JP2018039903A - Flame-retardant resin composition, and electric insulated wire, metal cable, optical fiber cable, wire harness for automobile and molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition having excellent flamer retardancy and abrasion resistance while having excellent recovery property when charged into water, and to provide an electric insulated wire, a metal cable, an optical fiber cable, a wire harness for automobile, and a molded article using the same.SOLUTION: A flame-retardant resin composition contains a base resin, 1 pt.mass or more and less than 10 pts.mass of calcium carbonate particles with respect to 100 pts.mass of the base resin, 0.5 pts.mass or more and 10 pts.mass or less of a silicone-based compound with respect to 100 pts.mass of the base resin, and 0.5 pts.mass or more and 10 pts.mass or less of a fatty acid-containing compound with respect to 100 pts.mass of the base resin, and contains a propylene-based resin in the base resin, where a density of the flame-retardant resin composition is less than 0.98 g/cm.SELECTED DRAWING: None

Description

  The present invention relates to a flame retardant resin composition, an insulated wire using the same, a metal cable, an optical fiber cable, an automobile wire harness, and a molded product.

  Flame retardant resin compositions are often used for coverings of cables such as metal cables and optical fiber cables, cable jackets, tubes, tapes, packaging materials, building materials, and the like. As such a flame-retardant resin composition, conventionally, for example, calcium carbonate particles blended at a ratio of 10 parts by mass or more with respect to 100 parts by mass of the base resin, and a silicone compound compounded at a ratio of more than 1 part by mass And a flame retardant composition containing a fatty acid-containing compound blended in a proportion greater than 3 parts by mass (see Patent Document 1 below).

JP 2014-94969 A

  By the way, in order to recycle the resin in the flame retardant resin composition, a mixture of the flame retardant resin composition and another resin composition is poured into water and the flame retardant is utilized by utilizing the difference in density from the mixture. When recovering the resin composition, it is desirable to reduce the density of the flame retardant resin composition as much as possible in order to improve the recoverability.

  However, the flame retardant resin composition described in Patent Document 1 has the following problems.

  That is, when trying to reduce the density of the flame retardant resin composition described in Patent Document 1, the flame retardancy or wear resistance of the flame retardant resin composition may be reduced.

  The present invention has been made in view of the above circumstances, and has a flame retardant resin composition having excellent flame retardancy and wear resistance while having excellent recoverability when introduced into water, It aims at providing the insulated wire used, the metal cable, the optical fiber cable, the wire harness for motor vehicles, and a molded article.

  The present inventors have studied to solve the above problems. As a result, the inventors set the density of the flame retardant resin composition to less than a predetermined value, and blend the calcium carbonate particles, the silicone compound, and the fatty acid-containing compound with a predetermined ratio with respect to the base resin, It has been found that the above problems can be solved by including a propylene-based resin in the base resin, and the present invention has been completed.

That is, the present invention provides a base resin, calcium carbonate particles blended at a ratio of 1 part by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the base resin, and 0.5 parts by mass with respect to 100 parts by mass of the base resin. Including a silicone compound compounded at a ratio of not less than 10 parts by mass and not more than 10 parts by mass, and a fatty acid-containing compound compounded at a ratio of not less than 0.5 parts by mass and not more than 10 parts by mass with respect to 100 parts by mass of the base resin, The base resin is a flame retardant resin composition containing a propylene-based resin, and the flame retardant resin composition has a density of less than 0.98 g / cm ³ .

Since the flame-retardant resin composition of the present invention has a low density of less than 0.98 g / cm ³ , it can float in water and, of course, has a high ascent rate when thrown into water. Moreover, the flame-retardant resin composition of the present invention can have excellent flame retardancy and wear resistance while having a low density of less than 0.98 g / cm ³ . Therefore, the flame retardant resin composition of the present invention can have excellent flame retardancy and wear resistance while having excellent recoverability when introduced into water.

  In addition, the present inventors guess as follows about the reason for the above effect.

  That is, in the present invention, the blending amount of the calcium carbonate particles that greatly contribute to the increase in density and excellent wear resistance is suppressed to a sufficiently low ratio. For this reason, sufficient density reduction of a flame-retardant resin composition is realizable. However, if the blending amount of the calcium carbonate particles is suppressed to a sufficiently low ratio, the wear resistance of the flame retardant resin composition is lowered. On the other hand, in the present invention, in order to compensate for this decrease in wear resistance, the base resin contains a propylene-based resin having excellent wear resistance. Therefore, the present inventors speculate that the above effect may be obtained.

  In the said flame-retardant resin composition, it is preferable that the said base resin consists of polyolefin resin and the content rate of the said propylene-type resin in the said polyolefin resin is 20 mass% or more.

  In this case, compared with the case where the content of the propylene-based resin in the polyolefin resin is less than 20% by mass, excellent low temperature embrittlement resistance and impact resistance characteristics can be obtained in the flame retardant resin composition.

  In the said flame-retardant resin composition, it is preferable that the content rate of the said propylene-type resin in the said polyolefin resin is 100 mass%.

  In this case, more excellent wear resistance can be obtained as compared with the case where the content of the propylene-based resin in the polyolefin resin is less than 100% by mass.

