JP2017004797A - Vinyl chloride resin composition, and insulated wire and cable using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a vinyl chloride resin composition which can suppress discoloration of an insulation layer or sheath surface caused by a base, can suppress occurrence of a rough surface and irregularities on the surface of the insulation layer or sheath surface, and further can make efficiency in electrical connection work good by maintaining uniform length of each exposed conductor after peeling of the insulation layer in a multi-core parallel insulated wire; and an insulated wire and cable using the same.SOLUTION: The insulated wire 10 comprises, on an outer periphery of a conductor 1 comprising a naked annealed copper wire, an insulation layer 2 comprising a vinyl chloride resin composition containing, in a base polymer containing a vinyl chloride resin, (A) a fatty acid metal salt, (B) a cyanuric acid derivative or isocyanuric acid derivative, (C) stearoyl benzoyl methane, and (D) a high density oxidized polyethylene wax, where a total content of the (A) to (D) relative to 100 pts.mass of the vinyl chloride resin is 1 to 4.5 pts.mass, and a mass content ratio (C/B) of the (C) stearoyl benzoyl methane relative to the (B) cyanuric acid derivative or the isocyanuric acid derivative is 0.25 to 6.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride resin composition, and an insulated wire and cable using the same, and in particular, a flame retardant vinyl chloride resin composition applicable to an electric wire in accordance with UL standards (commonly referred to as “UL electric wire”), and the same The present invention relates to insulated wires and cables using
To do.

  Insulated wires used for the internal wiring of electronic devices are required to be flame retardant so that the fire does not spread through the wires in the event of an ignition accident of the device.

  The flame retardance standard of the internal wiring material is determined by, for example, the UL758 standard in the United States. The vertical flammability test (hereinafter referred to as “VW-1 test”) is provided as an option for items required by UL758, but most insulated wires pass this test and are certified by UL. Nevertheless, the VW-1 test is an essential item.

  Conventionally, vinyl chloride resin (PVC) has been used as a main raw material for the covering material of such an insulated wire. Vinyl chloride resin contains chlorine, which is a halogen, in its chemical structure, and its flame retardancy is high. However, since vinyl chloride resin is hard, when used as an insulating material for electric wires, a large amount of a combustible plasticizer is added and used for softening. Therefore, unless the flame retardant is added, the above-described flame retardant standard cannot be satisfied.

  As this flame retardant, antimony trioxide has generally been used. However, since antimony trioxide is a powerful drug, strict management is required during production, and it is a material that should not be used. Furthermore, it is a rare metal and the price has been increasing recently.

  Therefore, metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used as a flame retardant instead of antimony trioxide (see, for example, Patent Document 1).

  Patent Document 1 discloses a vinyl chloride resin composition containing a vinyl chloride resin, aluminum hydroxide and / or magnesium hydroxide, a plasticizer and a non-lead stabilizer, and the aluminum hydroxide and / or hydroxide. There is disclosed a vinyl chloride resin composition having a magnesium content of 8 to 22 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, an antimony content of less than 1000 ppm, and crosslinked after molding. Yes.

  On the other hand, the vinyl chloride resin is heated to 170 ° C. or higher during the molding process, and chlorine is released from the molecular structure. Therefore, the tensile elongation is lowered, and the withstand voltage characteristic under a high temperature environment is also significantly lowered. In order to prevent this, lead and lead compound-based stabilizers that have long-term heat resistance effects have been used in the past, but these are environmentally hazardous substances that are designated as prohibited substances by the EU RoHS directive. Therefore, as an alternative, lead-free stabilizers are currently used in most insulated wires.

  Lead-free stabilizers are not as effective as lead and lead compound stabilizers, but barium zinc, calcium hydroxide, calcium zinc, hydrotalcite, metal octylate, etc. These lead-free stabilizers are used as appropriate (see, for example, Patent Documents 2 and 3).

JP 2011-26427 A Japanese Patent No. 3018367 JP 2003-40614 A

  However, in the above-described prior art, when a basic hydrate such as aluminum hydroxide or magnesium hydroxide is contained, discoloration due to the base occurs when an accelerated test is performed at 100 ° C. for about 20 days. When the wire shape is used, there is a problem that it is difficult to distinguish the hue. In addition, there is a problem that the surface is rough and uneven, and the appearance is deteriorated.

