JP2002275363A - Resin composition and wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in tensile elongation and flexibility and a wire having a covering layer for a conductor obtained using the resin composition. SOLUTION: The resin composition comprises 100 pts.wt. of a thermoplastic polyester resin (A) comprising one or a mixture of at least two, selected among (1) a PBT resin, (2) a thermoplastic copolyester resin obtained from terephthalic acid and a dimer acid as main acid components and 1,4-butanediol as a glycol component and containing 0.5-30 mole% of the dimer acid component and (3) a thermoplastic polyester elastomer resin comprising a PBT as a hard segment and a polyether or a polyester as a soft segment and, incorporated therewith, 0.01-2 pts.wt. of a metal-inactivating agent (B) for preventing undesirable effects by copper and 0.01-4 pts.wt. of a heat-resistant agent (C). The wire has a covering layer for a conductor obtained using the resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin composition having excellent heat deterioration resistance and an electric wire using the resin composition for a conductor coating layer.

[0002]

2. Description of the Related Art Polyolefins such as vinyl chloride resins and polyethylene resins are used as coating materials for electric wires and the like, utilizing their excellent properties such as tensile elongation and flexibility. However, regarding vinyl chloride resin, starting from environmental problems in recent years, conversion to other materials has been studied because of the suspicion of emitting a toxic substance similar to dioxin during combustion, and polyolefins such as polyethylene resin are heat-resistant and resistant. It has become impossible to achieve the increasing required performance in terms of abrasion.

[0003] In recent years, polyester-based materials have attracted attention as a coating material having high heat resistance, high abrasion resistance, and light weight. However, when a wire using an existing polyester-based material for the conductor coating layer is exposed to a high temperature for a long time, the elongation is reduced and the flexibility is lost, and in the worst case, the conductor coating layer is cracked. It became clear.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to have excellent tensile elongation and flexibility even when exposed to a high temperature for a long period of time. An object of the present invention is to provide a resin composition and an electric wire using the resin composition for a conductor coating layer.

[0005]

The object of the present invention is to provide (A):
Terephthalic acid and an ester-forming derivative thereof as an acid component, and a PBT resin obtained by using 1,4-butanediol as a glycol component, terephthalic acid and a dimer acid or an acid component mainly containing each ester-forming derivative,
A thermoplastic polyester resin obtained by using 1,4-butanediol as a glycol component, wherein the thermoplastic copolymer polyester contains 0.5 to 30 mol% of the dimer acid component in the acid component of the thermoplastic copolymer polyester resin. (B) With respect to 100 parts by weight of a thermoplastic polyester resin composed of one or two or more of a thermoplastic polyester elastomer resin composed of polyether or polyester with a resin or PBT as a hard segment and a soft segment composed of PBT as a soft segment. A resin composition comprising 0.01 to 2 parts by weight of a metal inactivator for preventing copper damage and 0.01 to 4 parts by weight of a heat-resistant agent (C) was used for the conductor coating layer. Achieved by electric wires.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The PBT resin used in the present invention mainly comprises terephthalic acid as an acid component and 1,4-butanediol as a glycol component.

The thermoplastic copolyester resin used in the present invention is mainly composed of terephthalic acid,
It comprises dimer acid and 1,4-butanediol as a glycol component.

It is important that the dimer acid composition in the acid component is 0.5 to 30 mol%, preferably 1 to 20 mol%, particularly preferably 3 to 15 mol%.

[0009] When the dimer acid composition exceeds 30 mol%, the tensile strength is significantly reduced. On the other hand, when the dimer acid content in the acid component is less than 0.5 mol%, terephthalic acid and 1,4
-Butanediol is equivalent in physical properties to PBT resin.

The raw material of dimer acid which is one of the acid components of the thermoplastic polyester resin used in the present invention is as follows:
C18 unsaturated fatty acids or lower alkyl esters thereof, for example, oleic acid, linoleic acid, linolenic acid, elaidic acid and the like. These are polymerized with a clay catalyst such as montmorillonite to obtain a mixture of a dimer acid having 36 carbon atoms, a trimer acid having 54 carbon atoms, and a monomer acid having 18 carbon atoms. This mixture is subjected to vacuum distillation, molecular distillation and hydrogenation to obtain the dimer acid used in the present invention.

