JP2003292689A - Flame-retardant nonhalogen resin composition and flame-retardant power supply cord - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant nonhalogen resin composition does not generate a harmful gas such as dioxins or the like, has a flame retardance passing both the 60°-inclined combustion test according to JIS C3005 and the vertical combustion test according to UL 1581 VW-1, has excellent softness (flexibility) and electrical insulation properties, and does not generate die tailings (deteriorated resin) even when subjected to long-time extrusion. <P>SOLUTION: This flame-retardant nonhalogen resin composition is prepared by compounding 100-200 pts.wt. metal hydrate and 0.3-10 pts.wt. fatty acid with 100 pts.wt. base polymer comprising at least one polymer selected from olefin polymers, synthetic rubbers, thermoplastic elastomers, and their modification products. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention does not generate a harmful gas such as a halogen gas at the time of combustion, has high flame retardancy, excellent flexibility (or flexibility), and electric insulation characteristics, and The present invention relates to a halogen-free flame-retardant resin composition that does not cause die cast (eyes) even when extrusion is performed for a long time, and a flame-retardant power cord using the same as a coating material.

[0002]

2. Description of the Related Art Conventionally, halogen-free flame-retardant resin compositions have been prepared by adding a large amount of magnesium hydroxide or aluminum hydroxide to a rubber material such as ethylene homopolymer, ethylene copolymer or ethylene propylene rubber. Blends are known and are used as coating materials for various molded products and electric wires and cables. However, since such a flame-retardant olefin polymer composition requires the addition of a large amount of magnesium hydroxide or the like as described above, the coating becomes too hard as a coating material for power cords, and Since the elongation is insufficient, there was a problem in terms of flexibility. Furthermore, when these resin compositions are subjected to extrusion coating for a long time for manufacturing electric wires / cables, for example, die casts (eyes) are generated in the extruder, and
The appearance of the cable may have failed.

[0003]

Therefore, the problem to be solved by the present invention is that it does not contain a halogen element and does not generate harmful gas such as dioxin during incineration.
JIS standard C3005 60 degree inclined combustion test and UL
It has flame retardancy that passes both of the vertical combustion tests specified in VW-1 of the standard 1581, and has excellent flexibility (flexibility) and electrical insulation properties, and it is extruded for a long time. (EN) It is intended to provide a non-halogen flame-retardant resin composition which does not generate a dicus (eyes) even when working, and a flame-retardant power cord in which a conductor is coated with the flame-retardant resin composition.

[0004]

In order to solve the above-mentioned problems, at least one selected from the olefin polymer, the synthetic rubber, the thermoplastic elastomer described in claim 1 and the above-mentioned polymer obtained by modifying them. 100 parts by weight of the base polymer consisting of one kind, 100-metal hydrate
This is solved by providing a halogen-free flame-retardant resin composition characterized by containing 200 parts by weight and 0.3 to 10 parts by weight of a fatty acid.

Further, as described in claim 2, with respect to 100 parts by weight of a base polymer composed of at least one selected from an olefin polymer, a synthetic rubber, a thermoplastic elastomer, and a polymer obtained by modifying these. , Metal hydrate 50 to 180 parts by weight, fatty acid compound 0.3 to 1
0 parts by weight and at least one selected from a nitrogen-based flame retardant auxiliary agent, a zinc-based flame retardant auxiliary agent, a silicone-based flame retardant auxiliary agent, and a phosphorus-based flame retardant auxiliary agent are blended. It is solved by providing a composition.

Further, as described in claim 3, a non-halogen flame-retardant resin composition according to claim 1 or 2 is extrusion-coated on a conductor to provide a flame-retardant power source. It is solved by making it a code.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The invention according to claim 1 is based on 100 parts by weight of a base polymer composed of at least one selected from an olefin polymer, a synthetic rubber, a thermoplastic elastomer, and a polymer obtained by modifying these, and the like. Thing 100 ~
A halogen-free flame-retardant resin composition containing 200 parts by weight and 0.3 to 10 parts by weight of a fatty acid, which has excellent flexibility and electrical insulation properties, high flame retardancy and excellent extrusion processing. It is a halogen-free flame-retardant resin composition having properties.

