JP5379352B2 - Insulating coating material for conductor or optical fiber, insulated wire or cable, and optical fiber cord or optical fiber cable - Google Patents

Description

As a non-petroleum-derived plastic raw material, it is expected to be used in consumer materials such as trays of lactic acid polymers having biodegradable characteristics and plastic tableware (see, for example, Patent Document 1).
However, these non-petroleum-derived plastic raw materials such as lactic acid-based polymers have been difficult to use for durable materials.
On the other hand, development of a polyester-based polybutylene succinate resin as a non-petroleum-derived plastic raw material has been carried out (for example, see Patent Document 2).
However, since polybutylene succinate resin is rigid and has poor molding processability, it cannot be used for a casing of an electronic device. Further, since the volume resistivity is very low, it is difficult to use as a wire covering material, and it is difficult to use as a plastic material for durable materials.

Japanese Patent Laid-Open No. 06-298236 JP 2002-121299 A

In view of the above problems, it has excellent mechanical properties and hydrolysis resistance, yet superior insulating coating applied is capable polybutylene succinate-based resin composition of the durable material having electrical properties The purpose is to provide electric wires and cables as materials.

  As a result of intensive studies to solve the above problems, the present inventors have used polybutylene succinate resin as a base resin, and by introducing polycarbodiimide, not only hydrolysis resistance but also mechanical strength , Found to improve electrical characteristics and so on.

That is, the present invention
(1) A resin composition containing 1 to 20 parts by mass of polycarbodiimide with respect to 100 parts by mass of a resin component containing a polybutylene succinate resin, and a sheet having a thickness of 1 mm is formed from the resin composition. An insulating coating material for a conductor or an optical fiber, comprising a resin composition having a volume resistivity of 1.0 × 10 ^{11 to} 2.0 × 10 ¹³ Ωcm based on JIS K 6723
(2) The conductor or optical fiber according to (1), wherein the polybutylene succinate resin has an MFR ( melt flow rate, 190 ° C., 2.16 kg) of 3 to 40 g / 10 min. Insulation covering material,
(3) The conductor or optical fiber insulation coating material according to (1) or (2), wherein the resin composition contains an ethylene-vinyl acetate copolymer or an acrylic resin;
(4) The resin or composition according to any one of (1) to (3), wherein the resin composition contains a fatty acid-based lubricant,
(5) An insulated wire or cable obtained by coating the insulating coating material according to any one of (1) to (4) around a conductor, and
(6) An optical fiber cord or an optical fiber cable in which the insulating coating material according to any one of (1) to (4) is coated around an optical fiber is provided.

  Since the resin composition of the present invention has hydrolysis resistance, excellent mechanical properties, and excellent electrical properties, an insulated wire can be provided by covering the conductor. Moreover, at the time of disposal such as landfill and combustion, it is possible to provide a resin composition that can reduce the burden on the environment. The resin composition of the present invention is also suitable as a coating for optical cords and cables.

First, the resin composition of the present invention will be described.
The resin composition of the present invention contains a polybutylene succinate resin and polycarbodiimide. Polycarbodiimide is generally known as a resin that enhances the hydrolyzability of polyester resins including polybutylene succinate resins. However, by mixing an appropriate amount of polycarbodiimide with polybutylene succinate resin, not only hydrolysis resistance but also mechanical strength and electrical characteristics, which were disadvantages of polybutylene succinate resin, are greatly improved. .
As the third component, polyolefin resin such as polyethylene and polypropylene, ethylene-α olefin copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene- (meth) acrylic acid copolymer It may contain an ethylene copolymer resin such as a coalescence, a styrene resin and / or an elastomer, an acrylic resin and / or an elastomer, and various modified resins.

  First, the resin components (a) and (b) used in the present invention will be described.

(A) Polybutylene succinate resin Polybutylene succinate resin is obtained by dehydration condensation polymerization of succinic acid and 1,4-butanediol and / or succinic acid, lactic acid, and 1,4-butanediol. Modification can also be made by adding phthalic acid or adipic acid as part of the acid component.
Examples of the polybutylene succinate resin are sold as GS-PLA (trade name) from Mitsubishi Chemical and as Bionore (trade name) from Showa Polymer.
This polybutylene succinate is a hard resin, but can be softened by adding a polyol during polymerization.
Such a polybutylene succinate-based resin has an MFR ( melt flow rate, 190 ° C., 2.16 kg) of about 1 to 8 g / 10 minutes when extrusion molding is performed, and 3 to 40 g / 10 minutes when injection molding is performed. Is appropriate.

