JP2000260228A - Covered wire - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the content of halogen without deteriorating characteristics such as wear resistance, flexibility and cold resistance by forming a base polymer with a vinyl chloride resin and a methacryl resin and by mixing calcium carbonate having an average particle diameter in a specific value range and a plasticizer in the base polymer within respective specific value ranges. SOLUTION: This vinyl chloride resin covered wire is covered with a covering composition containing a vinyl chloride resin as a base polymer. The base polymer comprises the vinyl chloride resin and a methacryl resin, and 5-30 parts by weight of calcium carbonate having an average particle diameter of 0.04-1 μm, and 25-50 parts by weight of a plasticizer are mixed in 100 parts by weight of the base polymer. The vinyl chloride resin normally used has a degree of polymerization of 1000-2500, and the molecular weight of the methacryl resin is preferably nearly in the range of 100000-300000 and the grade of the weight average molecular weight thereof is preferably standard. The calcium carbonate may be heavy, light or colloidal.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulated wire, and more particularly, to an insulated wire coated with a vinyl chloride resin having a low halogen content.

[0002]

2. Description of the Related Art Conventionally, as a coating material for wires, cables, wire harnesses and the like used for automobiles and industrial equipment, polyvinyl chloride (PVC) is used in view of appropriate flexibility, wear resistance and flame retardancy. )), A resin to which a plasticizer, a stabilizer and the like are added is often used.

In recent years, from the viewpoint of environmental measures, it has become necessary to reduce the content of halogens such as chlorine and bromine in conventionally used electric wire covering materials. In order to reduce the amount of halogen in the material, for example, instead of vinyl chloride resin, olefin-based resin such as ethylene or propylene, or a copolymer thereof was used as a base polymer, and a halogen-based or halogen-free flame retardant was blended. Some are used, but in order to use as a wire covering material, properties such as abrasion resistance and flexibility are required at a thickness of 0.2 to 0.3 mm. It is difficult for olefin resins to be added to balance these properties. In addition, there is a problem specific to olefin-based resins, such as a large necking as a wire covering material, and easy generation of whiskers at the cut when peeling.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and is intended to reduce the halogen content without impairing properties such as abrasion resistance, flexibility, and cold resistance. An object is to provide a covered electric wire.

[0005]

SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the invention of claim 1 is an electric wire coated with a coating composition using a vinyl chloride resin as a base polymer, comprising: Is composed of a vinyl chloride resin and a methacrylic resin, and 5 to 30 parts by weight of calcium carbonate having an average particle size of 0.04 to 1 μm and 25 to 50 parts by weight of a plasticizer per 100 parts by weight of the base polymer. It has features.

A second aspect of the present invention is an electric wire coated with a coating composition using a vinyl chloride resin as a base polymer, wherein the base polymer is composed of a vinyl chloride resin and a methacrylic resin, Per 100 parts by weight, 5 to 30 parts by weight of calcium carbonate having an average particle size of 0.04 to 2 μm, 25 to 50 parts by weight of a plasticizer, and 2 to 50 parts by weight of a methyl methacrylate-butadiene-styrene resin
It has the characteristic that it is blended in 20 parts by weight. Further, the methacrylic resin is preferably polymethyl methacrylate (the invention of claim 3).

The methacrylic resin is a polymer containing methacrylic acid or an ester thereof as a main component, and a typical example is polymethyl methacrylate (PMMA). These methacrylic resins are excellent in abrasion resistance, surface hardness, strength, heat resistance, electrical insulation and the like, and have good compatibility with vinyl chloride resin. Therefore, when the methacrylic resin is added to the vinyl chloride resin, the surface hardness and the strength (modulus) of the vinyl chloride resin are improved, and the wear resistance when used as a wire covering material is also improved.

