JPH06107919A - Flame-resistant polyester elastomer composition and its molding - Google Patents

Abstract

PURPOSE:To provide a flame-resistant polyester elastomer composition excellent in heat resistance and the free from the trouble of bleeding of composition-constituting components to the surface of its molding, and to provided a molding product therefrom. CONSTITUTION:(1) The heat-resistant and frame-resistant polyester elastomer composition is obtained by adding a carboxidiimide derivative and a halogen flame retardant excluding polybromodiphenyl ether to a polyester elastomer. (2) A tube is obtained by molding the composition into a prescribed shape and subsequently radiating the molding with ionizing radiation, (3) A thermally shrinkable tube is obtained by molding the composition into a prescribed shape, irradiation the molding with ionizing radiation, spreading the diameter of the irradiated molding, and subsequently fixing the spread product. (4) The insulated cable is obtained by coating the outer periphery of a single core or multicore twisted insulated cable comprising plural insulating electric wires with the composition and subsequently irradiating the coated insulated electric cable with ionizing radiation. (5) The halogen flame-retardant excluding the polybromodiphenyl ether includes a brominated ethylene bis-phthalimide derivative, bisbrominated phenylterephthalamide derivative, brominated bisphenol derivative, and perchloropentacyclodecane.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant polyester elastomer composition excellent in heat resistance and free from the problem of bleeding of constituent components of the composition on the surface of the product, and a molded article made from the same.
In particular, it relates to tubes, heat shrink tubes and insulated cables.

[0002]

2. Description of the Related Art Polyester elastomer is a material excellent in mechanical strength such as tension, impact, compression and the like, and also excellent in heat resistance and oil resistance. Therefore, it is used for automobiles such as hydraulic hoses, joint boots and air. It has been put to practical use as a material for springs, harness protection tubes, etc., or as a constituent material for various electronic parts of electronic equipment such as heat shrinkage tubes, and as an outer jacket material for insulated cables.

Polyester elastomers are typically block copolymers composed of crystalline (hard) segments and amorphous (soft) segments, and the crystalline segments are often polybutylene terephthalate and are amorphous. There are two types, a so-called polyether type using a polyether in a segment and a so-called polyester type using an aliphatic polyester.

As in the case of the polybutylene terephthalate resin, the polyester elastomer is prepared by blending a polyfunctional monomer such as ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, triacrylic formal, triallyl cyanurate and triallyl isocyanurate. By molding and irradiating with ionizing radiation such as accelerated electron beam to crosslink, a heat-resistant polyester elastomer molded article which does not melt and deform even when heated above the melting point can be obtained.

However, since the polyester elastomer itself is not flame-retardant, a flame-retardant is blended as necessary in the application where flame-retardant property is required. To make a polyester elastomer flame-retardant, like the case of making a polybutylene terephthalate resin flame-retardant,
It is common to use a brominated flame retardant such as polybromodiphenyl ether together with a flame retardant auxiliary such as antimony trioxide to make it flame-retardant. Among them, decabromodiphenyl ether is the number of parts added and the flame retardance of the composition. It is the most widely used flame retardant from the viewpoint of improvement effect.

For example, the limiting oxygen index of a polyether type polyester elastomer having a Shore D hardness of 40 is about 19, but, for example, polyester elastomer 100
By blending 20 parts by weight of tecabromodiphenyl ether and 10 parts of antimony trioxide with respect to parts by weight, the limiting oxygen index can be increased to about 26, and horizontal flame-retardant applications such as automobile harness protection tubes are required. It is possible to obtain a flame-retardant polyester elastomer composition that can also be applied to.

However, when a polyester elastomer composition containing polybromodiphenyl ether such as decabromophenyl ether or a molded product thereof is left for a long time, there is a problem that the polybromodiphenyl ether bleeds on the surface of the product. In this case, there was a problem that bleeding of the flame retardant caused whitening (whitening), which markedly impaired the appearance of the product.

On the other hand, flame retardants other than polybromodiphenyl ether, for example, organic bromine-containing flame retardants such as brominated ethylene bisphthalimide derivative, bis brominated phenyl terephthalamide, brominated bisphenol derivative, perchloropentacyclodecane. There is also known a method of making a polyester elastomer flame-retardant by using a chlorine-containing flame retardant such as.