[0008] That is, regarding the flexibility (flexibility), it has flexibility (flexibility) as a power cord by setting the mechanical characteristics such that the tensile strength as a standard is 10 MPa or more. Become. Regarding flame retardancy, the flame-retardant power cord manufactured by extruding and coating the above-mentioned halogen-free flame-retardant resin composition on a conductor is a JIS standard C3005 60-degree inclined combustion test and UL standard 15
It passes all of the vertical combustion tests specified in VW-1 of 81. Such a flame-retardant power cord is
The required flame retardancy is sufficient, and even if these flame-retardant power cords are incinerated, they do not generate harmful gases such as dioxin, and they are also electrically insulating. The resistance can be 50 MΩ · km or more. The flame-retardant resin composition is blended with a specific amount of fatty acid so that die cast (eyes) is not generated even when a long-time, for example, wire / cable extrusion coating work of 5000 m is performed. I have.

First, the base polymer of the halogen-free flame-retardant resin composition will be described. As the olefin polymer, low density polyethylene (LDPE), ultra low density polyethylene (VLDPE) linear low density polyethylene (LLDPE), etc. Olefin homopolymer and ethylene
Ethylene copolymers such as vinyl acetate copolymer (EVA), ethylene-ethyl acrylate (EEA), ethylene-methyl methacrylate (EMMA) and ethylene propylene diene copolymer (EPDM) are used. The ethylene copolymer is particularly preferable, and the EVA and the EEA can be used alone or in combination of two kinds. As the synthetic rubber, ethylene / propylene rubber (EPR), ethylene /
Acrylic rubber (EAC) and the like can be mentioned, but among them, the above EAC is preferably used. Further, as the thermoplastic elastomer, a styrene-based thermoplastic elastomer such as a styrene-ethylene-butylene-styrene copolymer (SEB
S) and styrene-ethylene-ethylene propylene-styrene copolymer (SEEPS) include olefin-based ones such as polypropylene-ethylene-propylene copolymer (PP-EP) and polyester-based elastomer. The SEBS is preferably used.

As the base polymer of the present invention, those obtained by acid-modifying the above-mentioned polymers can be used.
That is, olefin homopolymers such as low density polyethylene (LDPE), ultra low density polyethylene (VLDPE) linear low density polyethylene (LLDPE), and ethylene-
Vinyl acetate copolymer (EVA), ethylene-ethyl acrylate (EEA), ethylene-methyl methacrylate (EMMA), ethylene propylene diene copolymer (EPDM), ethylene-propylene rubber (EPR),
Ethylene / acrylic rubber (EAC), styrene / ethylene / butylene / styrene copolymer (SEBS), styrene / ethylene / ethylene propylene / styrene copolymer (SEEPS), polypropylene / ethylene / propylene copolymer (PP-EP) Polyester elastomers are acid-modified with maleic acid and maleic anhydride. Known examples of such modified polymers and the like are "HPR" manufactured by Mitsui DuPont Polychemical Co., Ltd., "Bondaine" manufactured by Sumitomo Chemical Co., Ltd., and the like.

The above base polymers may be used alone or as a mixture. That is, when used alone, 100 parts by weight of the above polymer or the like is used as a base polymer when 100% by weight of the mixture is used. As for the case of the mixture, in the case of the olefin polymer, a mixture of the ethylene copolymer is particularly preferable. Specifically, the EVA and the EE
The mixture of A is preferred. Also, a mixture of an ethylene copolymer and a styrene thermoplastic elastomer is used. Specifically, a mixture of the EVA and the SEBS copolymer is preferable. Further, a mixture composed of three kinds of polymers and the like is also preferable. Specifically, a mixture of an ethylene copolymer, a styrene thermoplastic elastomer, and an acrylic rubber that is a synthetic rubber is also used. Specifically, a mixture of EVA, SEEPS, and ethylene / acrylic rubber is preferable.
Further, a polymer obtained by acid-modifying the above polymer or the like may also be used alone or as a mixture.

Then, 100 to 200 parts by weight of a metal hydrate as a flame retardant and 0.3 to 10 parts by weight of a fatty acid are blended with 100 parts by weight of the base polymer to obtain a halogen-free flame-retardant resin composition. It is a thing. The metal hydrate exhibits self-extinguishing property by releasing moisture during combustion and causing an endothermic reaction at a high temperature, such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide or basic magnesium carbonate. It has been known. Of these, magnesium hydroxide is the most preferable. Further, the surface of the metal hydrate is preferably treated with a fatty acid, a silane coupling agent, a titanium coupling agent or the like in order to improve the dispersibility and compatibility with the resin mixture. And, the addition amount is set to 100 to 200 parts by weight, because the effect of flame retardancy is not exhibited when the amount is less than 1000 parts by weight, and the JIS standard C3005 60 degree inclined combustion test and UL standard 1581 which are the objects of the present invention. This is because it is not possible to pass both of the vertical combustion tests specified in VW-1. Further, if it is added in an amount of more than 200 parts by weight, the obtained flame-retardant resin composition cannot obtain the desired flexibility. That is, the tensile strength, which is a measure of the flexibility, is 10 MPa or less, which is not preferable as a coating material for the power cord. Further, with respect to the electric insulation characteristic, the insulation resistance (MΩ · km) becomes 50 or less, and it cannot be used.