  Insulated wires used for the internal wiring of electronic devices are connected to the control device or power device in the device with the insulation layer (insulator) peeled off and the conductor exposed. There are many. There is also a case where a heat treatment or the like is performed during the connection processing. In such an operation, as shown in FIG. 5, in the case of a multi-core parallel insulated wire such as a two-core parallel insulated wire 40, the length of each conductor 41 is not maintained uniformly after the insulating layer 42 is peeled off. There was a problem that the work efficiency at the time of connecting processing was deteriorated.

  Accordingly, an object of the present invention is to provide a vinyl chloride resin composition capable of suppressing discoloration caused by the base of the insulating layer or sheath and suppressing the occurrence of rough skin and irregularities on the surface of the insulating layer or sheath, and an insulated wire using the same. And providing a cable.

  In addition to the above object, the object of the present invention is to maintain a uniform length of each exposed conductor after the insulation layer is peeled off in a multi-core parallel insulated wire, and to improve work efficiency at the time of connection processing. Another object is to provide a vinyl chloride resin composition, and an insulated wire and cable using the same.

  In order to achieve the above object, the present invention provides the following vinyl chloride resin composition, and an insulated wire and cable using the same.

[1] A conductor and an insulating layer made of a vinyl chloride resin composition coated on the outer periphery of the conductor, wherein the conductor is a bare soft copper wire, and the vinyl chloride resin composition is made of a vinyl chloride resin. The base polymer contains (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, and (D) high-density oxidized polyethylene wax. The total content of (A) to (D) with respect to parts is 1 to 4.5 parts by mass, and (B) the content mass ratio of (C) stearoylbenzoylmethane to the (B) cyanuric acid derivative or isocyanuric acid derivative (C / B) Insulated wire with 0.25-6.
[2] The insulated wire according to [1], wherein the vinyl chloride resin composition contains 25 to 70 parts by mass of a plasticizer with respect to 100 parts by mass of the vinyl chloride resin.
[3] The insulated wire according to [2], wherein the plasticizer is trimellitic acid ester.
[4] The (A) fatty acid metal salt is a fatty acid metal salt other than (A1) fatty acid zinc salt and (A2) fatty acid zinc salt, and (A1) the fatty acid metal salt other than (A2) fatty acid zinc salt. The insulated wire according to any one of [1] to [3], wherein the mass ratio (A1 / A2) of the fatty acid zinc salt is 4 to 9.
[5] The insulated wire according to [4], wherein the fatty acid metal salt other than the (A2) fatty acid zinc salt is one or more selected from a fatty acid calcium salt, a fatty acid magnesium salt, and a fatty acid aluminum salt.
[6] The (D) high-density oxidized polyethylene wax has a viscosity at 150 ° C. in the range of 2500 to 85000 cps, and is contained in an amount of 0.01 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. The insulated wire according to any one of [1] to [5].
[7] (A) Fatty acid metal salt, (B) Cyanuric acid derivative or isocyanuric acid derivative, (C) Stearoylbenzoylmethane, and (D) Fatty acid (A) fatty acid relative to the total content of high-density oxidized polyethylene wax The insulated wire according to any one of [1] to [6], wherein the content of the metal salt is 35% by mass or more.
[8] The insulated wire according to any one of [1] to [7], further including hydrotalcite, aluminum hydroxide, calcined clay, and titanium oxide.
[9] Base polymer containing vinyl chloride resin contains (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, (D) high-density oxidized polyethylene wax, and plasticizer The total content of (A) to (D) is 1 to 4.5 parts by mass, and the plasticizer content is 25 to 70 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, The vinyl chloride resin composition whose content mass ratio (C / B) of the said (C) stearoyl benzoylmethane with respect to the said (B) cyanuric acid derivative or an isocyanuric acid derivative is 0.25-6.
[10] An insulated wire provided with an insulating layer made of the vinyl chloride resin composition according to [9].
[11] The insulated wire according to any one of [1] to [8], [10], which is a multi-core parallel insulated wire.
[12] A plurality of conductors and an insulating layer made of a vinyl chloride resin composition coated on the outer periphery of the plurality of conductors, wherein the plurality of conductors have a tin plating thickness of 0.05 to 0 2 μm tin-plated annealed copper wire, and the vinyl chloride resin composition comprises (A) a fatty acid metal salt, (B) a cyanuric acid derivative or an isocyanuric acid derivative, (C) stearoylbenzoyl Methane, (D) high density oxidized polyethylene wax, and a plasticizer are contained, and the total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin is 1 to 4.5 parts by mass; Content of the said plasticizer is 25-70 mass parts, Comprising: Content mass ratio of the said (C) stearoyl benzoylmethane with respect to the said (B) cyanuric acid derivative or an isocyanuric acid derivative ( / B) of multi-core parallel insulated wire which is 0.25 to 6.
[13] Base polymer containing vinyl chloride resin contains (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, (D) high-density oxidized polyethylene wax, and plasticizer The total content of (A) to (D) is 1 to 4.5 parts by mass, and the plasticizer content is 25 to 70 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, The cable provided with the sheath which consists of a vinyl chloride resin composition whose content mass ratio (C / B) of the said (C) stearoyl benzoyl methane with respect to the said (B) cyanuric acid derivative or an isocyanuric acid derivative is 0.25-6.
[14] The cable according to [13], including the insulated wire according to any one of [1] to [8] and [10] to [12].