[0009]

These flame retardants have the advantage of less bleeding on the product surface than polybrominated diphenyl ethers, but on the other hand reduce the heat aging resistance of polyester elastomers and, compared with polybrominated diphenyl ethers. However, since the flame-retardant effect is small with the same number of parts, it is necessary to add a large amount, and there is a problem that the heat aging resistance of the composition is further reduced.

[0010]

Means for Solving the Problems As a result of earnest studies on such problems, the present inventor has found that halogen-based flame retardants other than polybromodiphenyl ether, such as brominated ethylene bisphthalimide derivatives and bisbrominated phenyl terephthalate, are used as flame retardants for polyester elastomers. Even when flame-retarded by using amide derivative, brominated bisphenol derivative, other organic bromine-containing flame retardant or chlorine-containing flame retardant such as perchloropentacyclodecane, if carbodiimide derivative is blended, heat aging resistance The inventors have found that the problem of reduction of the above can be solved, and have completed the present invention based on such findings.

That is, the present invention relates to a heat-resistant flame-retardant polyester elastomer composition comprising a polyester elastomer containing a halogen-based flame retardant other than polybromodiphenyl ether and a carbodiimide derivative. The halogen-based flame retardant other than polybrominated diphenyl ether is a mixture of one or more selected from the group consisting of brominated ethylene bisphthalimide derivative, bisbrominated phenylterephthalamide derivative, brominated bisphenol derivative and perchloropentacyclodecane. It is characterized in that further,

A heat-resistant and flame-retardant polyester obtained by molding a heat-resistant and flame-retardant polyester elastomer composition containing a polyester elastomer containing a halogen-based flame retardant other than polybromodiphenyl ether and a carbodiimide derivative into a tube and irradiating it with ionizing radiation. It relates to an elastomer tube. The halogen-based flame retardant other than polybrominated diphenyl ether is a mixture of one or more selected from the group consisting of brominated ethylene bisphthalimide derivative, bisbrominated phenylterephthalamide derivative, brominated bisphenol derivative and perchloropentacyclodecane. Another feature is the heat-resistant flame-retardant polyester elastomer tube. Furthermore,

A heat-resistant flame-retardant polyester elastomer composition obtained by mixing a halogen-based flame retardant other than polybromodiphenyl ether and a carbodiimide derivative in a polyester elastomer is molded into a tube shape, irradiated with ionizing radiation, and then expanded in a radial direction. The present invention relates to a heat-resistant and flame-retardant polyester elastomer heat-shrinkable tube that is fixed. The halogen-based flame retardant other than polybrominated diphenyl ether is a mixture of one or more selected from the group consisting of brominated ethylene bisphthalimide derivative, bisbrominated phenylterephthalamide derivative, brominated bisphenol derivative and perchloropentacyclodecane. It is characterized by the heat-resistant flame-retardant polyester elastomer heat-shrinkable tube. further,

A heat-resistant and flame-retardant polyester elastomer composition comprising a polyester elastomer containing a halogen-based flame retardant other than polybromodiphenyl ether and a carbodiimide derivative is provided on the outer periphery of a single-core or multi-stranded twisted insulated wire of a plurality of insulated wires. The present invention relates to a heat-resistant and flame-retardant polyester elastomer insulation cable, which is coated and the coating layer is irradiated with ionizing radiation. The halogen-based flame retardant other than polybrominated diphenyl ether is a mixture of one or more selected from the group consisting of brominated ethylene bisphthalimide derivative, bisbrominated phenylterephthalamide derivative, brominated bisphenol derivative and perchloropentacyclodecane. It is characterized by the heat-resistant and flame-retardant polyester elastomer insulation cable.

The present invention will be described in detail below. The carbodiimide derivative used in the present invention is a compound having a carbodiimide bond in the molecule, and examples thereof include those represented by the general formulas [1] and [2]. Examples thereof include compounds such as dicyclohexylcarbodiimide, diphenylcarbodiimide and dibenzylcarbodiimide, and polycarbodiimide compounds represented by the general formula [2] (polymers having a carbodiimide bond as a repeating unit).

[0016]

Embedded image R ₁ —N═C═N—R ₂ [1] (wherein R ₁ and R ₂ represent an alkyl group, a cycloalkyl group or an aromatic hydrocarbon group such as a phenyl or benzyl group, and R 1 ₁ and R ₂ may be the same or different.)