The dimer acid obtained has a chain form, an aromatic ring,
It is a mixture having each structure of an alicyclic monocyclic ring and an alicyclic polycyclic ring. When the content of linoleic acid, which is a raw material of dimer acid, is large, the chain structure decreases and the cyclic structure increases.

Preferable specific examples of the dimer acid, which is one of the acid components of the thermoplastic copolyester resin used in the present invention, include PRIPOL 100 manufactured by Unichema.
8, PRIPOL 1009, and even PRIPOL 1
008 as an ester-forming derivative of Uniquema
RIPLAST 3008, PRIPLAST 189 as an ester-forming derivative of PRIPOL 1009
9 is given.

Other acid components of the thermoplastic polyester resin used in the present invention include, for example, isophthalic acid and 2,6-naphthalenedicarboxylic acid.

It is important that the glycol component of the thermoplastic polyester resin used in the present invention is 1,4-butanediol.

[0015] The thermoplastic polyester elastomer resin used in the present invention is polybutylene terephthalate (P).
A polyether ester elastomer resin having a BT) unit as a hard segment and a polyether such as polytetramethylene glycol (PTMG) as a soft segment (JP-B-49-48195, 49-31558);
BT unit is hard segment, polycaprolactone (P
CL) and other polyester units having a soft segment as a soft segment (Japanese Patent Publication No. 48-78)
No. 4116, JP-A-59-12926) and the like can be used.

The method for producing each of the PBT resin, the thermoplastic copolymer polyester resin, and the thermoplastic polyester elastomer resin in the present invention is not particularly limited, and can be carried out according to a known method.

For example, in a PBT resin, terephthalic acid and 1,4-butanediol are directly or simultaneously esterified or transesterified, and then subjected to transesterification.
A polymerization method can be adopted. At the time of these polymerization or transesterification reactions, various known catalysts, stabilizers, modifiers or additives may be used.

In the thermoplastic copolyester resin,
A method in which terephthalic acid, dimer acid, and 1,4-butanediol are directly or simultaneously esterified or transesterified, and then polymerized. During these polymerization or transesterification reactions,
Known various catalysts, stabilizers, modifiers or additives may be used.

The thermoplastic polyester elastomer resin (polyether ester type) includes terephthalic acid, 1,4
-A method of directly or simultaneously esterifying butanediol and polytetramethylene glycol or carrying out transesterification followed by polymerization can be employed. At the time of these polymerization or transesterification reactions, various known catalysts, stabilizers, modifiers or additives may be used. Further, in the case of a thermoplastic polyester elastomer resin (polyester ester type), it can be obtained by a method in which a PBT resin is melted and kneaded with ε-caprolactone. At the time of the melt kneading, various known catalysts, stabilizers, modifiers or additives may be used. Further, as the thermoplastic polyester elastomer resin, commercially available materials such as Hytrel (Toray Dupont) and Perprene (Toyobo) can be used without any problem.

The metal deactivator for preventing copper damage used in the present invention has a structure capable of forming a complex compound with copper and tin and has both high temperature processing stability during resin modification and molding. It is important. Specifically, for example, 3- (N-
Salicyloyl) amino-1,2,4-triazole, decamethylenedicarboxylic acid disalicyloyl hydrazide,
N, N'-bis [3- (3,5-di-t-butyl-4-
[Hydroxyphenyl) propionyl] hydrazine.

Among the so-called heavy metal deactivators, alkyl acid phosphate compounds used for the purpose of deactivating a catalyst used in a transesterification reaction or a polycondensation reaction. With distearyl acid phosphate, the purpose cannot be achieved.

In the present invention, the compounding amount of the metal deactivator for preventing copper damage is (A) a PBT resin obtained by using terephthalic acid and its ester-forming derivative as an acid component and 1,4-butanediol as a glycol component. A thermoplastic copolymer polyester resin obtained by using terephthalic acid and dimer acid or an ester-forming derivative thereof as an acid component, and 1,4-butanediol as a glycol component. One of a thermoplastic copolymer polyester resin containing 0.5 to 30 mol% of the dimer acid component in the acid component, and a thermoplastic polyester elastomer resin made of polyether or polyester with PBT as a hard segment and a soft segment. Or a thermoplastic polyester resin 10 comprising a mixture of two or more For the parts by weight, 0.01
It is important that the amount is from 2 to 2 parts by weight, and particularly preferably from 0.1 to 1 part by weight. When the amount is less than 0.01 part by weight, the effect of maintaining tensile elongation and flexibility is not exhibited. When the amount is more than 2 parts by weight, further improvement of the effect is not recognized. The coloring of a plurality of electric wires by the coloring of yellow by the agent causes inconvenience.