  ADVANTAGE OF THE INVENTION According to this invention, the vinyl chloride resin composition which can suppress the discoloration by the base of an insulating layer or a sheath, and can suppress the generation | occurrence | production of the rough skin and the unevenness | corrugation of an insulating layer or a sheath surface, and an insulated wire and a cable using the same Can be provided.

  Moreover, according to the present invention, in addition to the above effects, it is possible to maintain the length of each exposed conductor after the insulation layer is peeled uniformly in a multi-core parallel insulated wire, and to improve the work efficiency at the time of connection processing. A vinyl chloride resin composition, and an insulated wire and cable using the same can be provided.

It is a cross-sectional view which shows an example of the insulated wire which concerns on embodiment of this invention. It is a cross-sectional view which shows an example of the insulated wire which concerns on embodiment of this invention. It is a cross-sectional view showing an example of a cable according to an embodiment of the present invention. It is a top view which shows an example of the insulated wire which concerns on embodiment of this invention. It is a cross-sectional view which shows an example of the conventional insulated wire.

[Vinyl chloride resin composition]
The vinyl chloride resin composition according to the embodiment of the present invention includes (A) a fatty acid metal salt, (B) a cyanuric acid derivative or an isocyanuric acid derivative, (C) stearoylbenzoylmethane, and ( D) High density oxidized polyethylene wax is contained, and the total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin is 1 to 4.5 parts by mass, and (B) cyanuric acid The content ratio (C / B) of the (C) stearoylbenzoylmethane to the derivative or isocyanuric acid derivative is 0.25 to 6.

(Base polymer including vinyl chloride resin)
The vinyl chloride resin composition according to the embodiment of the present invention contains a vinyl chloride resin as a base polymer.

  Examples of the vinyl chloride resin include vinyl chloride homopolymers (that is, polyvinyl chloride), copolymers of vinyl chloride and other copolymerizable monomers, and mixtures thereof. Examples of the monomer copolymerizable with vinyl chloride include vinyl acetate, vinylidene chloride, (meth) acrylic acid, acrylonitrile and the like.

  It is preferable to use a vinyl chloride resin having an average degree of polymerization of 1000 to 2500. Those having an average degree of polymerization of 1000 to 2000 are more preferred in terms of heat resistance, cold resistance and moldability. When the degree of polymerization is lowered, moldability is improved, but heat resistance and cold resistance are lowered. Conversely, when the degree of polymerization is increased, heat resistance and cold resistance are improved, but moldability is deteriorated.

  If necessary, two or more types of vinyl chloride resins having different degrees of polymerization may be blended and used. In addition, as long as the effects of the present invention are exhibited, an ethylene / vinyl acetate copolymer, chlorinated polyethylene, or the like may be added to the base polymer as necessary. The content ratio of the vinyl chloride resin in the base polymer is preferably 80% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.

((A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, and (D) high density oxidized polyethylene wax)
The vinyl chloride resin composition according to the embodiment of the present invention includes (A) a fatty acid metal salt, (B) a cyanuric acid derivative or an isocyanuric acid derivative, (C) stearoylbenzoylmethane, and ( D) High density oxidized polyethylene wax is contained. The total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin in the base polymer is 1 to 4.5 parts by mass. The effect of the present invention is achieved by setting the total content within the above range. The total content of (A) to (D) is preferably 1.1 to 4.1 parts by mass and more preferably 1.2 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. More preferably, the content is 1.3 to 2.5 parts by mass.

A: Fatty acid metal salt As the fatty acid metal salt, for example, a fatty acid zinc salt is preferably used, and a fatty acid zinc salt and a fatty acid calcium salt are more preferably used in combination. If necessary, a fatty acid magnesium salt or a fatty acid aluminum salt may be used in combination to adjust the heat-resistant balance. When using these, it is preferable that the content ratio (A1 / A2) of the (A1) fatty acid zinc salt to the fatty acid metal salt other than the (A2) fatty acid zinc salt is 4 to 9.