[0008] The addition of methacrylic resin does not lower the electrical insulation required for covering the electric wires, and since the compatibility between the two resins is good as described above, the physical properties such as elongation of the coating also deteriorate. Hateful. In the base polymer used in the present invention, the blending amount of the methacrylic resin is 1 per 100 parts by weight of the total of the vinyl chloride resin and the methacrylic resin.
It is preferably from 0 to 50 parts by weight.

Further, 5 to 30 parts by weight of calcium carbonate and 25 to 30 parts by weight of a plasticizer per 100 parts by weight of the base polymer
The reason for blending 50 parts by weight is to reduce the halogen concentration in the coating material by blending calcium carbonate as a filler more than usual, and to maintain flexibility by blending a plasticizer. However, if the amount of the calcium carbonate is too large, the wear resistance and the cold resistance are reduced. Therefore, it is preferable to mix the calcium carbonate within the above range.

Further, the reason why the average particle size of calcium carbonate is set in the range of 0.04 to 1 μm is that if the average particle size is larger than 1 μm, the cold resistance is reduced. is there. When a methyl methacrylate-butadiene-styrene resin (MBS resin) is blended, the average particle size of calcium carbonate can be in the range of 0.04 to 2 μm. this is,
This is because the cold resistance of the resin composition is improved by blending the MBS resin. The MBS resin is preferably blended in the range of 2 to 20 parts by weight based on 100 parts by weight of the base polymer. The average particle size in the present application indicates a weight average particle size.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The vinyl chloride resin used in the present invention may be a vinyl chloride resin used for a conventional electric wire covering material, and usually has a degree of polymerization of 1,000 to 2,500. The molecular weight of the methacrylic resin is not particularly limited,
Standard grades with a weight average molecular weight preferably in the range of about 100,000 to 300,000 are preferred.

The calcium carbonate may be heavy, light, or colloidal, and may be surface-treated with a fatty acid or the like. Examples of the plasticizer include phthalic acid type, trimellitic acid type, polyester type, epoxy type, etc., but are not limited thereto, and any plasticizer compatible with the vinyl chloride resin may be used alone or in combination of two or more. To use.

Further, a stabilizer may be added. Examples of the stabilizer for the vinyl chloride resin include a lead type such as tribasic lead sulfate, a tin type, a calcium-zinc type, and a barium-zinc type. The stabilizer is added to 100 parts by weight of the base polymer.
It is preferable to add in the range of 2 to 10 parts by weight. Further, in addition to the above, an antioxidant, an antioxidant, a copper damage inhibitor, a light stabilizer, a lubricant, a flame retardant, and the like can be appropriately added.

The coated electric wire of the present invention can be manufactured by using the above-mentioned resin composition by the same manufacturing method as in the case of a conventional vinyl chloride resin electric wire. The thickness of the coating is not particularly limited, and may be appropriately determined depending on the use of the electric wire. By using the above resin composition, a coated electric wire having a low halogen content can be obtained while maintaining the same characteristics as those of the related art.

[0015]

EXAMPLES Examples 1 to 4 of the present invention and Comparative Examples 1 to 8 were made of polyvinyl chloride having a degree of polymerization of 1300, polymethyl methacrylate of a standard grade, an average particle size of 0.04 μm,
A resin composition was prepared in which 0.7 μm and 1.3 μm of calcium carbonate, a phthalic acid-based plasticizer, a calcium-zinc-based stabilizer, and a methyl methacrylate-butadiene-styrene resin were blended in proportions shown in Tables 1 to 3. These resin compositions are applied to a 7-strand / circularly compressed conductor around a conductor having a thickness of 0.2 mm.
mm to produce a coated electric wire. In addition, thickness is 1m
m and 2 mm sheets were prepared

The polymethyl methacrylate is Delpet 80N (trade name) manufactured by Asahi Kasei Corporation, the plasticizer is DUP, and the stabilizer is Rup110S manufactured by Asahi Denka Kogyo Co., Ltd.
(Product name) was used.