[0017]

Embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image wherein :-( R−N═C═N—) _n [2] (wherein R represents an alkyl group, a cycloalkyl group, or an aromatic hydrocarbon such as a phenyl or benzyl group).

The polyester elastomer used in the present invention generally has a structure of a (AB) _n type multiblock copolymer composed of crystalline (hard) segment A and amorphous (soft) segment B. The structurally crystalline segment is a polyester such as polybutylene terephthalate or polyethylene terephthalate, and the amorphous segment is a polyether type such as polyethylene glycol or polypropylene glycol and a polyester type such as an aliphatic polyester. To be

To produce polyester elastomers, one generally provides the desired elastomeric properties,
It suffices that the crystalline segment and the amorphous segment can be multiblock copolymerized in a desired ratio, and usually aromatic dicarboxylic acid, aliphatic dicarboxylic acid and / or, dicarboxylic acid such as alicyclic dicarboxylic acid or a lower thereof. The alkyl ester component (a) and a low molecular weight glycol (b) such as ethylene glycol and propyne glycol (b) and / or a polyoxyalkylene glycol (c) such as polyoxyethylene glycol and polyoxypropylene glycol (a) are added as described above. A polyester elastomer is obtained by treating it in the presence of a polycondensation catalyst according to a conventional method (ester exchange method, esterification method, polycondensation method, etc.) with a combination capable of forming a polyester elastomer composed of a crystalline segment and an amorphous segment. be able to.

Examples of the halogen-based flame retardant used in the present invention include organic bromine- or chlorine-containing flame retardants such as brominated ethylene bisphthalimide derivative, bisbrominated phenylterephthalamide derivative, brominated bisphenol derivative and perchloropentacyclodecane. It can be used.

The ratio of each component constituting the polyester elastomer composition of the present invention is not particularly limited, but 10 to 40 parts by weight of a halogen-based flame retardant per 100 parts by weight of the polyester elastomer, in view of the balance between the flame retardant action and the anti-bleeding action, 15 to 35 parts by weight and 0.5 to 5 parts by weight, preferably 1 to 2 parts by weight are desirable.

In the above case, if the halogen-based flame retardant is less than 10 parts by weight, the desired flame retardant effect cannot be imparted to the polyester elastomer, and if it exceeds 40 parts by weight, a predetermined amount of the carbodiimide derivative is added. Even if it is compounded, it becomes insufficient to suppress the deterioration of the heat aging resistance of the polyester elastomer.

If the amount of the carbodiimide derivative is less than 0.5 part by weight, it becomes difficult to suppress the heat aging resistance of the polyester elastomer, and if the amount exceeds 5 parts by weight, the effect is not changed.

The polyester elastomer composition of the present invention contains optional additives such as flame retardant aids such as antimony trioxide, polyfunctional monomers, and antioxidants such as amine-based and hindered phenol-based stabilizers. A light stabilizer such as a benzophenone-based compound, a benzotriazole-based compound or a hindered amine-based compound, a processing aid, a pigment or a filler can be added.

These additives, the specific halogen-based flame retardant and the carbodiimide derivative according to the present invention are blended with the polyester elastomer in advance by means such as kneading after the production of the polyester elastomer, and molding powder such as pellets is obtained. After processed into a polyester elastomer molded product by various molding means.

Specifically, the polyester elastomer composition of the present invention can be molded into various molded articles by known molding means such as extrusion coating, extrusion molding, injection molding, press molding, and the like, such as tubes, heat shrinkable tubes, and insulated cables. To In the case of the present invention, the obtained polyester elastomer molded article is then cross-linked by irradiation with known ionizing radiation (electron beam etc.) in order to improve heat resistance, chemical resistance, etc., to obtain a cross-linked molded article. . In this case, it is preferable to preliminarily add a polyfunctional monomer as a crosslinking accelerator.

Further, in the case of the molded article of the present invention, various molded articles can be formed by the following molding means. That is, the heat-resistant and flame-retardant polyester elastomer composition of the present invention can be extruded into a tube.

Further, after the tube is crosslinked by irradiating with ionizing radiation, for example, compressed air is blown into the molded article under heating conditions to expand the diameter and cool and fix the tube. Can also be

Further, the heat-resistant flame-retardant polyester elastomer composition of the present invention is coated on the outer periphery of a multi-core twisted insulated wire of a single core or a plurality of insulated wires made of a conductor such as copper by a molding means such as extrusion coating. Further, an insulating cable can be obtained by further irradiating with ionizing radiation and crosslinking.