  (A) It is preferable that the content rate of a fatty-acid metal salt is 35 mass% or more with respect to the total content of (A)-(D).

The role of the fatty acid metal salt will be described below using calcium salt and zinc salt as examples.
(C ₁₇ H ₃₅ COO) ₂ Zn + 2HCL → ZnCL ₂ + C ₁₇ H ₃₅ COOH
(C ₁₇ H ₃₅ COO) ₂ Ca + ZnCL ₂ → (C ₁₇ H ₃₅ COO) ₂ Zn + CaCL ₂

  The metal soap captures hydrogen chloride generated from the vinyl chloride resin by heat and light, and a metal salt is generated. When fatty acid zinc and fatty acid calcium are compared, zinc chloride is first produced because fatty acid zinc has higher scavenging power. If zinc chloride is present in the vinyl chloride resin blend, it will have a short wavelength tone and coloration will be improved. However, zinc chloride promotes the dehydrochlorination of the vinyl chloride resin and the addition of a large amount of fatty acid zinc requires the addition of an appropriate amount because the system of the admixture becomes excessive in external lubricity. On the other hand, in addition to capturing hydrogen chloride, fatty acid calcium also acts to suppress dehydrochlorination because an exchange reaction with zinc chloride proceeds as shown in the above formula.

  Fatty acid magnesium salt has better hydrogen chloride scavenging ability than calcium salt, and the chloride produced in the example shown in the above zinc salt does not further promote the dehydrochlorination reaction from the vinyl chloride resin. It is preferably used in combination with a salt.

  As a fatty acid which comprises a fatty acid metal salt, a C8-C22 saturated fatty acid and a C8-C22 unsaturated fatty acid can be used, for example. In particular, a stearic acid metal salt is preferable, but any fatty acid species may be used as long as the added amount is a combination of metal equivalents. The fatty acid species may be used not only alone but also in combination of two or more.

B: Cyanuric acid derivative or isocyanuric acid derivative As the cyanuric acid derivative or isocyanuric acid derivative, it is preferable to use an isocyanuric acid derivative, for example, it is particularly preferable to use isocyanuric acid tris (2-hydroxyethyl). Here, “or” includes not only the case where the cyanuric acid derivative and the isocyanuric acid derivative are used alone, but also the case where the cyanuric acid derivative and the isocyanuric acid derivative are used in combination.

  The role of the cyanuric acid derivative or isocyanuric acid derivative (for example, isocyanuric acid tris (2-hydroxyethyl)) is to suppress dehydrochlorination from the vinyl chloride resin due to chelation of the metal salt.

  Metal chlorides are known to form π complexes with polyenes and become colored. However, since this material forms a colorless chelate compound, the effect is also exhibited in reducing coloring. However, since this system material is inferior in compatibility with a vinyl chloride resin, an appropriate amount is required.

C: Stearoyl benzoylmethane The role of stearoyl benzoylmethane will be described below.
In general, dibenzoylmethane (DBM) has been used as an allyl salt stabilizer for vinyl chloride resins. Works under the following formulas (I) and (II) under fatty acid salts and metal compounds. That is, by stabilizing the allyl salt, it acts as a color inhibitor as a result.

Although it is known that DBM has photosensitization as a drawback of DBM, it requires a 1/2 mole metal salt to stabilize the allyl salt, and the reaction is in two stages. It is. In the present invention, stearoylbenzoylmethane was used as a material for stabilizing the allyl salt earlier in one stage. Reaction formula (III) is shown below. In the presence of a metal salt, the allyl salt is stabilized in one step.

  The content ratio (C / B) of the (C) stearoylbenzoylmethane to the (B) cyanuric acid derivative or isocyanuric acid derivative is 0.25 to 6. The effect of this invention is show | played by making the said content mass ratio into the said range. A preferable content ratio (C / B) is 0.25 to 5, more preferably 0.25 to 4, and still more preferably 0.25 to 3.