  In the flame retardant resin composition, the propylene resin includes a polar group-containing propylene resin containing a polar group, and the content of the polar group-containing propylene resin in the base resin is 1 to 10 mass. % Is preferred.

  In this case, compared with the case where the content of the polar group-containing propylene-based resin in the base resin is less than 1% by mass, the compatibility of the base resin with the calcium carbonate particles, the silicone-based compound, and the fatty acid-containing compound is increased. Generation is suppressed, and more excellent wear resistance is obtained. On the other hand, compared with the case where the content of the polar group-containing propylene resin in the base resin exceeds 10% by mass, the processability of the flame-retardant resin composition is further improved and the increase in cost can be suppressed more sufficiently. it can.

  In the flame retardant resin composition, the polar group is preferably a maleic anhydride group.

  In this case, even when the content of the polar group-containing propylene-based resin in the base resin is smaller, the above-described effects can be obtained, so that deterioration in physical properties such as mechanical properties can be sufficiently suppressed.

  Moreover, this invention is an insulated wire provided with the conductor and the insulating layer which coat | covers the said conductor, and the said insulating layer is comprised with the said flame-retardant resin composition.

According to this insulated wire, the insulating layer is composed of the flame retardant resin composition, and the flame retardant resin composition has a low density of less than 0.98 g / cm ^{3 and} can float in water. Of course, the ascent rate is high when thrown into water. For this reason, the recoverability of the insulating layer is improved when the insulating layer is peeled from the insulated wire and poured into water. Therefore, the insulated wire of the present invention is excellent in recyclability. Moreover, since the said flame-retardant resin composition has a low density less than 0.98 g / cm < ³ >, an insulated wire is fully reduced in weight. Furthermore, the flame retardant resin composition has excellent flame retardancy and wear resistance while having a low density of less than 0.98 g / cm ³ . For this reason, the insulated wire can also have excellent flame retardancy and wear resistance.

  The present invention also includes a conductor, an insulated wire having an insulating layer covering the conductor, and a coating layer provided so as to surround the insulated wire, wherein at least one of the insulating layer and the coating layer is It is a metal cable comprised with the said flame-retardant resin composition.

According to this metal cable, at least one of the insulating layer and the coating layer is composed of the flame retardant resin composition, and the flame retardant resin composition has a low density of less than 0.98 g / cm ³ , As a matter of course, the ascent rate is high when it is put into water. For this reason, the recoverability of the insulating layer or the covering layer when the insulating layer and the covering layer made of the flame retardant resin composition are peeled from the metal cable and put into water is improved. Therefore, the metal cable of the present invention is excellent in recyclability. Moreover, since the said flame retardant resin composition has a low density of less than 0.98 g / cm < ³ >, a metal cable is fully reduced in weight. Furthermore, the flame retardant resin composition has excellent flame retardancy and wear resistance while having a low density of less than 0.98 g / cm ³ . For this reason, the metal cable can also have excellent flame retardancy and wear resistance.

  Furthermore, the present invention includes an optical fiber and a covering portion that covers the optical fiber, and the covering portion includes an insulator that directly covers the optical fiber, and the insulator includes the flame-retardant resin composition. It is an optical fiber cable composed of objects.

According to this optical fiber cable, the insulator in the covering portion of the optical fiber cable is composed of the flame retardant resin composition, and the flame retardant resin composition has a low density of less than 0.98 g / cm ^3. Of course, it is possible to float in water. For this reason, the recoverability of the insulator when the outer skin is peeled from the optical fiber cable and poured into water is improved. Therefore, the optical fiber cable of the present invention is excellent in recyclability. Moreover, since the said flame retardant resin composition has a low density of less than 0.98 g / cm < ³ >, an optical fiber cable is fully reduced in weight. Furthermore, the flame retardant resin composition has excellent flame retardancy and wear resistance while having a low density of less than 0.98 g / cm ³ . For this reason, the optical fiber cable can also have excellent flame retardancy and wear resistance.

  The present invention is an automotive wire harness having at least one selected from the group consisting of an insulated wire, a metal cable and an optical fiber cable, wherein the insulated wire is composed of the insulated wire, and the metal cable is It is comprised by the said metal cable, and the said optical fiber cable is a wire harness for motor vehicles comprised by the said optical fiber cable.

  The automotive wire harness of the present invention includes at least one selected from the group consisting of an insulated wire, a metal cable, and an optical fiber cable having excellent flame retardancy and wear resistance, and thus has excellent flame retardancy and wear resistance. Have sex. Therefore, the automotive wire harness of the present invention is suitable for automotive applications. Moreover, since the wire harness for motor vehicles of this invention is equipped with at least 1 sort (s) chosen from the group which consists of the insulated wire, metal cable, and optical fiber cable which have the outstanding recyclability, it is excellent in recyclability.

  Moreover, this invention is a molded article containing the said flame retardant resin composition.

Since the flame retardant resin composition has excellent flame retardancy and wear resistance, the molded article of the present invention can also have excellent flame retardancy and wear resistance. Further, the flame retardant resin composition has a low density of less than 0.98 g / cm ^{3 and} can float in water, and of course has a high ascent rate when thrown into water. For this reason, the recoverability at the time of throwing into the water what is comprised with the said flame-retardant resin composition among molded articles improves. Therefore, the molded product of the present invention is excellent in recyclability. Furthermore, since the flame retardant resin composition has a low density of less than 0.98 g / cm ³ , the molded article of the present invention is sufficiently lightened.