As the polyfunctional monomer to be used, diacrylate type such as diethylene glycol, dimethacrylate type such as ethylene glycol methacrylate and dipropylene glycol dimethacrylate, triacrylate type such as trimethylolethane triacrylate and trimethylolpropane triacrylate. , Trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate and other trimethacrylates, triallyl cyanurate, triallyl isocyanurate, diallyl cyanurate, diallyl phthalate and the like.

The polyester elastomer composition and the molded article of the present invention can be used in such a manner that the polyester elastomer composition is excellent in mechanical strength such as tension, impact and compression.
Further, in addition to having excellent heat resistance and oil resistance, etc., it is also a material with good heat aging resistance and bleed resistance, so as a material for hydraulic hoses used in automobiles, joint boots, air springs, harness protection tubes, etc. Alternatively, it is practically used as a constituent material of various electronic parts of electronic equipment such as a heat-shrinkable tube and a jacket material of an insulated cable.

[0032]

As described above, for example, when 20 parts by weight of tecabromodiphenyl ether and 10 parts of antimony trioxide are mixed with 100 parts by weight of a polyether type polyester elastomer having a Shore D hardness of 40, the limiting oxygen index is about 26. A flame-retardant polyester elastomer composition can be obtained.

This composition was molded into a sheet having a thickness of 1 mm by using a pressing device or the like, cross-linked by irradiating with an electron beam having an accelerating voltage of 1 MeV at 100 kGy, punched into a dumbbell and set in a gear oven set at 158 ° C. As a result of comparing the tensile strength and the elongation of the dumbbell sample before and after heat aging for 168 hours, the tensile strength before heat aging was 1.9 kg / mm ² ,
The elongation is 650%.

On the other hand, this composition shows that after heat aging,
The tensile strength is 1.4 kg / mm ² , the elongation is 574%,
In addition, the retention of tensile strength and elongation after heat aging with respect to the initial value is 70% or more, and good heat aging resistance is exhibited.

However, when a brominated ethylene bisphthalimide derivative represented by the following structural formula 2 is used as a flame retardant in this composition, in order to make the limiting oxygen index about 26,
For 100 parts by weight of the same polyester elastomer,
It was necessary to mix 30 parts by weight of the flame retardant and 10 parts by weight of antimony trioxide.

This composition was similarly shaped into a sheet having a thickness of 1 mm, and then crosslinked by irradiation with an accelerated electron beam to give 158
Heat aged for 168 hours in a gear oven set at ℃,
As a result of comparing the tensile strength and elongation of the dumbbell sample before and after heat aging, the tensile strength before heat aging was 1.8 kg / mm ² , and the elongation was 6
71% and the same results as when using decabromodiphenyl ether as a flame retardant were obtained, whereas after heat aging 0.7 kg / mm ² , elongation was 483%, especially the decrease in tensile strength was large and heat aging The sex was found to be inadequate.

However, even with a composition containing 30 parts by weight of the above brominated ethylene bisphthalimide derivative,
A similar heat aging test was conducted on the composition according to the present invention containing 0.5 part by weight of dicyclohexylcarbodiimide. As a result, the tensile strength before heat aging was 1.8 kg / m.
m ² , elongation 644%, 1.3 kg / after heat aging
It was found that the composition had a mm ² and an elongation of 623%, and showed the same heat aging resistance as a composition using decabromodiphenyl ether as a flame retardant.

Similarly, even in the case of a halogen-based flame retardant, in the case of a composition in which 20 parts by weight of decabromodiphenyl ether is blended to make it flame-retardant, 1 part by weight of dicyclohexylcarbodiimide is added to 100 parts by weight of the polyester elastomer. Even after blending, the heat aging characteristics were 1.4 kg / mm ² and the elongation was 558%, and the heat aging resistance was almost unchanged even when the carbodiimide compound was blended.

The carbodiimide compound used in the present invention is known as a compound having an effect of suppressing the hydrolysis reaction of the polyester elastomer. Therefore, it is expected that the composition obtained by blending the carbodiimide compound in the polyester elastomer flame-retarded by blending the specific halogen-based flame retardant or the molded article from the composition may be improved in water resistance or hot water resistance. is there.