D: High density oxidized polyethylene wax For polyolefin wax, polyethylene homopolymer type, oxidized polyethylene type, high density oxidized polyethylene type, polypropylene type, ethylene / acrylic acid copolymer type, ethylene / vinyl acetate copolymer type, ethylene oxide / acetic acid Various waxes exist such as vinyl copolymer type, low molecular weight ionomer type, ethylene-maleic anhydride copolymer type, propylene-maleic anhydride copolymer type. Among these, high-density oxidized polyethylene wax was selected by focusing on the following points.
(1) It is a wax having a polar group in consideration of compatibility with vinyl chloride resin and (B) cyanuric acid derivative or isocyanuric acid derivative or (C) stearoylbenzoylmethane.
(2) The wax has a dropping point based on the international standard ASTM-D3954 near the kneading temperature (130 to 150 ° C.) of the vinyl chloride resin composition of the present invention.
(3) A wax having a high viscosity around the kneading temperature of the vinyl chloride resin composition of the present invention and acting as an internal lubricant.

The high density oxidized polyethylene wax in the embodiment of the present invention preferably has a density of 0.95 to 1.1 g / cm ³ , an acid value of 1 to 45 KOHmg / g, and a softening point of 100 to 150 ° C. The density is more preferably 0.96 to 1.0 g / cm ³ , and the acid value is more preferably 7 to 41 KOH mg / g.

  Moreover, the high density oxidized polyethylene wax in the embodiment of the present invention has a viscosity at 150 ° C. in the range of 2500 to 85000 cps, and is contained in an amount of 0.01 to 2 parts by mass with respect to 100 parts by mass of the aforementioned vinyl chloride resin. It is preferred that The viscosity at 150 ° C. is in the range of 8500 to 85000 cps, and 0.04 to 0.1 parts by mass with respect to 100 parts by mass of the aforementioned vinyl chloride resin is more preferable from the viewpoint of improving the kneading efficiency.

  Moreover, as long as the effect of the present invention is exhibited, a polyolefin wax other than the high density oxidized polyethylene wax may be further added as necessary.

(Plasticizer)
A conventionally known plasticizer can be added as a plasticizer to the vinyl chloride resin composition according to the embodiment of the present invention. Although not particularly limited, it is preferable to use a trimellitate plasticizer from the viewpoint of adhesion to an annealed copper wire and heat resistance, such as trimellitic acid tri-2-ethylhexyl, trimellitic acid tri-normal alkyl, trimellitic acid triisodecyl, etc. Of trimellitic acid esters. From the viewpoint of heat resistance and cost, it is more preferable to use tri-2-ethylhexyl trimellitic acid. It is difficult to obtain sufficient heat resistance with phthalates. Further, polyester plasticizers may cause hydrolysis. The plasticizer content is preferably 25 to 70 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and more preferably 25 to 50 parts by mass from the viewpoint of suppressing the amount of thermal deformation. If it is less than 25 parts by weight, it is difficult to obtain necessary cold resistance.

(Stabilizer)
A conventionally known stabilizer can be added as a stabilizer to the vinyl chloride resin composition according to the embodiment of the present invention. Although not particularly limited, it is preferable in terms of laws and regulations to use a lead-free stabilizer that does not contain lead. Examples of non-lead stabilizers include hydrotalcite stabilizers and calcium-zinc composite stabilizers. When calcium stearate, zinc stearate, or the like is added as the aforementioned fatty acid metal salt, these can also function as a stabilizer.

(Other additives)
In addition to the above additives, the vinyl chloride resin composition according to the embodiment of the present invention includes, as necessary, a flame retardant, a filler, a crosslinking agent, a crosslinking aid, an ultraviolet absorber, a light stabilizer, a lubricant, Antioxidants, colorants, processability improvers, and other modifiers may be used alone or in combination of two or more.

  Examples of the flame retardant include antimony trioxide and metal hydrate. As the metal hydroxide, magnesium hydroxide, aluminum hydroxide, hydrotalcite, calcium aluminate hydrate, calcium hydroxide, barium hydroxide, hard clay and the like are used.

  Examples of the filler include calcined clay, hydrated clay, carbon black, silica, calcium carbonate, aluminum silicate, titanium oxide, ferrite magnetic powder, and talc.

  The vinyl chloride resin composition according to the embodiment of the present invention may be crosslinked after molding. A conventionally known method can be used as the crosslinking method, and there is no particular limitation, but methods such as chemical crosslinking, silane crosslinking, and radiation crosslinking can be used. The degree of crosslinking is preferably 40 to 65%, more preferably 49 to 60% in terms of gel fraction.

  As a crosslinking aid, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, or the like can be used. For example, 2 to 20 parts by mass can be added to 100 parts by mass of the vinyl chloride resin. If it is less than 2 parts by mass, crosslinking may be insufficient, and if it exceeds 20 parts by mass, it may be crosslinked during molding.