  According to the present invention, a flame retardant resin composition having excellent flame retardancy and wear resistance while having excellent recoverability when thrown into water, an insulated wire, a metal cable, an optical Fiber cables, automotive wire harnesses, and molded articles are provided.

It is a partial side view which shows one Embodiment of the metal cable of this invention. It is sectional drawing along the II-II line of FIG. It is sectional drawing which shows embodiment of the optical fiber cable of this invention. It is sectional drawing which shows embodiment of the wire harness for motor vehicles of this invention.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 1 and 2.

[Metal cable]
FIG. 1 is a partial side view showing an embodiment of a metal cable according to the present invention. FIG. 2 is a cross-sectional view taken along the line II-II in FIG. As shown in FIGS. 1 and 2, the metal cable 10 includes an insulated wire 4 and a coating layer 3 that covers the insulated wire 4. The insulated wire 4 includes a conductor 1 and an insulating layer 2 that covers the conductor 1.

Here, the insulating layer 2 and the coating layer 3 are composed of a flame retardant resin composition, and the flame retardant resin composition is 1 part by mass or more and 10 parts by mass with respect to 100 parts by mass of the base resin and the base resin. With respect to 100 parts by mass of calcium carbonate particles compounded at a ratio of less than 10 parts, a silicone compound compounded at a ratio of 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base resin. And a fatty acid-containing compound blended at a ratio of 0.5 parts by mass or more and 10 parts by mass or less, and the base resin contains a propylene-based resin. The density of the flame retardant resin composition is less than 0.98 g / cm ³ .

The insulating layer 2 and the coating layer 3 are composed of the flame retardant resin composition, and the flame retardant resin composition has a low density of less than 0.98 g / cm ^{3 and} can float in water. Needless to say, the ascent rate is high when thrown into water. For this reason, the recoverability of the insulating layer 2 or the coating layer 3 when the insulating layer 2 or the coating layer 3 is peeled from the metal cable 10 and poured into water is improved. Therefore, the metal cable 10 is excellent in recyclability. Further, since the flame retardant resin composition has a low density of less than 0.98 g / cm ³ , the metal cable 10 is sufficiently lightened. Furthermore, the flame retardant resin composition has excellent flame retardancy and wear resistance while having a low density of less than 0.98 g / cm ³ . For this reason, the metal cable 10 can also have excellent flame retardancy and wear resistance.

  Hereinafter, the flame retardant resin composition constituting the insulating layer 2 and the coating layer 3 will be described in detail.

(Flame retardant resin composition)
As described above, the flame retardant resin composition includes the base resin, calcium carbonate particles blended at a ratio of 1 part by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the base resin, and 100 parts by mass of the base resin. Fatty acid content blended at a ratio of 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base compound and a silicone compound blended at a ratio of 0.5 parts by mass or more and 10 parts by mass or less Compound.

As described above, the density of the flame retardant resin composition is less than 0.98 g / cm ³ . In this case, the flame retardant resin composition floats in water, as well as the ascending speed when poured into water, compared to the case where the density of the flame retardant resin composition is 0.98 g / cm ³ or more. It becomes larger and the recoverability of the flame retardant resin composition is further improved. The density of the flame retardant resin composition is preferably 0.95 g / cm ³ or less. In this case, when the flame retardant resin composition is poured into water, the rising speed of the flame retardant resin composition is further increased. However, the density of the flame retardant resin composition is preferably 0.93 g / cm ³ or more. In this case, the flame retardant resin composition has more excellent wear resistance and flame retardancy.

(Base resin)
As described above, the base resin only needs to contain a propylene-based resin.

  The propylene-based resin is a resin containing propylene as a structural unit. Examples of the propylene-based resin include homopolypropylene, propylene block copolymer, propylene random copolymer, and a copolymer containing a propylene-α olefin copolymer. Among them, homopolypropylene or propylene block copolymer is preferable from the viewpoint of heat resistance and wear resistance, and propylene block copolymer is particularly preferable from the viewpoint of low-temperature embrittlement characteristics.

  The propylene-based resin may further include a polar group-containing propylene-based resin containing a polar group. Here, the content of the polar group-containing propylene resin in the base resin is not particularly limited, but is preferably 1 to 10% by mass. Compared with the case where the content of the polar group-containing propylene resin in the base resin is less than 1% by mass, the compatibility of the base resin with the calcium carbonate particles, the silicone compound, and the fatty acid-containing compound is increased, and the occurrence of bloom is generated. In addition to being suppressed, better wear resistance is obtained. On the other hand, compared with the case where the content of the polar group-containing propylene resin in the base resin exceeds 10% by mass, the processability of the flame-retardant resin composition is further improved and the increase in cost can be suppressed more sufficiently. it can. The content of the polar group-containing propylene resin in the base resin is more preferably 2 to 5% by mass.

  Examples of the polar group of the polar group-containing propylene resin include a maleic acid group, a methacrylic acid group, a fumaric anhydride group, a maleic anhydride group, a hydroxyl group, and a carboxyl group. Among these, as the polar group, a maleic anhydride group is preferable. In this case, since the above-mentioned effect can be obtained even when the content of the polar group-containing propylene resin in the base resin is small, a decrease in physical properties such as mechanical properties can be suppressed.