The composition of the present invention may further contain a heat-resistant agent (for example, hindered phenol, hindered amine, benzotriazole, hydroquinone, thioether,
(Including phosphites and their substituted products and combinations thereof). Specifically, 3,9-bis [2- [3- (t-butyl-4-hydroxy-5-methylphenyl) propoxy] -1,1
-Dimethylethyl] -2,4,8,10-tetraoxaspiro (5.5) undecane, pentaerythritritetrakis (3-laurylthiopropionate), triethyleneglycol-bis [3- (3-t- Butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-
Butyl 4-hydroxyphenyl) propionate], N,
N'-hexamethylenebis (3,5-di-t-butyl-
4-hydroxy-hydroxynamamide), tris (2,4-di-t-butylphenyl) phosphite,
Trisnonylphenyl phosphite, and the like.

In the present invention, the compounding amount of the heat-resistant agent is 0.0
It is important to mix 1 to 4 parts by weight.

When the amount is less than 0.01 part by weight,
Thermal degradation occurs during the compounding process and the coating process when forming an electric wire, and the coating thickness becomes unstable due to, for example, a decrease in viscosity due to a decrease in the molecular weight of the base resin. In addition, the elongation is significantly reduced by the heat treatment.

When the amount is more than 4 parts by weight, no further effect of improving the addition is observed, and when the wire is used, poor appearance may be caused.

The composition of the present invention may contain an ultraviolet absorber (eg, resorcinol, salicylate, benzotriazole, benzophenone, etc.), a lubricant (eg, magnesium stearate, calcium stearate, etc.) as long as the object of the present invention is not impaired. Coloring including release agents (eg, montanic acid and its salts, stearic acid and its salts, stearyl alcohol, stearylamide, silicone resins, etc.), dyes (eg, nitrosine, etc.) and pigments (eg, carbon black, cadmium sulfide, phthalocyanine, etc.) One or more kinds of agents, additives impregnating liquids (for example, silicone oil, etc.) and flame retardants (for example, organic halogens, combinations of organic halogens and flame retardant assistants such as antimony trioxide) can be added.

In the composition of the present invention, (A) a thermoplastic polyester resin, (B) a metal deactivator for preventing copper damage and (C) a heat-resistant agent are sufficiently kneaded and dispersed until a final molded article is obtained. is important. The method for this is not limited, but for example, it can be melt-kneaded using a twin-screw kneading extruder.

The conductor used for the electric wire of the present invention may be a single copper wire or a plurality of twisted or braided wires, and the copper wire is subjected to tin plating by dipping or electrolysis. You may. Further, the cross-sectional shape of the conductor is not limited to a circle, and there is no problem even if a slit is formed from a plate-like copper plate or a rectangular shape obtained by rolling a round wire.

The electric wire of the present invention is an electric wire having the resin composition as a conductor coating layer. Specific examples include power cables such as insulated wires for communication cables, general fixed wires, wires for ships, and wires for vehicles.

As a method for manufacturing an electric wire according to the present invention, a known method can be used. That is, the resin composition can be obtained by extruding the resin composition into a single conductor or a plurality of conductors using a normal extrusion molding line. Alternatively, a method of processing the resin composition into a sheet or a film and then laminating a conductor may be used.

[0032]

The resin composition of the present invention has excellent tensile elongation and flexibility even when exposed to a high temperature for a long period of time, and is useful as an electric wire coating material. An electric wire in which an object is used as a conductor coating layer of an electric wire is useful because the coating layer does not crack or the like even when exposed to a high temperature for a long period of time.

[0033]

Embodiments will be described below with reference to embodiments. The evaluation was performed according to the following method. Tensile elongation: Measurement was performed at a tensile speed of 100 mm / min using a tube-shaped test piece created by extracting and extracting a core wire of an electric wire. Appearance evaluation of coated electric wire: visual observation. Evaluation of the same diameter winding of the covered electric wire:
After the heat treatment for 12 hours, after leaving at room temperature for more than 12 hours,
The presence or absence of cracks on the surface after winding around a core material having the same diameter as the coated electric wire (x in case of cracks).