[Insulated wire]
An insulated wire according to an embodiment of the present invention includes a conductor and an insulating layer made of the vinyl chloride resin composition according to the embodiment of the present invention, which is coated on the outer periphery of the conductor.

FIG. 1 is a cross-sectional view showing an example of an insulated wire according to an embodiment of the present invention.
As shown in FIG. 1, the insulated wire 10 according to the present embodiment includes a conductor 1 and an insulating layer 2 covered on the outer periphery of the conductor 1. As the conductor 1 to be coated, for example, a conductor having an outer diameter of about 0.15 to 7 mmφ can be used. Although the conductor etc. which twisted the tin plating annealed copper wire can be used conveniently, it is not limited to this. The number of conductors 1 is not limited to one as shown in FIG. 1, and a plurality of conductors may be used.

FIG. 2 is a cross-sectional view showing another example of the insulated wire according to the embodiment of the present invention.
As shown in FIG. 2, the insulated wire 20 according to the present embodiment includes two parallel conductors 21 and an insulating layer 22 that is collectively covered on the outer periphery of the two conductors 21. As the conductor 21, it is desirable to use a soft copper wire that is not tin-plated, that is, a bare soft copper wire, from the viewpoint of adhesion to the resin composition that constitutes the insulating layer 22. For example, a conductor having an outer diameter of about 0.15 to 7 mmφ can be used as the conductor 21. A conductor formed by twisting a plurality of bare soft copper wires (seven in FIG. 2) can be preferably used, but is not limited thereto. The conductor 21 is not limited to the case where two cores are arranged in parallel as shown in FIG. 2, and may be a single core or three or more cores.

  Insulating layers 2 and 22 are constituted from the above-mentioned vinyl chloride resin composition concerning an embodiment of the invention. In particular, the insulating layer 22 is preferably composed of a vinyl chloride resin composition containing the above-described plasticizer in the above-described content ratio. After being coated as an insulating layer by molding means such as extrusion coating, an insulated wire can be obtained by crosslinking the vinyl chloride resin by a method such as electron beam irradiation. The extrusion coating is a conventionally known electric wire extruder in which the vinyl chloride resin composition before crosslinking is kneaded with a roll, a banbury, an extruder, etc., and the resulting pellet compound and conductor are attached with a crosshead die. It can be carried out by, for example, wire-coating extrusion molding.

  In this embodiment mode, the insulating layer may be a single layer or a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.

〔cable〕
A cable according to an embodiment of the present invention is characterized by using the above-described vinyl chloride resin composition according to an embodiment of the present invention as a coating material (sheath or insulating layer and sheath).

FIG. 3 is a cross-sectional view showing an example of a cable according to the embodiment of the present invention.
As shown in FIG. 3, the cable 30 according to the present embodiment includes a three-core stranded wire obtained by twisting three insulated wires 10 with a conductor 1 covered with an insulating layer 2 together with an interposition 4 such as paper, and the like. A presser wound tape 5 is provided on the outer periphery of the stranded wire, and a sheath 3 is coated on the outer periphery by extrusion coating. Not only a three-core stranded wire but also one insulated wire (single core) or a multi-core stranded wire other than a three-core stranded wire may be used.

  The sheath 3 is comprised from said vinyl chloride resin composition which concerns on embodiment of this invention. The insulating layer 2 may also be comprised from said vinyl chloride resin composition. After being coated as an insulating layer or a sheath layer by molding means such as extrusion coating, a cable can be obtained by crosslinking the vinyl chloride resin by a method such as electron beam irradiation.

  In the present embodiment, the sheath may be composed of a single layer or a multilayer structure. Furthermore, you may give a separator, a braiding, etc. as needed.

  The outer diameter of the insulated wire or cable according to the embodiment of the present invention is, for example, 0.4 to 11 mmφ. Examples of the use include wiring in a high-temperature part in equipment such as a dryer, a rice cooker, a transformer outlet, a lighting fixture, and an air conditioner.

[Effect of the embodiment of the present invention]
(1) According to the embodiment of the present invention, even if a basic hydrate such as aluminum hydroxide or magnesium hydroxide is contained, discoloration due to the base of the insulating layer or sheath can be suppressed, and the insulating layer or sheath It is possible to provide a vinyl chloride resin composition capable of suppressing the occurrence of surface roughness and unevenness (allowing a good appearance), and an insulated wire and cable using the same.