However, the heat aging test at 158 ° C. for 168 hours is, so to speak, a heat aging test under an absolutely dry condition in a gear oven. Further, in the case of a composition in which the flame retardant is decabromodiphenyl ether, considering that there is no difference in the heat aging characteristics depending on the presence or absence of the carbodiimide compound, it is difficult to consider the effect of water on the heat aging resistance, and the carbodiimide. It is considered that the compound exerts some particularly preferable action in a flame-retardant polyester elastomer composition system using a halogen flame retardant other than decabromodiphenyl ether.

[0041]

The present invention is illustrated by the following examples, which do not limit the scope of the invention. (Examples 1 to 6 and Comparative Examples 1 to 11) Each material was set to 140 ° C. in accordance with the composition shown in Tables 1 to 8 below.
After kneading with an inch roll mixer, press the kneaded material to 150 ° C and use a press machine with a thickness of 1 mm
And a 2 mm sheet.

In addition to the compounding compositions shown in Tables 1 to 3, 10 parts by weight of antimony trioxide, 2 parts by weight of trimethylolpropane trimethacrylate, and 1 part by weight of carbon black were commonly compounded. Next, the sheet-shaped molded product was irradiated with an electron beam having an acceleration voltage of 1 MeV at 100 kGy to be crosslinked.

To evaluate the characteristics of the sample, a sheet-shaped molded product having a thickness of 1 mm was punched into a JIS No. 3 dumbbell, and a tensile test and a tensile test after heat aging for 168 hours in a gear oven set at 158 ° C. were carried out at n = 3. It was

The bleeding test of the compound was carried out by observing the presence or absence of the bleeding substance on the surface of the sheet after allowing a sheet having a thickness of 1 mm to stand at room temperature for 6 months. The flame retardancy was evaluated by measuring the limiting oxygen index of a sheet-shaped molded product having a thickness of 2 mm. The oxygen limit index as used herein refers to the minimum oxygen concentration required to sustain combustion when a sheet-shaped molded product is burned in a mixed gas of oxygen and nitrogen.

[0045]

[Table 1]

* 1; Polyether type polyester elastomer (Shore D hardness 32, melting point 132 ° C., melt flow rate 20) * 2; compound of structural formula 1 * 3; compound of structural formula 2 * 4; antioxidant Uniroyal Chem ． Made
Product name (phenolic) * 5; Antioxidant Kawaguchi Chemical product name (amine)

[0047]

[Table 2]

[0048]

[Table 3]

Brominated ethylene bisphthalamide derivatives, bisbrominated phenyl terephthalamide derivatives and perchloropentacyclodecane were used as flame retardants as in Examples 1 to 6, and heat-resistant and flame-retardant polyesters blended with carbodiimide compounds. The elastomer composition has no problem of bleeding of the compound, and even the sample after heat aging in a gear oven at 158 ° C for 168 hours shows about 70% or more of the initial value in both tensile strength and elongation, and also has excellent heat aging resistance. I understand that.

On the other hand, it is understood that the polyester elastomer composition using the decabromodiphenyl ether of Comparative Example 1 as a flame retardant has a problem of bleeding of the compound. Further, Comparative Example 2 is a composition in which the carbodiimide compound is added to Comparative Example 1, but the heat aging resistance is the same as that of Comparative Example 1 in which the carbodiimide compound is not added.

On the other hand, as in Comparative Examples 3 to 7, a brominated ethylenebisphthalamide derivative, a bisbrominated phenylterephthalamide derivative, and perchloropentacyclodecane are used as flame retardants, and no carbodiimide compound is incorporated in the molecule. The polyester elastomer composition has no problem of bleeding of the compound, but has a large decrease in tensile strength after heat aging and is inferior in heat aging resistance. In particular, even in the case where the number of parts of the flame retardant compounded was 20 parts by weight as in Comparative Examples 4 and 6, the characteristics after heat aging were deteriorated, and the limiting oxygen index did not reach 25.

In Comparative Example 8, the compounding amount of the antioxidant of Comparative Example 3 was doubled, but the characteristics after heat aging were not significantly improved, and conversely, the limiting oxygen index decreased to 24. There is.
In Comparative Example 9, the type of antioxidant used in Comparative Example 3 was changed, but no improvement in properties after heat aging was observed.