Next, the fatty acids added to improve the extrusion processability will be described. As such fatty acids, unsaturated fatty acids are preferable, and linear fatty acids such as stearic acid and palmitic acid are preferable. . The amount of addition is 0.3 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the base polymer. This is because if the addition amount is less than 0.3 parts by weight, it will be 5 in the case of long-time extrusion work, for example, in the case of wire / cable extrusion coating.
For extrusion work of 000m length, die cast
This is because the occurrence cannot be prevented. Further, if it is added in excess of 10 parts by weight, the mechanical properties are lowered, that is, the tensile strength becomes 10 MPa or less, which is not preferable as a coating material for the power cord.

Further, the halogen-free flame-retardant resin composition of the present invention comprises at least one selected from olefin polymers, synthetic rubbers, thermoplastic elastomers and the above-mentioned polymers modified with them as described in claim 2. Metal hydrate 5 per 100 parts by weight of the base polymer consisting of seeds
0 to 180 parts by weight, 0.3 to 10 parts by weight of fatty acid, and at least one selected from nitrogen flame retardant aids, zinc flame retardant aids, silicone flame retardant aids and phosphorus flame retardant aids. The non-halogen flame-retardant resin composition described above is preferable.
As a result, flame retardancy is improved and JIS standard C300
It is possible to reliably pass both the 60 degree inclined combustion test of 5 and the VW-1 of the vertical combustion test of UL standard 1581.

That is, the halogen-free flame-retardant resin composition according to claim 1 is further selected from a nitrogen-based flame retardant auxiliary agent, a zinc-based flame retardant auxiliary agent, a silicone-based flame retardant auxiliary agent, and a phosphorus-based flame retardant auxiliary agent. At least one kind of compound is added. The blending amount is not particularly limited, but is added within a range that does not impair the mechanical properties and electrical properties. The amount is approximately 5 to 100 parts by weight. And, as the nitrogen-based flame retardant aid, for suppressing combustion by generating a large amount of nitrogen gas or the like during combustion, ammonium polyphosphate, powdered melamine, melamine cyanurate and the like, but among them melamine cyanurate It is preferably used. Further, the zinc-based flame retardant aid is considered to contribute to the flame retardancy by forming a flame-retardant shell called char during combustion. Specifically, zinc borate, hydroxy Examples include zinc stannate and zinc stannate. Further, as the silicone-based flame retardant aid, silicone gum, silicone powder, silica or the like is used. Furthermore, as phosphorus-based flame retardant aids, red phosphorus, titanium surface-treated red phosphorus, ammonium polyphosphate and the like can be used. Such a halogen-free flame-retardant resin composition has a flame-retardant property according to JIS C300.
It will pass both the 60 degree inclined combustion test of 5 and the VW-1 of the vertical combustion test of UL standard 1581, and the flame-retardant power cord using this as a coating material has sufficient characteristics in flame retardancy. Is to have. The flame-retardant power cord coated with such a flame-retardant resin has sufficient flame retardancy required.

Further, even if the flame-retardant power cords are incinerated, they do not generate harmful gas such as dioxin and cause no environmental problem. The non-halogen flame-retardant resin composition also has a sufficient insulation resistance (MΩ · km) in terms of electrical insulation. In addition,
The halogen-free flame-retardant composition of the present invention described above,
Various additives that are usually added when used as a coating material for electric wires and cables can be blended in required amounts. Examples include anti-aging agents, coloring agents, cross-linking agents, UV absorbers, lubricants, plasticizers and the like.