(2) According to the embodiment of the present invention, the content ratio (C / B) of (C) stearoylbenzoylmethane to the (B) cyanuric acid derivative or isocyanuric acid derivative is low (for example, 1 or less, and further 0.1. 5 or less, and even less than 0.4), it is possible to provide a vinyl chloride resin composition capable of suppressing discoloration due to the base of the insulating layer or sheath, and an insulated wire and cable using the same. The material cost (manufacturing cost) can be reduced.

(3) If the mass ratio (A1 / A2) of (A1) fatty acid zinc salt to fatty acid metal salt other than (A2) fatty acid zinc salt is 4 or more, kneading time tends to take longer due to excessive slipperiness. However, according to the embodiment of the present invention, the kneading time is shortened even if the mass ratio (A1 / A2) of (A1) fatty acid zinc salt to fatty acid metal salt other than (A2) fatty acid zinc salt is 4 or more. It is possible to provide an electric wire coating material with improved kneadability and an insulated electric wire and a cable using the same.

(4) According to the embodiment of the present invention, even if pretreatment such as heat treatment is performed after the insulation layer is peeled off in the multi-core parallel insulated wire using bare soft copper wire as the conductor, one side does not protrude as shown in FIG. As shown in FIG. 4, a vinyl chloride resin composition capable of maintaining a uniform length of each exposed conductor and improving work efficiency during connection processing, and an insulated wire and cable using the same are provided. can do.

  In addition, according to the embodiment of the present invention in which the insulating layer is composed of the above-mentioned vinyl chloride resin composition containing the above-mentioned plasticizer in the above-mentioned content ratio, a multi-core parallel insulated wire using a tin-plated annealed copper wire as a conductor However, the occurrence rate of one conductor protruding after the insulating layer is peeled can be suppressed to some extent. In this case, the incidence rate can be further reduced by reducing the tin plating thickness of the tin-plated annealed copper wire. It is considered that when the tin plating thickness is reduced to about 0.05 to 0.2 μm (for example, 0.1 μm), an oxide alloy layer of tin and copper is formed.

  Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited thereto.

  The insulated wire 10 having the structure of FIG. 1 and the insulated wire 20 having the structure of FIG. 2 were manufactured and evaluated by the following methods.

(1) Preparation of vinyl chloride resin composition Each material shown in Tables 1 and 2 was blended in the stated ratio, kneaded and mixed with an open roll mixer heated to 140 ° C, and pelletized. A vinyl chloride resin composition was obtained. The materials used are as shown in Table 3.

As a result of the evaluation of kneadability by the following method as a reference, the results were ○ in Examples 1 to 6 and Comparative Example 1, and × in Comparative Examples 2 to 3.
When kneading with an open roll mixer heated to 140 ° C, within 5 minutes, the admixture sheet wound around the front roll has a smooth appearance that does not cause sagging, and rough appearance and sagging occur in the sheet. Was marked with x. The case of x is a phenomenon caused by excessive external lubricity, and when mass-produced with a continuous kneader or batch mixer, a uniformly dispersed kneaded material cannot be obtained.

(2) Production of insulated wire (2-1) Production of insulated wire 10 having the structure of FIG. 1 (Examples 1 to 6 and Comparative Examples 1 to 3)
As a conductor, an outer diameter 0.16 mmφ tin-plated annealed copper wire 26 stranded conductor (outer diameter 0.94 mmφ, tin plating thickness 0.5 μm) was used. The vinyl chloride resin composition produced based on Table 1 in (1) above was extruded on the conductor by a melt extrusion method to obtain a sample (insulated wire) in which the conductor was coated with each vinyl chloride resin composition. The thickness of the insulating layer made of the vinyl chloride resin composition was 0.5 mm. The electric wire was manufactured under the conditions of a cylinder temperature of 170 ° C., a head temperature of 180 ° C., and a wire speed of 400 m / min.

(2-2) Production of insulated wire 20 having the structure of FIG. 2 (Examples 7 to 14 and Comparative Examples 4 to 6)
As a conductor, an outer diameter 0.16 mmφ annealed copper wire (bare annealed copper wire) is used in Examples 7 to 10, and an outer diameter 0.16 mmφ tinned annealed copper wire is twisted in Examples 11 to 14 and Comparative Examples 4 to 6. Conductors (outer diameter 0.94 mmφ, tin plating thickness 0.5 μm (Examples 11 to 12 and Comparative Examples 4 to 6), tin plating thickness 0.1 μm (Examples 13 to 14)) were used. The vinyl chloride resin composition produced based on Table 2 in (1) above was extruded on the conductor by a melt extrusion method to obtain a sample (two-core parallel insulated wire) in which the conductor was coated with each vinyl chloride resin composition. It was. The thickness (X shown in FIG. 2) of the obtained 2-core parallel insulated wire was 1.3 mm, and the width (Y shown in FIG. 2) was 2.6 mm. The electric wire was manufactured under the conditions of a cylinder temperature of 180 ° C., a head temperature of 190 ° C., and a linear speed of 250 m / min. Examples 11 and 13 and Examples 12 and 14 differ only in the tin plating thickness of the tinned annealed copper wire.