Using these electric wires, a scrape abrasion resistance test was performed. The scrape abrasion test is based on JIS D
The measurement was carried out under the conditions of a temperature of 23 ° C. and a load of 7 N by a blade reciprocation method of 611-94. Further, a cold resistance test of a sheet having a thickness of 2 mm and a tensile strength and an elongation of a sheet having a thickness of 1 mm were performed based on JIS K 6723. further,
With respect to the modulus of the sheet having a thickness of 1 mm, the load was measured when the sheet was extended by 2%, 5%, and 100% with respect to the distance between marked lines (2 cm). The evaluation results are shown in Tables 1 to 3.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

As shown in Comparative Examples 3, 4 and 5, PVC
By blending PMMA, it is possible to greatly reduce the halogen content as compared with the conventional examples not containing PMMA shown in Comparative Examples 1 and 2. For example, in Comparative Example 4 in which the proportion of PMMA was 20 parts by weight of the whole base polymer, the halogen content was reduced by about 20% as compared with Comparative Examples 1 and 2.

The amount of halogen can be further reduced by blending calcium carbonate. For example, in Examples 2 and 3 and Comparative Example 7 in which 20 parts by weight of calcium carbonate were blended per 100 parts by weight of the base polymer, Comparative Examples 1 and 2 were used. Compared to No. 2, the halogen content is reduced by about 30%. However, when the average particle size of the calcium carbonate to be blended as in Comparative Example 7 is large, the cold resistance is reduced.
It is preferably in the range of 04 to 1 μm. Even if calcium carbonate having a small average particle size is used,
As can be seen from Examples 2 and 3 and Comparative Example 7, the amount of halogen can be reduced at the same ratio as when a material having a large average particle size is used.

The average particle size of the calcium carbonate is 1 μm.
Even below, when the compounding amount is increased to 40 parts by weight as shown in Comparative Examples 9 and 10, the abrasion resistance of the electric wire,
Cold resistance tends to decrease. Therefore, the content of calcium carbonate is preferably 30 parts by weight or less.

Further, as shown in Example 4, when the MBS resin is blended, even if calcium carbonate having a relatively large average particle diameter of 1.3 μm is used, the cold resistance can be maintained without lowering the wear resistance. Can be improved. In addition,
When blending the MBS resin, it is a matter of course that calcium carbonate having an average particle size smaller than 1.3 μm may be used.

[0025]

As described above, according to the coated electric wire of the present invention, a part of the vinyl chloride resin is replaced with a methacrylic resin containing no halogen, and calcium carbonate having an appropriate particle size, a plasticizer, and an MBS resin are appropriately used. By mixing the amount
The halogen content can be significantly reduced without deteriorating the characteristics such as abrasion resistance and cold resistance required for the coated electric wire.

Continued on the front page F-term (reference) 4J002 BD02W BG06X BN16Y DE236 EH147 FD027 FD030 GQ01 5G305 AA02 AB35 BA13 BA15 BA26 CA03 CA07 CA08 CA37 CA51 CC11 CD01 CD17

Claims (3)

[Claims] 1. An electric wire coated with a coating composition containing a vinyl chloride resin as a base polymer, wherein the base polymer comprises a vinyl chloride resin and a methacrylic resin, and has an average particle size per 100 parts by weight of the base polymer. Contains 5 to 30 parts by weight of 0.04 to 1 μm of calcium carbonate and 25 to 50 parts by weight of a plasticizer. 2. An electric wire coated with a coating composition comprising a vinyl chloride resin as a base polymer, wherein the base polymer comprises a vinyl chloride resin and a methacrylic resin, and has an average particle size per 100 parts by weight of the base polymer. Contains 5 to 30 parts by weight of calcium carbonate having a particle size of 0.04 to 2 μm, 25 to 50 parts by weight of a plasticizer, and 2 to 20 parts by weight of a methyl methacrylate-butadiene-styrene resin. 3. The coated electric wire according to claim 1, wherein the methacrylic resin is polymethyl methacrylate.