In Comparative Example 10, the compounding amount of the antioxidant of Comparative Example 9 was doubled, but the characteristics after heat aging were not significantly improved, and conversely, the limiting oxygen index decreased to 24. There is. In Comparative Example 11, the type of antioxidant used in Comparative Example 5 was changed, but no improvement in the properties after heat aging was observed.

(Examples 7 to 8 and Comparative Examples 11 to 13) Next, the five types of polyester elastomer compositions of Examples 1 and 2 and Comparative Examples 1, 3 and 4 were pelletized to obtain 50 m.
The extrusion temperature was set to 160 ° C using a mφ single-screw melt extruder (L / D = 22), the inner diameter was 6.4 mmφ, and the wall thickness was 0.5.
A tubular molded product of mm was produced.

An acceleration voltage of 1 is applied to these tubular moldings.
The electron beam of MeV was irradiated at 100 kGy to crosslink. The initial tensile strength and elongation of the tube and the tensile strength and elongation of the tube heat aged for 168 hours in a gear oven set at 158 ° C were measured at n = 3, respectively.

Regarding the flame retardancy of the tube, a flame-retardant polyethylene electric wire [conductor: 0.18 mmφ tin-plated annealed copper wire 2
Bundling 0 strands, insulation outer diameter 2.0 mmφ; Irax B electric wire (trade name of Sumitomo Electric Industries, Ltd.)], wrap them with the above polyester elastomer tube, and JAS
A horizontal combustion test in accordance with O standard D608 was performed at n = 5 and evaluated.

The heat resistance of the tube is further 25
A soldering iron heated to 0 ° C. was brought into contact with the tube with a load of 500 g for 30 seconds to examine the melt deformability. Regarding the presence or absence of bleeding of the compound on the surface of the tube, the tube was left at room temperature for 6 months, and the surface of the tube was observed. The results are shown in Table 4.

[0058]

[Table 4]

As in Examples 7 and 8, a brominated ethylene bisphthalamide derivative represented by the following structural formula 1 and a bisbrominated phenylterephthalamide derivative represented by the following structural formula 2 were used as flame retardants, and a carbodiimide bond was formed in the molecule. The tubular molded product using the flame-retardant polyester elastomer composition containing the compound having the above-mentioned composition passed the horizontal combustion test, and the sample after heat aging also shows good properties. Structural formula 1 (brominated ethylene bisphthalimide derivative)

[0058]

[Chemical 3] Structural formula 2 (bis-brominated phenyl terephthalamide derivative)

[0059]

[Chemical 4]

On the other hand, the tubular molded article using decabromodiphenyl ether of Comparative Example 12 as a flame retardant is excellent in horizontal combustion test and heat aging resistance, but bleeding of the compound occurs when left at room temperature, which is preferable. Absent.

Comparative Example 13 uses a composition containing 30 parts by weight of a brominated ethylene bisphthalamide derivative as a flame retardant and not containing a carbodiimide compound. The subsequent decrease in tensile strength is large and the heat aging resistance is poor. (Comparative Example 14)

Comparative Example 14 uses a composition containing 20 parts by weight of a brominated ethylene bisphthalamide derivative as a flame retardant and not containing a carbodiimide compound, but some samples failed the horizontal combustion test. Also, the decrease in tensile strength after heat aging is large.

(Examples 9 to 10) Next, a flame-retardant polyethylene electric wire [conductor 2: 0.18 mmΦ tin-plated annealed copper wire 20]
Main twist, insulation outer diameter 2.0 Φ: Irax B electric wire (trade name of Sumitomo Electric Industries, Ltd.)], and a 50 mm Φ single-axis melt extruder (L / D)
= 22), the pellets of the heat and flame retardant polyester elastomer composition of Examples 7 and 8 are extruded at an extrusion temperature of 160.
The coating is extrusion-coated so that the outer diameter is 6.0 mmΦ by setting the temperature to ℃, and 100 kGy of an electron beam with an accelerating voltage of 1 MeV is irradiated, and the heat-resistant and flame-retardant polyester elastomer having the structure shown in FIG. Insulated cable 1 was obtained.