  The base resin may be made of only a polyolefin resin, or may be made of a polyolefin resin and a resin other than the polyolefin resin, but the base resin is preferably made of only a polyolefin resin. In this case, the polyolefin resin has good compatibility with the propylene-based resin, and more excellent wear resistance can be obtained.

  When the base resin is made of only a polyolefin resin, the polyolefin resin contains a propylene-based resin. Here, the polyolefin resin may be composed only of a propylene resin, or may be composed of a propylene resin and a resin other than the propylene resin.

  The content of the propylene-based resin in the polyolefin resin is not particularly limited, but is preferably 20% by mass or more. In this case, compared with the case where the content of the propylene-based resin in the polyolefin resin is less than 20% by mass, excellent low temperature embrittlement resistance and impact resistance characteristics can be obtained in the flame retardant resin composition.

  Here, it is preferable that the content rate of the propylene-type resin in polyolefin resin is 100 mass%. In this case, superior wear resistance can be obtained as compared with the case where the base resin contains a resin other than the propylene-based resin.

  In addition, when the content rate of the propylene-type resin in polyolefin resin is less than 100 mass%, polyolefin resin consists of resin other than propylene-type resin and propylene-type resin. Examples of the resin other than the propylene resin include polybutene, polyethylene resin, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate copolymer.

(Calcium carbonate particles)
The calcium carbonate particles may be either heavy calcium carbonate or light calcium carbonate.

  The average particle size of the calcium carbonate particles is not particularly limited, but is preferably 0.7 μm or more. In this case, more excellent flame retardancy can be obtained as compared with the case where the average particle diameter of the calcium carbonate particles is less than 0.7 μm.

  However, the average particle size of the calcium carbonate particles is preferably 1.8 μm or less. In this case, compared to the case where the average particle diameter of the calcium carbonate particles exceeds 1.8 μm, the generation of bubbles when forming the insulating layer 2 and the coating layer 3 can be sufficiently suppressed. For this reason, in the insulating layer 2 and the coating layer 3, the non-flammability nonuniformity and the wear-resistant fall can fully be suppressed.

  The calcium carbonate particles are blended at a ratio of 1 part by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the base resin. In this case, more excellent wear resistance can be obtained as compared with the case where the proportion of the calcium carbonate particles is less than 1 part by mass with respect to 100 parts by mass of the base resin. Further, when the blending ratio of the calcium carbonate particles with respect to 100 parts by mass of the base resin is within the above range, the flame retardant resin is compared with the case where the blending ratio of the calcium carbonate particles with respect to 100 parts by mass of the base resin is 10 parts by mass or more. The density of the composition can be reduced, and the recoverability when the flame retardant resin composition is added to water is further improved.

  Moreover, it is more preferable that the calcium carbonate particles are blended at a ratio of 5 to 8 parts by mass with respect to 100 parts by mass of the base resin. Compared with the case where the blending ratio of the calcium carbonate particles with respect to 100 parts by mass of the base resin is out of the above range, excellent wear resistance can be obtained while sufficiently ensuring the flame retardancy of the flame retardant resin composition.

(Silicone compound)
The silicone compound functions as a flame retardant aid, and examples of the silicone compound include polyorganosiloxane. Here, the polyorganosiloxane has a siloxane bond as a main chain and an organic group in a side chain. Examples of the organic group include alkyl groups such as a methyl group, an ethyl group, and a propyl group; a vinyl group; and a phenyl group. Aryl groups and the like. Specific examples of the polyorganosiloxane include dimethylpolysiloxane, methylethylpolysiloxane, methyloctylpolysiloxane, methylvinylpolysiloxane, methylphenylpolysiloxane, and methyl (3,3,3-trifluoropropyl) polysiloxane. Is mentioned. Examples of the polyorganosiloxane include silicone powder, silicone gum, and silicone resin. Among these, silicone gum is preferable. In this case, compared to the case where the silicone compound is a silicone compound other than silicone gum, blooming is less likely to occur in the flame retardant resin composition.

  As described above, the silicone compound is blended at a ratio of 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base resin. In this case, more excellent flame retardancy can be obtained as compared with the case where the blending ratio of the silicone compound to 100 parts by mass of the base resin is less than 0.5 parts by mass. Moreover, when the compounding ratio of the silicone compound with respect to 100 parts by mass of the polyolefin resin is within the above range, the silicone compound in the flame retardant resin composition is more than when the compounding ratio of the silicone compound is larger than 10 parts by mass. The bloom of can be suppressed more fully.

  The silicone compound is preferably blended at a ratio of 1.5 to 3 parts by mass with respect to 100 parts by mass of the base resin. In this case, more excellent flame retardancy can be obtained, and when printing is performed on the coating layer 3, printing can be performed more clearly.

(Fatty acid-containing compound)
The fatty acid-containing compound functions as a flame retardant aid. The fatty acid-containing compound refers to a compound containing a fatty acid or a metal salt thereof. Here, as the fatty acid, for example, a fatty acid having 12 to 28 carbon atoms is used. Examples of such fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, tuberculostearic acid, oleic acid, linoleic acid, arachidonic acid, behenic acid and montanic acid. Among these, stearic acid is preferable as the fatty acid. In this case, more excellent flame retardancy can be obtained as compared with the case of using a fatty acid other than stearic acid.