(B) Polycarbodilite Polycarbodiimide is synthesized by decarboxylation condensation reaction of diisocyanate. Industrially, those sold by Nisshinbo Co., Ltd. as Carbodilite (trade name) can be mentioned.
By adding polycarbodiimide to the polybutylene succinate resin, not only hydrolyzability is prevented, but also the mechanical strength and electrical characteristics are greatly improved. The polycarbodiimide is preferably added at a ratio of 1 to 20 parts by mass with respect to 100 parts by mass of the polybutylene succinate resin. If this amount is less than 1 part by mass, the effect of substantially improving the mechanical strength and electrical characteristics is poor, and if this amount is more than 20 parts by mass, the electrical characteristics are adversely decreased.

In the present invention, various resins may be appropriately mixed and used as the third component of the resin containing polybutylene succinate resin and polycarbodiimide. For example, polyolefin resins such as polyethylene and polypropylene, ethylene-α-olefin copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, ethylene such as ethylene- (meth) acrylic acid copolymer A copolymer resin, a styrene resin and / or an elastomer, an acrylic resin and / or an elastomer, and various modified resins may be mixed. The resin to be mixed is not limited to these resins.

  In the resin composition of the present invention, various commonly used additives such as antioxidants, metal deactivators, flame retardants (auxiliaries), fillers, lubricants and the like are used for the purpose of the present invention. It can mix | blend suitably in the range which is not impaired.

  Antioxidants such as 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, 2,2,4-trimethyl-1,2-dihydroquinoline polymer, etc. Agent, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ), Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-) Phenolic antioxidants such as 4-hydroxybenzyl) benzene, bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl) s Fido, 2-mercapto Ben Uz imidazole and its zinc salt, pentaerythritol - tetrakis (3-lauryl - thiopropionate) sulfur based antioxidants such as and the like.

  Examples of metal deactivators include N, N′-bis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.

In addition, flame retardants (auxiliaries) and fillers include metal hydrates, halogen flame retardants, carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compounds, quartz , Talc, calcium carbonate, magnesium carbonate, zinc borate, white carbon and the like.
Examples of the lubricant include hydrocarbons, fatty acids, fatty acid amides, esters, alcohols, and metal soaps.

The resin composition of the present invention is processed into a molded body by injection molding, extrusion molding, blow molding or the like.
In the case of extrusion molding, the head temperature is preferably molded at 160 to 220 ° C, and in the case of injection molding and blow molding, it is preferably molded at 200 to 250 ° C.
The insulated wire and the optical fiber core of the present invention have a coating layer made of the resin composition of the present invention on a conductor (for example, a single wire or stranded conductor made of annealed copper) or an optical fiber, and this coating The layer is composed of a resin composition.
The cable of the present invention is formed by forming the resin composition of the present invention on the outside of an insulated wire, an optical fiber core wire, a strand, or a conductor.
In the insulated wire of the present invention, the resin composition can be crosslinked after forming the coating layer. As a crosslinking method, a conventional electron beam crosslinking method or chemical crosslinking method can be employed.
In the insulated wire of the present invention, the thickness of the insulating coating layer formed around the conductor is not particularly limited, but is usually 0.15 mm to 3 mm.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.
(Examples 1-6, Comparative Examples 1-4)
First, each component shown in the table was dry blended at room temperature and melt-kneaded using a Banbury mixer to prepare each resin composition for an insulating coating layer.
A sheet having a thickness of 1 mm was formed from the obtained resin using a T-die. Further, a 3 mm thick plate was formed by injection molding.
Next, the insulation coating resin composition previously melt-kneaded on the conductor (conductor diameter: 0.8 mmφ tin-plated annealed copper twisted wire configuration: 1 piece / 0.8 mmφ) using an extrusion coating apparatus for electric wire production. The insulated wire corresponding to each Example and Comparative Example was manufactured by covering by an extrusion method. The outer diameter was 1.6 mm.

About each obtained sheet | seat and each insulated wire, the tensile characteristic, the heat-resistant characteristic, the wet heat characteristic, and the volume specific resistance were evaluated, and the result was combined with the table | surface and shown. The test method and evaluation conditions are shown below.
・ (Sheet)
Tensile properties A 1 mm sheet was punched with a JIS No. 3 dumbbell and measured according to JIS K 6723. The tensile speed is 200 mm / min, and the distance between the marked lines is 20 mm.
Moisture and heat resistance A 1 mm sheet was punched with a JIS No. 3 dumbbell, placed in a thermostatic chamber at 60 ° C. and 95% for 2 weeks, and then taken out and subjected to a tensile test based on JIS K 6723.
Heat resistance A 1 mm sheet was punched with a JIS No. 3 dumbbell, placed in a constant temperature bath at 70 ° C. for 7 days, taken out, and then subjected to a tensile test based on JIS K 6723.
Volume resistivity The volume resistivity was measured based on JIS K 6723.