Further, as described in claim 3, a flame-retardant power source cord obtained by extruding and coating the above halogen-free flame-retardant resin composition on a conductor has a high degree of flame retardancy and excellent flexibility. (Flexibility) and electrical insulation characteristics can be excellent. That is, regarding the flame retardancy, the JIS standard C3005 60-degree inclined combustion test and UL standard 158
In any of the vertical combustion tests specified in VW-1 of 1,
It definitely passes. And such a flame-retardant power cord is sufficient for the required flame-retardant property, and the flame-retardant power cords may generate a harmful gas such as dioxin during combustion. There is no environmental problem. Regarding the flexibility, the tensile strength is 10 MPa or more, and those having such characteristic values can have sufficient flexibility as a power cord. Furthermore, regarding electrical insulation, the insulation resistance (MΩ ・ km) is also 50.
It has a sufficient margin against. The term "power cord" here means an electric wire or cable usually called an insulated electric wire or a cabtire cord in which a conductor made of a copper conductor or the like is extruded and coated with the flame-retardant composition in a single core or flat shape. The coating layer is usually about 0.5 to 1.5 mm and is extruded and coated on the conductor. And since this flame-retardant power cord uses a non-halogen flame-retardant resin composition that is excellent in extrudability for a long time as described above, there is no problem of poor appearance due to diecus (eyes or the like) in the coating layer. Is.

[0018]

EXAMPLES The effects of the halogen-free flame-retardant resin composition and the flame-retardant power cord of the present invention will be clarified by showing concrete examples below. Using various halogen-free flame-retardant compositions having the contents shown in Table 1, the tensile strength (MPa) as a measure of flexibility is based on JIS K7113 and insulation resistance (MΩ · km). Was measured according to the Electrical Appliance and Material Safety Law. Furthermore, as flame retardancy, these halogen-free flame-retardant resin compositions were applied to a stranded copper conductor having a wire diameter of 0.18 mm × 30 and a thickness of 0.8 m.
m is extruded and coated to make a flame-retardant power cord, and JIS
60 degree inclined combustion test of standard C3005 and UL standard 1
A vertical burning test was performed according to VW-1 of 581. The results are listed as pass and fail. In addition, what is described as passing in the vertical burning test of UL standard is the case where all the five power cord samples have passed. In addition, the extrudability of this flame-retardant resin composition was adjusted to 5
The generation state of die casks in the extruder when continuously produced for 000 m was examined, and those without die casks were indicated as pass, and those that were generated were indicated as fail. The numerical values of the compounded materials in the table are shown in parts by weight.

[0019]

[Table 1]

As is clear from Table 1, the halogen-free flame-retardant resin compositions shown in Examples 1 to 12 have a tensile strength of 1
It was confirmed that it has excellent flexibility (flexibility) for the power cord of the present invention of 0 MPa or more. In addition, flame-retardant power cords using these flame-retardant resin compositions are JI
All of them passed both the S standard C3005 60-degree inclined combustion test and the UL standard 1581 vertical combustion test according to VW-1. Regarding the extrudability, no die-casing was observed even when the power cord was continuously extruded for 5000 m. Specifically, Examples 1 and 2 using the EVA or the EEA alone as the base polymer, Examples 3 to 6 using the mixture of the EVA and the EEA or the mixture of the EVA and the ethylene-acrylic rubber as the base polymer. , Again EVA,
Examples 7 to 10 using the mixture of SEEPS and ethylene-acrylic rubber as a base polymer and the EV
In Examples 11 and 12 using A, the SEEPS and the ethylene / acrylic rubber as base polymers, 50 to 200 parts by weight of magnesium hydroxide was added singly, and a nitrogen-based flame retardant aid, zinc. Even when used in combination with a flame-retardant auxiliary agent, a silicone-based flame-retardant auxiliary agent, or a phosphorus-based flame-retardant auxiliary agent, it has excellent flexibility (flexibility), high flame-retardant properties, and good extrusion processing. It can be seen that it has a property. Regarding the electrical insulation characteristics, the insulation resistance is 50
It was confirmed that it was more than MΩ · km.

Next, a comparative example will be described with reference to Table 2. Tensile strength (MPa), insulation resistance (MΩ · km) of various halogen-free flame-retardant resin compositions produced in the same manner as in the above-mentioned examples and out of the compounding composition range of the present invention
Also, the extrusion processability was measured by the same method as in the example. In addition, a flame-retardant power cord was produced in the same manner as in the example, and a vertical combustion test was performed in the same manner as in the example according to JIS standard C3005 60-degree tilt combustion test and UL standard 1581 VW-1. It was judged. The results were also displayed. The numerical values of the compounded materials in the table are shown in parts by weight.