  Examples of the metal constituting the fatty acid metal salt include magnesium, calcium, zinc and lead. As the metal salt of fatty acid, magnesium stearate or calcium stearate is preferable, and magnesium stearate is particularly preferable. In this case, compared with the case where fatty acid metal salts other than magnesium stearate or calcium stearate are used, excellent flame retardancy can be obtained with a smaller addition amount in the flame retardant resin composition.

  As described above, the fatty acid-containing compound is blended at a ratio of 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base resin. In this case, more excellent flame retardancy is obtained as compared with the case where the blending ratio of the fatty acid-containing compound is less than 0.5 parts by mass with respect to 100 parts by mass in the base resin. Further, when the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the base resin is within the above range, the flame-retardant resin composition is compared with the case where the blending ratio of the fatty acid-containing compound with respect to 100 parts by mass of the base resin is larger than 10 parts by mass. Moisture absorption by objects can be more sufficiently suppressed.

  The fatty acid-containing compound is preferably blended at a ratio of 1.5 to 5 parts by mass with respect to 100 parts by mass of the base resin. In this case, as compared with the case where the ratio of the fatty acid-containing compound is out of the above range, more excellent flame retardancy is obtained in the flame retardant resin composition, and moisture absorption by the flame retardant resin composition can be more sufficiently suppressed. .

  The flame retardant resin composition may further contain a filler such as an antioxidant, a metal deactivator, an ultraviolet degradation inhibitor, a processing aid, a color pigment, a lubricant, and carbon black as necessary.

[Metal cable manufacturing method]
Next, the manufacturing method of the metal cable 10 mentioned above is demonstrated.

<Conductor>
First, the conductor 1 is prepared. The conductor 1 may be configured by only one strand, or may be configured by bundling a plurality of strands. The material of the conductor 1 is not particularly limited, but is preferably aluminum or an aluminum alloy from the viewpoint of weight reduction. As for the cross-sectional area of the conductor, it is not particularly limited, in view of the small-diameter and weight, preferably less than 5 mm ^2, and more preferably 3 mm ² or less. However, from the viewpoint of the strength and conductivity of the conductor 1, the cross-sectional area of the conductor 1 is preferably 0.13 mm ² or more.

<Insulating layer>
Next, the conductor 1 is covered with the flame retardant resin composition, and the insulating layer 2 is formed so as to surround the conductor 1. Specifically, the flame retardant resin composition is kneaded using an extruder to form a tubular extrudate. Then, the tubular extrudate is continuously coated on the conductor 1. Thus, the insulated wire 4 is obtained.

  The kneading can be performed with a kneading machine such as a Banbury mixer, a tumbler, a pressure kneader, a kneading extruder, a twin screw extruder, a mixing roll, and the like. At this time, from the viewpoint of improving the dispersibility of the silicone compound, a part of the base resin and the silicone compound are kneaded, and the obtained master batch (MB) is mixed with the remaining base resin, calcium carbonate particles and fatty acid. You may knead | mix with a containing compound etc.

  The thickness of the insulating layer 2 is not particularly limited, but is preferably less than 0.7 mm. In this case, compared with the case where the thickness of the insulating layer 2 is 0.7 mm or more, the metal cable 10 can be reduced in weight and diameter. The thickness of each insulating layer 2 is more preferably 0.6 mm or less, and further preferably 0.5 mm or less. However, from the viewpoint of wear resistance, the thickness of the insulating layer 2 is preferably 0.1 mm or more. The thickness of the insulating layer 2 is more preferably 0.15 mm or more, and particularly preferably 0.2 mm or more.

<Coating layer>
Finally, one insulated wire 4 obtained as described above is prepared, and this insulated wire 4 is covered with the coating layer 3 produced using the above-mentioned flame-retardant resin composition. The covering layer 3 protects the insulating layer 2 from physical or chemical damage.

  Although the thickness of the coating layer 3 is not specifically limited, It is preferable that it is less than 0.7 mm. In this case, the metal cable 10 can be further reduced in weight compared to the case where the thickness of the coating layer 3 is 0.7 mm or more. The thickness of the coating layer 3 is more preferably 0.6 mm or less, and further preferably 0.5 mm or less. However, from the viewpoint of wear resistance, the thickness of the coating layer 3 is preferably 0.4 mm or more.

  The metal cable 10 is obtained as described above.

  The present invention is not limited to the above embodiment. For example, although the metal cable 10 has one insulated wire 4 in the above embodiment, the metal cable of the present invention may have two or more insulated wires 4 inside the coating layer 3. Further, a shield layer formed by braiding a metal wire such as copper or aluminum may be provided between the covering layer 3 and the insulated wire 4. That is, the metal cable of the present invention may be a coaxial cable.

  Moreover, in the said embodiment, although the insulating layer 2 and the coating layer 3 of the insulated wire 4 are comprised with said flame-retardant resin composition, the insulating layer 2 is comprised with normal insulation resin, and only the coating layer 3 is comprised. The flame retardant resin composition constituting the insulating layer 2 may be used.