As the PBT resin used in the present invention, PBT120 manufactured by Kanebo Gosen Co., Ltd. was used.

The thermoplastic copolymer polyester resin used in the present invention was produced as follows. Charge 24.3 kg of 1,4-butanediol, 5 g of tetra-n-butyl titanate and 23.5 kg of dimethyl terephthalate as a transesterification catalyst in a 100 L reactor, and heat to 210 ° C. at a rate of 40 ° C./hour. Then, generated methanol was distilled out of the system, and a transesterification reaction was performed.
After the methanol distillation was almost completed, 5 g of tetra-n-butyl titanate and 8 kg of dimer acid (PRIPOL 1009 manufactured by Unichema) were added as esterification catalysts, and the mixture was heated to a heating rate of 20 ° C. per hour to 230 ° C. per hour. And an esterification reaction. Next, the reaction product was transferred to a polymerization machine, and 5 g of tetra-n-butyl titanate was added as a polymerization catalyst.
The pressure was raised to 7 Pa, and then polycondensation was performed for 3 hours.
The obtained thermoplastic copolymer polyester resin had a relative viscosity of 2.0 and a melting point of 205 ° C. The obtained thermoplastic copolymer polyester resin was called TPE.

As the thermoplastic polyester elastomer resin used in the present invention, Hytrel 6347 manufactured by Toray Dupont Co., Ltd. was used.

The composition ratios of Examples 1 to 8 and Comparative Examples 1 to 5 are shown in Table 1.

The mixture was melt-kneaded at a temperature of 250 ° C. using a twin-screw kneader (TEX-30α manufactured by Nippon Steel Works) with the composition shown in Table 1 to form pellets.

[0039]

[Table 1]

Further, an electric wire coating test was performed using a single-layer extrusion molding line (screw diameter: 30φ, copper core wire: 0.18 mm × 50 strands) for coating the electric wire. Table 2 shows the results of visual appearance evaluation of the obtained electric wires.

With respect to the obtained electric wire, the same diameter winding evaluation results after heat treatment at 150 ° C. for 96 hours and 192 hours are also shown in Table 2.

The obtained wire was heated at 150 ° C. for 96 hours.
The results of the tensile elongation evaluation before and after the heat treatment for a long time are also shown in Table 2.

[0043]

[Table 2]

As described above, a resin composition comprising a thermoplastic polyester resin, a metal inhibitor for preventing copper damage and a heat-resistant agent, and an electric wire using the resin composition for a conductor coating layer are exposed to a high temperature for a long period of time. In this case, it has excellent tensile elongation and flexibility, which is preferable.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C09K 3/00 108 C09K 3/00 108C 108D H01B 3/42 H01B 3/42 E 7/02 7/02 Z (72) Inventor Toshio Honma 4-1 Kanebo-cho, Hofu-shi, Yamaguchi Prefecture F-term (reference) 4K002 CF00X CF00Y CF07W CF07X CF10Y CF17Y EJ067 EL127 EQ026 EU166 EV067 EW067 FD206 FD207 GQ01 5G305 AA12 CB11 CD09 5G309 RA01 RA12

Claims (3)

[Claims] (A): A PBT resin, terephthalic acid and dimer acid or an ester-forming derivative thereof each obtained by using terephthalic acid and its ester-forming derivative as an acid component and 1,4-butanediol as a glycol component. As a main acid component, a thermoplastic copolymer polyester resin obtained by using 1,4-butanediol as a glycol component, wherein the dimer acid component in the acid component of the thermoplastic copolymer polyester resin is 0.5 to 30 mol. % Of thermoplastic polyester resin composed of one or two or more of a thermoplastic polyester elastomer resin composed of polyether or polyester with PBT as a hard segment and a soft segment composed of PBT as a soft segment. For the part, (B)
A resin composition comprising 0.01 to 2 parts by weight of a metal deactivator for preventing copper damage and 0.01 to 4 parts by weight of a heat-resistant agent (C). 2. The metal deactivator for preventing copper damage is N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl] hydrazine, 3- (N-salicyloyl). 2.) A single compound or a mixture of two or more of amino-1,2,4-triazole and decamethylenedicarboxylic acid disalicyloylhydrazide.
3. The resin composition according to item 1. 3. A resin comprising a copper wire, a copper plate or a tin-plated copper wire, wherein the resin composition according to claim 1 is used as a conductor coating layer of an electric wire. Electrical wire.