[0022]

[Table 2]

As is clear from the results shown in Table 2, Comparative Examples 1, 7, 9 and 10 were carried out on the flame retardancy of JIS C3005 60 ° inclined combustion test and UL standard 1581 VW-1 vertical combustion test. Did not pass the UL standard. This is because the amount of metal hydrate as a flame retardant is too small at 40 parts by weight. The same applies when a flame retardant aid is used in combination. Further, regarding the tensile strength (MPa) as a measure of flexibility, even the comparative examples 2, 4, 6, and 8 which are the above-mentioned comparative examples having flame retardancy are aimed at by the present invention. It was 10 MPa or less, which was not preferable. Further, regarding the extrudability, Comparative Examples 1, 3, 5 in which the addition amount of stearic acid was less than 0.3 parts by weight,
7 and 9 in the 5000 m long run test,
Diecus was seen. As described above, those described as comparative examples are not preferable as the flame-retardant power source cords in view of flame retardancy, flexibility (flexibility) and extrudability.

[0024]

As described above, the non-halogen flame-retardant composition of the present invention is a base comprising at least one selected from olefin polymers, synthetic rubbers, thermoplastic elastomers, and the above polymers modified with these. 100 to 200 parts by weight of a metal hydrate and 0.3 to 10 parts by weight of a fatty acid are blended with 100 parts by weight of a polymer, and an olefin polymer, a synthetic rubber, a thermoplastic elastomer, and the above-mentioned polymer obtained by modifying them. Metal hydrate 50 to 180 parts by weight, fatty acid 0.3 to 100 parts by weight with respect to 100 parts by weight of the base polymer composed of at least one selected from the grouped materials.
10 parts by weight and at least one selected from a nitrogen-based flame retardant auxiliary agent, a zinc-based flame retardant auxiliary agent, a silicone-based flame retardant auxiliary agent, and a phosphorus-based flame retardant auxiliary agent are blended to obtain excellent flexibility (flexibility). Properties), electrical insulation properties, high flame retardancy and excellent extrudability, and is a halogen-free flame-retardant resin composition.

That is, regarding the flexibility (flexibility), it is assumed that the power cord has flexibility (flexibility) by having mechanical characteristics such that the tensile strength as a standard is 10 MPa or more. Become. Regarding flame retardancy, the flame-retardant power cord manufactured by extruding and coating the above-mentioned halogen-free flame-retardant resin composition on a conductor is a JIS standard C3005 60-degree inclined combustion test and UL standard 15
It passes all of the vertical combustion tests specified in VW-1 of 81. Such a flame-retardant power cord is
The required flame retardancy is sufficient, and even if these flame-retardant power cords are incinerated, they do not generate harmful gases such as dioxins, and they also have insulation resistance in terms of electrical insulation. Can be 50 MΩ · km or more. Further, this flame-retardant resin composition has a workability that does not generate a dicus (eyes) even after performing extrusion coating work of 5000 m for a long time, for example, as an electric wire / cable by blending a fatty acid. is there.

Further, as described in claim 3, a flame-retardant power cord obtained by extrusion-coating the non-halogen flame-retardant resin composition on a conductor is used, and a 60-degree inclined combustion test of JIS C3005 and UL standard 158
It will certainly pass any of the vertical combustion tests specified in VW-1 of 1. Such flame-retardant power cords are sufficient for the required flame-retardant properties, and even if these flame-retardant power cords are incinerated, they may generate harmful gases such as dioxin. In addition, it has a sufficient insulation resistance of 50 MΩ ・ km in terms of electrical insulation.
It can be more than one. By blending a fatty acid in the flame-retardant resin composition, die-casting (eyes) does not occur even if extrusion work of 5000 m as an electric wire / cable is performed for a long time, and the flame-retardant property is improved. The power cord has no appearance defect.

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Claims (3)

[Claims] 1. A base polymer 10 comprising at least one selected from an olefin polymer, a synthetic rubber, a thermoplastic elastomer, and a polymer obtained by modifying these.
A halogen-free flame-retardant resin composition comprising 100 to 200 parts by weight of a metal hydrate and 0.3 to 10 parts by weight of a fatty acid with respect to 0 part by weight. 2. A base polymer 10 comprising at least one selected from an olefin polymer, a synthetic rubber, a thermoplastic elastomer, and a polymer obtained by modifying these.
50 to 180 parts by weight of metal hydrate, 0.3 to 10 parts by weight of fatty acid, and nitrogen-based flame retardant aid, zinc-based flame retardant aid, silicone-based flame retardant aid and phosphorus-based flame retardant relative to 0 part by weight. A halogen-free flame-retardant resin composition comprising at least one selected from a combustion aid. 3. A flame-retardant power cord, characterized in that a conductor is extrusion-coated with the halogen-free flame-retardant resin composition according to claim 1 or 2.