  Furthermore, the flame-retardant resin composition constituting the insulating layer 2 and the covering layer 3 of the insulated wire 4 in the above embodiment can be applied as a covering portion for covering an optical fiber in an optical fiber cable. For example, FIG. 3 is a sectional view showing a drop type optical fiber cable as an example of the optical fiber cable of the present invention. As shown in FIG. 3, the optical fiber cable 20 includes a support wire 21, two tension members 22 and 23, an optical fiber 24, and a covering portion 25 that covers them. Here, the coating | coated part 25 is comprised with the insulator which coat | covers the optical fiber 24 directly, and an insulator is the flame-retardant resin composition which comprises the insulating layer 2 and the coating layer 3 of the insulated wire 4 in the said embodiment. Composed.

In the optical fiber cable 20, the insulator constituting the covering portion 25 is composed of the flame retardant resin composition, and the flame retardant resin composition has a low density of less than 0.98 g / cm ^3. Of course, it is possible to float in water. For this reason, the recoverability of the insulator is improved when the insulator is peeled from the optical fiber cable 20 and poured into water. Therefore, the optical fiber cable 20 is excellent in recyclability. Moreover, since the said flame retardant resin composition has a low density of less than 0.98 g / cm < ³ >, the optical fiber cable 20 is fully reduced in weight. The flame-retardant resin composition has excellent flame retardancy and wear resistance while having a low density of less than 0.98 g / cm ³ . For this reason, the optical fiber cable 20 can also have excellent flame retardancy and wear resistance.

  In the optical fiber cable 20, the covering portion 25 is made of an insulator, but the covering portion 25 may further include a covering body that covers the insulator. Here, the covering may be used as an outer skin. The optical fiber cable 20 includes one optical fiber 24, but the optical fiber cable of the present invention may include a plurality of optical fibers 24.

[Automotive wire harness]
FIG. 4 is a cross-sectional view showing an example of an automotive wire harness according to the present invention. As shown in FIG. 4, the automotive wire harness 30 includes a plurality of insulated wires 4 and a tape 31 that bundles the plurality of insulated wires 4. The tape 31 does not necessarily cover the plurality of insulated wires 4 along the length direction, and partially covers the plurality of insulated wires 4 at necessary portions along the length direction. If you do.

  Since the automotive wire harness 30 includes the insulated wire 4 having excellent flame retardancy and wear resistance, it can have excellent flame retardancy and wear resistance. Therefore, this automotive wire harness 30 is suitable for automotive applications. Moreover, since this wire harness 30 for motor vehicles is equipped with the insulated wire 4 which has the outstanding recyclability, it is excellent in recyclability.

  In the automotive wire harness 30, the tape 31 may be composed of a flame retardant resin composition that constitutes the insulating layer 2 and the covering layer 3 of the insulated wire 4 in the above embodiment, or other composition. It may be comprised.

  The automotive wire harness 30 includes a plurality of insulated wires 4, but may include only one insulated wire 4. In the automotive wire harness 30, the metal cable 10 or the optical fiber cable 20 can be used instead of the insulated wire 4. In the automotive wire harness 30, one type of the insulated wire 4, the metal cable 10, and the optical fiber cable 20 may be used alone, or two or more types may be used in combination.

  In addition, the automobile wire harness 30 includes a tape 31, but the automobile wire harness 30 may use a binding band or the like instead of the tape 31.

[Molding]
Moreover, in the said embodiment, the flame-retardant resin composition which comprises the insulating layer 2 and the coating layer 3 of the insulated wire 4 is applicable also to the material which comprises a molded article.

Since the flame retardant resin composition has excellent flame retardancy and wear resistance, a molded article composed of the flame retardant resin composition can also have excellent flame retardancy and wear resistance. . Further, the flame retardant resin composition has a low density of less than 0.98 g / cm ^{3 and} can float in water, and of course has a high ascent rate when thrown into water. For this reason, the recoverability at the time of throwing into the water what is comprised with the said flame-retardant resin composition among molded articles improves. Therefore, the molded product of the present invention is excellent in recyclability. Since the flame retardant resin composition has a low density of less than 0.98 g / cm ³ , a molded article composed of the flame retardant resin composition is sufficiently lightened.

<Application>
The flame-retardant resin composition of the present invention can be applied to an insulating layer of an insulated wire for automobiles, an insulating layer or a covering layer of a control cable or a power cable, a molded product, and the like.

  Hereinafter, the content of the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to the following examples.

(Examples 1 to 29 and Comparative Examples 1 to 13)
A base resin, a silicone masterbatch (silicone MB), a fatty acid-containing compound and calcium carbonate particles are blended in the blending amounts shown in Tables 1 to 6, and kneaded at 170 ° C. for 30 minutes by an open roll. Got. In Tables 1 to 6, the unit of the blending amount of each blending component is part by mass. In Tables 1 to 6, the compounding amount in the base resin column is not 100 parts by mass, but the resin is also contained in the silicone MB, and the compounding amount in the base resin column and the resin in the silicone MB If the blending amount is totaled, the total is 100 parts by mass.

  Specific examples of the base resin, silicone MB, calcium carbonate particles, and fatty acid-containing compounds are as follows.

