficient, which is not preferable. Moreover, when it exceeds 10 mm, the softness | flexibility of a coating material will be impaired and it is not preferable.
The molded body of the present invention is preferably used as an electric wire or cable.

  The electric wire or cable obtained by the present invention is excellent in chemical resistance, tensile elongation, flame retardancy, and excellent dielectric properties in the high frequency range, and therefore suitable for various electric wires or cables such as high-frequency coaxial cables, optical fiber cables, and instrumentation cables. Used for.

  While the embodiments of the present invention have been described above, the embodiments of the present invention disclosed above are merely examples, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is defined by the terms of the claims, and further includes meanings equivalent to the description of the claims and all modifications within the scope.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, these are only illustrations and this invention is not limited to these.

(1) Dielectric constant measurement Using an injection molding machine set to a cylinder temperature of 290 ° C., a test plate having a thickness of 2 mm was prepared from the resin pellets, and 23 ° C. and 50% using HP 4291A RF impedance / material analyzer manufactured by Hewlett Packard. The dielectric constant and dielectric loss tangent at 1 GHz were measured under RH conditions.
(2) Combustion test The flammability was measured according to the UL-94 VTM standard. For the test piece, a raw material was press-molded to obtain a sheet having a thickness of 0.1 mm, and then a strip having a length of 200 mm and a width of 50 mm was cut out and used.
(3) Flexibility (bending test)
A coated portion of the coated copper wire was cut out to a length of 200 mm, and further cut in the take-off direction to open a strip-shaped test piece made of only the coating material. The obtained test piece was subjected to MIT bending tester MIT-D type manufactured by Toyo Seiki Co., Ltd., in accordance with JIS P-8115, load 1 kgf, bending surface radius of curvature 2 mm, bending speed 135 times / The bending test was performed in minutes, and the number of times that the test piece was broken was measured.
Reference Example 1 (1) Liquid Crystalline Polyester of Component (A) 16.6 kg (120 mol) of p-hydroxybenzoic acid, 8.4 kg (45 mol) of 6-hydroxy-2-naphthoic acid and 18.6 kg (182 mol) of acetic anhydride ) Was added to a polymerization tank equipped with a comb-shaped stirring blade, heated while stirring in a nitrogen gas atmosphere, and polymerized at 320 ° C. for 1 hour and further under a reduced pressure of 2.0 torr at 320 ° C. for 1 hour. During this time, acetic acid produced as a by-product continued to be distilled out of the system. Thereafter, the system was gradually cooled, and the polymer obtained at 180 ° C. was taken out of the system.
The obtained polymer was pulverized with a hammer mill manufactured by Hosokawa Micron Co., Ltd. to obtain particles of 2.5 mm or less. This was further treated in a rotary kiln under a nitrogen gas atmosphere at 240 ° C. for 5 hours to obtain a wholly aromatic polyester composed of the following repeating units in the form of particles having a flow start temperature of 270 ° C.
Hereinafter, the liquid crystal polyester is abbreviated as A-1. This polymer exhibited optical anisotropy at 280 ° C. or higher under pressure.
The ratio of the repeating structural unit of the liquid crystal polyester A-1 is as follows.

なお、ここでいう流動開始温度は、毛細管レオメーター（（株）島津製作所製フローテスターＣＦＴ−５００）を用い、４℃／分の昇温速度で加熱溶融された樹脂を１００ｋｇ／ｃｍ² の加重下で、内径１ｍｍ、長さ１０ｍｍのノズルから押し出したときに、該溶融粘度が４８，０００ポイズを示す温度である。

In addition, the flow start temperature here uses a capillary rheometer (Flow Tester CFT-500 manufactured by Shimadzu Corporation), and a resin heated and melted at a heating rate of 4 ° C./min is applied with a load of 100 kg / cm ² . Below, when extruded from a nozzle having an inner diameter of 1 mm and a length of 10 mm, the melt viscosity is a temperature showing 48,000 poise.

(2) Component (B-1)
According to the method described in Example 5 of JP-A-61-127709, methyl acrylate / ethylene / glycidyl methacrylate = 59.0 / 38.7 / 2.3 (weight ratio), Mooney viscosity = 15 Got rubber. Hereinafter, the rubber may be abbreviated as B-1.
Here, the Mooney viscosity is a value measured using a large rotor at 100 ° C. according to JIS K6300. The heat of fusion was 10 ° C / min. Per 10 mg sample using a Shimadzu DSC-50 having a sensitivity of 0.01 J / g. Measured with The melting point could not be detected and the heat of fusion could not be measured.

(3) Component (B-2)
Bond First 7L manufactured by Sumitomo Chemical Co., Ltd. was used. The copolymer composition is methyl acrylate / ethylene / glycidyl methacrylate = 30/67/3 (weight ratio). Hereinafter, the copolymer may be abbreviated as B-2.

Reference example 2
Using a TEX-30 twin screw extruder manufactured by Nippon Steel Co., Ltd. at a blending ratio of 93% by weight of A-1 and 7% by weight of B-1, at a cylinder set temperature of 290 ° C. and a screw rotation speed of 220 rpm Melt kneading was performed to obtain composition pellets having A-1 as a continuous phase and B-1 as a dispersed phase. This pellet is abbreviated as P-1.

Reference example 3
Composition pellets were obtained in the same manner as in Reference Example 2 except that A-1 was changed to 97 wt% and B-2 was changed to 3 wt%. A-1 was a continuous phase and B-2 was a dispersed phase. The pellet is abbreviated as P-2.