・ (Insulated wire)
Tensile properties (tensile strength, elongation at break)
The covering layer of each insulated wire is formed into a tubular piece, and its tensile strength (tensile strength) (MPa) and elongation (%) are measured using a tensile tester between 25 mm and a tensile speed of 500 mm / min. It measured on condition of this. The required properties of tensile strength and elongation are 10 MPa or more and 100% or more, respectively.
Moisture and heat resistance The tubular piece was placed in a thermostatic chamber at 60 ° C. and 95% for 2 weeks, and after taking out, a tensile test was performed based on the above method of tensile properties.
Heat resistance After the tubular piece was taken out from a thermostatic bath at 70 ° C. for 7 days, a tensile test was performed based on the above-described method of tensile properties.
Insulation resistance About each insulated wire, the insulation resistance prescribed | regulated to JISC3005 was measured, and it converted into the volume specific resistance with the following formula | equation.
ρ = (L / 3.665) · (1 / (log10 (D / d))) · 10 ⁷
Where ρ: volume resistivity (Ω · cm), L: length of the wire (mm), D: insulator outer diameter (mm), d: conductor outer diameter (mm), G: insulation resistance (MΩ) is there.

Each component material shown in the table is as follows.
(01) Polybutylene succinate
AZ92W (trade name, manufactured by Mitsubishi Chemical Corporation)
MFR = 4.5 g / 10 min (02) Polycarbodiimide
Carbodilite LA-1 (trade name, manufactured by Nisshinbo Co., Ltd.)
(03) Polycarbodiimide
Carbodilite HMV-8CI (trade name, manufactured by Nisshinbo)
(04) Hindered phenol anti-aging agent
Irganox 1010 (trade name, manufactured by Ciba-Gaigi)
(05) Calcium stearate
Calcium stearate (Nippon Yushi Co., Ltd.)
(06) Acrylic ester block copolymer LA-2250 (trade name, manufactured by Kuraray Co., Ltd.)
(07) Ethylene vinyl acetate copolymer V-527-4 (trade name, manufactured by Mitsui DuPont Polychemical Co., Ltd.)

As is clear from Table 2, in Comparative Example 1 and Comparative Example 3 in which no polycarbodiimide was blended, both the heat resistance and the heat resistance were poor in either case of the sheet or the insulated wire. Regarding volume resistivity, Comparative Example 1 is inferior to Examples 1 to 3 in which the blending amounts of other resin components are the same, and volume resistivity of Comparative Example 3 is the same as that of other resin components. This is inferior to Examples 5 and 6. Moreover, also in the comparative example 2 with few compounding quantities of polycarbodiimide, in any case of a sheet | seat or an insulated wire, it is inferior to heat-and-moisture resistance and heat resistance. In Comparative Example 4 where the amount of polycarbodiimide is large, the tensile strength and elongation characteristics are poor, and the volume resistivity is inferior.
On the other hand, the sheet | seat or insulated wire using resin of Examples 1-6 was excellent in mechanical characteristics, moist heat resistance, heat resistance, and volume specific resistance.

Claims (6)

A resin composition containing 1 to 20 parts by mass of polycarbodiimide with respect to 100 parts by mass of a resin component containing a polybutylene succinate resin, and a sheet having a thickness of 1 mm is formed from the resin composition An insulating coating material for a conductor or an optical fiber, comprising a resin composition having a volume resistivity based on JIS K 6723 of 1.0 × 10 ^{11 to} 2.0 × 10 ¹³ Ωcm. 2. The conductor or optical fiber insulation coating according to claim 1, wherein the polybutylene succinate resin has an MFR ( melt flow rate, 190 ° C., 2.16 kg) of 3 to 40 g / 10 minutes. Wood.   The conductor or optical fiber insulation coating material according to claim 1 or 2, wherein the resin composition contains an ethylene-vinyl acetate copolymer or an acrylic resin.   The conductor or optical fiber insulation coating material according to claim 1, wherein the resin composition contains a fatty acid-based lubricant.   An insulated wire or cable, wherein the insulation coating material according to any one of claims 1 to 4 is coated around a conductor. An optical fiber cord or an optical fiber cable, wherein the insulating coating material according to any one of claims 1 to 4 is coated around an optical fiber.