(1) Base resin (propylene resin)
PP-1: Polypropylene block copolymer (trade name “E701G”, manufactured by Prime Polymer Co., Ltd.)
PP-2: Homopolypropylene (trade name “E111G”, manufactured by Prime Polymer Co., Ltd.)
PP-3: Low melting point polypropylene (trade name “WMG03”, manufactured by Nippon Polypro Co., Ltd.)
PP-4 (polar group-containing): maleic anhydride-modified propylene resin (trade name “Admer QE800”, manufactured by Mitsui Chemicals, Inc.)
(Polybutene)
Polybutene: Polybutene-1 (trade name “Buron 5050N”, manufactured by Mitsui Chemicals, Inc.)
(Polyethylene resin)
PE-1: High-density polyethylene (trade name “Hizex5305E”, manufactured by Prime Polymer Co., Ltd.)
PE-2: Low density polyethylene (trade name “Excellen GMH CB2001”, manufactured by Sumitomo Chemical Co., Ltd.)

(2) Silicone MB
Silicone MB-1: (trade name “X-22-2125H”, manufactured by Shin-Etsu Chemical Co., Ltd.)
Silicone MB-2 containing 50% by mass silicone gum and 50% by mass low-density polyethylene: (trade name “X-22-2101”, manufactured by Shin-Etsu Chemical Co., Ltd.)
Contains 50% by weight silicone gum and 50% by weight propylene-based resin

(3) Calcium carbonate particle average particle size 1.7 μm (trade name “NCC_P”, manufactured by Nitto Flour Chemical Co., Ltd.)

(4) Fatty acid-containing compound Mg stearate (trade name “Efco Chem MGS”, manufactured by ADEKA)

Next, this flame retardant resin composition is put into an extruder (25 mm extruder, manufactured by Mars Seiki Co., Ltd.), the extrudate is extruded from the extruder, and seven strands having a diameter of 0.6 mm are twisted together. Thus, a conductor having a cross-sectional area of 2 mm ² was coated to a thickness of 0.2 mm. Thus, an insulated wire was obtained.

About the flame retardant resin composition obtained as mentioned above, the density was measured using the electronic hydrometer (made by Alpha Mirage). The results are shown in Tables 1-6. In Tables 1 to 6, the unit of density is g / cm ³ .

  About the flame-retardant resin compositions and insulated wires of Examples 1 to 29 and Comparative Examples 1 to 13 obtained as described above, flame retardancy, wear resistance, floatability in water as follows, The recoverability and bloom resistance when put into water were evaluated.

<Flame retardance>
About the insulated wire obtained from the said flame-retardant resin composition of Examples 1-29 and Comparative Examples 1-13, the horizontal combustion test, the 45 degree inclination combustion test, and the 60 degree inclination combustion test were done. Each combustion test is shown below.
(Horizontal combustion test)
About the insulated wire obtained from the said flame-retardant resin composition of Examples 1-29 and Comparative Examples 1-13, the horizontal combustion test based on JASO D618 was done. The results are shown in Tables 1-6. In Tables 1 to 6, after flame contact until the insulated wire burns, the product that self-extinguishes within 30 seconds from the start of combustion is indicated as “◯” as being excellent in flame retardancy, and self-extinguishing within 30 seconds What was not done was described as "x" as inferior in a flame retardance.
(45 degree inclined combustion test)
About the insulated wire obtained from the said flame-retardant resin composition of Examples 1-29 and Comparative Examples 1-13, the 45 degree inclination combustion test based on ISO6722-1 was done. The results are shown in Tables 1-6. In Tables 1-6, the insulated wire was flamed for 15 seconds and then self-extinguished within 70 seconds was marked as “◯” as having excellent flame retardancy, and was not self-extinguished within 70 seconds. Was marked as “x” as being inferior in flame retardancy.
(60 degree inclined combustion test)
About the insulated wire obtained from the said flame-retardant resin composition of Examples 1-29 and Comparative Examples 1-13, the 60 degree inclination combustion test based on JISC3005 was done. The results are shown in Tables 1-6. In Tables 1 to 6, after flame contact until the insulated wire burns, the self-extinguishing within 60 seconds from the start of combustion is indicated as “◯” as being excellent in flame retardancy, and self-extinguishing within 60 seconds. What was not done was described as "x" as inferior in a flame retardance.
(passing grade)
Flame retardancy was evaluated by the horizontal combustion test described above, and was self-extinguished within 30 seconds from the start of combustion.

<Abrasion resistance>
Abrasion resistance was evaluated by performing a scrape wear test in accordance with JASO D618 on the insulated wires obtained from the flame retardant resin compositions of Examples 1 to 29 and Comparative Examples 1 to 13 and the number of times until conduction. . The results are shown in Tables 1-6. In Tables 1 to 6, “A” is indicated as being particularly excellent in wear resistance when the number of times until conduction is 5000 times or more, and excellent in wear resistance when it is 2000 to 4999 times. As “B”, when it is 750 to 1999 times, it is written as “C” as being slightly superior in wear resistance, and when it is less than 750 times, it is written as “D” as being inferior in wear resistance. did. In addition, about abrasion resistance, "A", "B", or "C" was set as the pass.