Reference example 4
Composition pellets were obtained in the same manner as in Reference Example 2 except that A-1 was changed to 50% by weight and B-2 was changed to 50% by weight. Part of the composition obtained had B-2 as a continuous layer. This pellet is abbreviated as P-3.

Example 1 In order to make the shape of a conductor-coated resin-coated electric wire, a coated molded body was prototyped using a tubular extrusion molding machine. From the center of the die to a conductor (cross-sectional area: 1.0 mm ^{2, obtained} by twisting and compressing 5 annealed copper wires having a strand diameter of 0.50 mm), P-1 as a covering material, and a thickness of 0.1 mm. An object coating was applied. The die nipples used at that time were 1.50 mmφ and 1.25 mmφ, and the extrusion temperature was as follows: the cylinder was 290 ° C., the die was 280 ° C., and the linear speed was 30 m / min.

Example 2
A coated copper wire was obtained in the same manner as in Example 1 except that the liquid crystal polyester P-1 was changed to the liquid crystal polyester resin composition P-2.

Comparative Example 1
A coated copper wire was obtained in the same manner as in Example 1 except that A-1 was used instead of P-1.

Comparative Example 2
A coated copper wire was obtained in the same manner as in Example 1 except that the liquid crystal polyester P-1 was changed to the liquid crystal polyester resin composition P-3.

The molded article of the present invention is excellent in flame retardancy, has low dielectric constant and dielectric loss, and excellent in flexibility. Therefore, it is used as an electric conductor for an electric wire, an electric cable, etc., and as an optical conductor for an optical fiber, an optical cable, etc. Can be. In addition, since the dielectric constant and the dielectric loss are particularly small, when used for a high frequency cable of gigahertz band or higher, it exhibits excellent transmission characteristics and high reliability can be obtained.

Claims (15)

(A) A liquid crystal polyester resin composition comprising a liquid crystal polyester as a continuous phase and (B) a liquid crystal polyester resin composition having a functional group having reactivity with the liquid crystal polyester as a dispersed phase is coated on a base material which is an electrical conductor. A method for producing a molded body, wherein a liquid crystal polyester resin composition is extruded from a tubing type extruder into an annular die having a circular channel in a molten state, and is an electrical conductor introduced from the center of the annular die. The manufacturing method of the molded object characterized by coat | covering a base material. The process for producing a molded article of claim 1 the substrate is a conductor of electricity, characterized in that a metal. The base material, which is an electrical conductor, is made of a simple substance of iron, aluminum, gold, silver, or copper, or is a metal conductive wire made of a metal alloy containing at least 50% by weight of one of these simple metals. method for producing a molded article according to claim 1 or 2. (A) A liquid crystal polyester resin composition comprising a liquid crystal polyester as a continuous phase and (B) a liquid crystal polyester resin composition having a functional group having reactivity with the liquid crystal polyester as a dispersed phase is coated on a base material that is a light conductor. A method for producing a molded body, wherein a liquid crystal polyester resin composition is extruded from a tubing type extruder into an annular die having a circular flow path in a molten state, and is a light conductor introduced from the center of the annular die. The manufacturing method of the molded object characterized by coat | covering a base material. 5. The method for producing a molded body according to claim 4 , wherein the base material which is a light conductor is a light conducting wire made of glass or plastic. The liquid crystal polyester resin composition comprises (A) 56.0 to 99.9% by weight of liquid crystal polyester, and (B) 44.0 to 0.1% by weight of a copolymer having a functional group reactive with the liquid crystal polyester. It is a composition to contain, The manufacturing method of the molded object in any one of Claims 1-5 characterized by the above-mentioned. The method for producing a molded article according to any one of claims 1 to 6, wherein the functional group having reactivity with the liquid crystal polyester is an oxazolyl group, an epoxy group or an amino group. The method for producing a molded article according to any one of claims 1 to 7 , wherein the functional group having reactivity with the liquid crystal polyester is an epoxy group. The copolymer (B) having a functional group reactive with the liquid crystal polyester is a copolymer containing 0.1 to 30% by weight of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units. The manufacturing method of the molded object in any one of Claims 1-8 characterized by these. The copolymer (B) having a functional group having reactivity with the liquid crystal polyester has a (meth) acrylic acid ester unit of 40 to 96.9% by weight, an ethylene unit of 3 to 50% by weight, and an unsaturated carboxylic acid glycidyl ester. The method for producing a molded body according to any one of claims 1 to 9 , wherein the rubber is composed of 0.1 to 30% by weight of units and / or unsaturated glycidyl ether units. The copolymer (B) having a functional group having reactivity with the liquid crystal polyester has (a) 50 to 99% by weight of ethylene units, (b) unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units. 0.1 to 30 wt%, according to any one of claims 1 to 10, characterized in that an epoxy group-containing ethylene copolymer consisting of 0-50% by weight (c) ethylenically unsaturated ester compound unit A method for producing a molded article. The method for producing a molded article according to any one of claims 1 to 11 , wherein the liquid crystal polyester (A) contains at least 30 mol% of the following repeating structural units.

The liquid crystal polyester (A) is obtained by reacting an aromatic dicarboxylic acid, an aromatic diol, and an aromatic hydroxycarboxylic acid. The molded article according to any one of claims 1 to 12 , Production method. The method for producing a molded article according to any one of claims 1 to 13 , wherein the liquid crystal polyester (A) is obtained by reacting a combination of different kinds of aromatic hydroxycarboxylic acids. The method for producing a molded body according to any one of claims 1 to 14 , wherein the molded body is an electric wire or a cable.