This insulated cable 1 is JASO standard D6.
A horizontal burning test according to 08 was performed at n = 5. The presence or absence of bleeding of the compound on the surface of the insulated cable 1 was determined by observing the surface of the sheath material by leaving the cable at room temperature for 6 months. The results are shown in Table 5 below together with the mechanical properties of the sheath material before and after heat aging.

[0065]

[Table 5]

Although dicyclohexylcarbodiimide was described as an example of the carbodiimide derivative in Examples 9 and 10, diphenylcarbodiimide,
Dibenzylcarbodiimide and R in the general formula [2]
Is a polycarbodiimide compound represented by the following group (n =
Similar results were obtained for 3, molecular weight = about 1,000).

Group;

[Chemical 5]

[0068]

According to the present invention, a flame-retardant polyester elastomer composition free from the problem of bleeding of the compound and excellent in heat aging resistance can be obtained. Further, if this composition is molded into a predetermined shape and then irradiated with ionizing radiation, there is no problem of burits, and a flame-retardant polyester elastomer molded article excellent in heat aging resistance and heat distortion resistance, particularly a tube, a heat shrinkable tube. Insulated cables can be obtained and have great utility value in the field of polyester elastomer applications.

[Brief description of drawings]

FIG. 1 is a schematic view showing a cross section of an insulated cable having a heat-resistant and flame-retardant polyester elastomer composition as a sheath material produced according to Examples 9 to 10 of the present invention.

[Explanation of symbols]

 1 Insulated cable 2 Conductor 3 Insulation coating 4 Sheath material

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location H01B 3/30 N 9059-5G // H01B 7/34 B 7244-5G

Claims (8)

[Claims] 1. A heat-resistant and flame-retardant polyester elastomer composition comprising a polyester elastomer containing a halogen-based flame retardant other than polybromodiphenyl ether and a carbodiimide derivative. 2. A halogen-based flame retardant other than polybromodiphenyl ether is one or more selected from the group consisting of brominated ethylene bisphthalimide derivatives, bisbrominated phenylterephthalamide derivatives, brominated bisphenol derivatives, and perchloropentacyclodecane. The heat-resistant flame-retardant polyester elastomer composition according to claim 1, which is a mixture of seeds. 3. A heat-resistant and flame-retardant polyester elastomer composition comprising a polyester elastomer containing a halogen-based flame retardant other than polybromodiphenyl ether and a carbodiimide derivative, which is molded into a tube and irradiated with ionizing radiation. A heat-resistant and flame-retardant polyester elastomer tube. 4. A halogen-based flame retardant other than polybromodiphenyl ether is one or more selected from the group consisting of brominated ethylene bisphthalimide derivatives, bisbrominated phenylterephthalamide derivatives, brominated bisphenol derivatives, and perchloropentacyclodecane. The heat-resistant flame-retardant polyester elastomer tube according to claim 3, which is a mixture of seeds. 5. A heat-resistant and flame-retardant polyester elastomer composition comprising a polyester elastomer containing a halogen-based flame retardant other than polybromodiphenyl ether and a carbodiimide derivative is molded into a tube shape, and is irradiated with ionizing radiation, and then radially. A heat-shrinkable, flame-retardant polyester elastomer heat-shrinkable tube characterized by having a wide diameter fixed. 6. A halogen-based flame retardant other than polybromodiphenyl ether is one or more selected from the group consisting of brominated ethylene bisphthalimide derivatives, bisbrominated phenylterephthalamide derivatives, brominated bisphenol derivatives, and perchloropentacyclodecane. The heat-resistant flame-retardant polyester elastomer heat-shrinkable tube according to claim 5, which is a mixture of seeds. 7. A heat-resistant and flame-retardant polyester elastomer composition comprising a polyester elastomer containing a halogen-based flame retardant other than polybromodiphenyl ether and a carbodiimide derivative on the outer periphery of a single-core or multi-stranded twisted insulated wire of a plurality of insulated wires. A heat-resistant and flame-retardant polyester elastomer insulation cable, characterized in that it is coated with an object and the coating layer is irradiated with ionizing radiation. 8. A halogen-based flame retardant other than polybromodiphenyl ether is one or more selected from the group consisting of brominated ethylene bisphthalimide derivatives, bisbrominated phenylterephthalamide derivatives, brominated bisphenol derivatives and perchloropentacyclodecane. A heat-resistant flame-retardant polyester elastomer insulated cable according to claim 7, characterized in that it is a mixture of seeds.