<Floatability in water>
The floatability was evaluated based on whether the flame retardant resin compositions of Examples 1 to 29 and Comparative Examples 1 to 13 were put in pure water and floated on the water surface. The results are shown in Tables 1-6. In Tables 1 to 6, those that floated on the water surface were denoted as “◯”, and those that did not float on the water surface were denoted as “x”.

<Recoverability when thrown into water>
The recoverability when put into water was evaluated as follows. That is, five test specimens having a diameter of 20 mm and a thickness of 1 mm prepared by processing the flame retardant resin compositions of Examples 1 to 29 and Comparative Examples 1 to 13 were prepared, and these specimens were submerged in water having a depth of 1 m. The specimen was released horizontally and the time until the specimen floated was measured. The same evaluation was performed on the five test specimens, and the average of the time until rising (average time) was obtained. The recoverability was evaluated by this average time. The results are shown in Tables 1-6. In Tables 1 to 6, when the time until all the test specimens floated was 60 seconds or less, it was indicated as “と し て” because it was particularly excellent in recoverability, and it was regarded as acceptable. Next, when the time until all the test specimens were lifted was 70 seconds or less, it was indicated as “◯” because it was excellent in recoverability. On the other hand, when the time until all the specimens surfaced exceeded 70 seconds, it was indicated as “x” because it was inferior in recoverability, and was rejected.

<Broom resistance>
The bloom resistance is about 85 ° C. and 90% RH constant temperature and humidity chamber (manufactured by Enomoto Kasei Co., Ltd.) for the insulated wires obtained from the flame retardant resin compositions of Examples 1 to 29 and Comparative Examples 1 to 13. Evaluation was carried out by observing the surface of the sample that had been left for 6 months by visual observation and using a microscope (manufactured by Keyence Corporation). The results are shown in Tables 1-6. In Tables 1 to 6, when the magnification of the microscope was 50 times, bloom was not confirmed, but it was marked as “◎” as being particularly excellent in bloom resistance, and the magnification of the microscope was 50 times If the amount of bloom is slightly confirmed, it is indicated as “○” as being excellent in bloom resistance, and if it is confirmed by visual inspection, it is indicated as “△” as being slightly inferior in bloom resistance. In the case where the bloom was clearly confirmed at, “×” was indicated as being inferior in bloom resistance.

  From the results shown in Tables 1 to 6, the flame retardant resin compositions of Examples 1 to 29 reached the acceptance criteria for flame retardancy, wear resistance, and recoverability when introduced into water. On the other hand, the flame retardant resin compositions of Comparative Examples 1 to 13 did not reach the acceptance criteria for at least one of flame retardancy, wear resistance, and recoverability when put into water.

  From this, it was confirmed that the flame retardant resin composition of the present invention has excellent flame retardancy and abrasion resistance while having excellent recoverability when it is put into water.

DESCRIPTION OF SYMBOLS 1 ... Conductor 2 ... Insulating layer 3 ... Covering layer 4 ... Insulated electric wire 10 ... Metal cable 20 ... Optical fiber cable 24 ... Optical fiber 25 ... Covering part 30 ... Wire harness 31 for motor vehicles 31 ... Outer skin

Claims (10)

A base resin;
Calcium carbonate particles blended at a ratio of 1 part by weight or more and less than 10 parts by weight with respect to 100 parts by weight of the base resin;
A silicone compound blended at a ratio of 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base resin;
A fatty acid-containing compound blended at a ratio of 0.5 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the base resin,
The base resin is a flame retardant resin composition containing a propylene-based resin,
The flame retardant resin composition wherein the density of the flame retardant resin composition is less than 0.98 g / cm ³ .   The flame-retardant resin composition according to claim 1, wherein the base resin is made of a polyolefin resin, and the content of the propylene-based resin in the polyolefin resin is 20% by mass or more.   The flame-retardant resin composition according to claim 2, wherein the content of the propylene-based resin in the polyolefin resin is 100% by mass. The propylene-based resin includes a polar group-containing propylene-based resin containing a polar group,
The flame retardant resin composition according to any one of claims 1 to 3, wherein a content of the polar group-containing propylene resin in the base resin is 1 to 10% by mass.   The flame retardant resin composition according to claim 4, wherein the polar group is a maleic anhydride group. Conductors,
An insulating layer covering the conductor,
The said insulated layer is an insulated wire comprised with the flame-retardant resin composition as described in any one of Claims 1-5. An insulated wire having a conductor and an insulating layer covering the conductor;
A coating layer provided so as to surround the insulated wire,
The metal cable in which at least one of the said insulating layer and the said coating layer is comprised with the flame-retardant resin composition as described in any one of Claims 1-5. Optical fiber,
A coating portion for coating the optical fiber,
The covering portion has an insulator directly covering the optical fiber;
An optical fiber cable in which the insulator is composed of the flame retardant resin composition according to any one of claims 1 to 5. An automotive wire harness having at least one selected from the group consisting of insulated wires, metal cables and optical fiber cables,
The insulated wire is composed of the insulated wire according to claim 6,
The metal cable is composed of the metal cable according to claim 7,
An automotive wire harness comprising the optical fiber cable according to claim 8.   The molded article containing the flame-retardant resin composition as described in any one of Claims 1-5.

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