(3) Evaluation 1 of insulated wires (change in hue)
About the insulated wire of each said example, the electric wire cut | disconnected to the length of 300 mm was exposed to gear oven (forced circulation type air heating aging test machine) at 100 degreeC for 500 hours, and the hue change before and behind exposure was confirmed. Hue change was evaluated by visual comparison test by 5 people, before and after exposure all 5 people judged no discoloration ◎ 4 people judged no discoloration ○, 0-3 people judged no discoloration Was marked with x. Tables 1 and 2 show the evaluation results.

(4) Evaluation 2 of insulated wires (appearance)
About the insulated wire of each said example, the external appearance was evaluated visually. The case where the surface was glossy and the surface was smooth was marked with ◎, the surface where the surface was smooth but in a matte state was marked with ○, and the surface with rough or uneven surface was marked with ×. Tables 1 and 2 show the evaluation results.

(5) Evaluation of insulated wire 3 (Conductor length uniformity after insulation layer peeling)
The two-core parallel insulated wire produced in the above (2-2) was cut to a length of 500 mm, and the insulating layer was peeled off 5 mm from the tip of the wire, resulting in the state shown in FIG. Then, after heating in a gear oven at 120 ° C. for 3 hours, it was taken out from the gear oven and the length of the two-core conductor was measured. If the length of the two-core conductor after heat treatment is in the range of 4.5 to 5.5 mm is judged as a non-defective product, the length of any of the two-core conductors is less than 4.5 mm or more than 5.5 mm Were determined to be defective. The test was conducted at N = 20. A sample in which 20 of 20 pieces were non-defective products was marked by ◎, a sample in which 20 to 20 pieces in 20 pieces were non-defective products, and a case in which less than 16 pieces in 20 pieces were non-defective items.

(6) Comprehensive judgment In the comprehensive judgment, all the evaluations 1 to 2 or 1 to 3 were で or ◯. The results are shown in Tables 1 and 2.

  In Examples 1 to 6, both the hue change and the appearance were good, and the comprehensive judgment was acceptable.

  In Examples 7 to 14, all of the hue change, appearance, and uniformity of the conductor length after peeling of the insulating layer were good, and the overall judgment was acceptable.

  In Comparative Example 1, since (D) high-density oxidized polyethylene wax was not contained, the total content of A + B + C + D was small, and the mass ratio of C / B and A1 / (A2 + A3) were small. The result of the change was bad and the overall judgment was unacceptable.

  In Comparative Example 2, it contains polyethylene wax, but does not contain (D) high-density oxidized polyethylene wax, and because the mass ratio of C / B and the mass ratio of A1 / (A2 + A3) are large, the hue change and Both the appearance and the result were bad, and the comprehensive judgment was unacceptable.

  In Comparative Example 3, (C) stearoyl benzoylmethane and (D) high-density oxidized polyethylene wax were not contained, and the mass ratio of C / B and A1 / (A2 + A3) were small. The result was bad and the overall judgment was unacceptable.

  In Comparative Example 4, since (D) high-density oxidized polyethylene wax was not contained, the total content of A + B + C + D was small, and the mass ratio of C / B and A1 / (A2 + A3) were small. The result of the change was bad. Moreover, since the tin-plated annealed copper wire was used as the conductor and the amount of the plasticizer was large, the result of the uniformity of the conductor length after the insulating layer was peeled was also poor. Therefore, the comprehensive judgment was unacceptable.

  In Comparative Example 5, since the mass ratio of C / B and the mass ratio of A1 / (A2 + A3) were large, both the hue change and the appearance were bad. Further, since tin-plated annealed copper wire was used as the conductor and the amount of plasticizer was slightly small, the result of the uniformity of the conductor length after peeling off the insulating layer was also 10% or more. Therefore, the comprehensive judgment was unacceptable.

  In Comparative Example 6, a tinned annealed copper wire was used as the conductor, the total content of A + B + C + D was large, and the mass ratio of A1 / (A2 + A3) was small. More than 20% of the results of length uniformity were rejected. Therefore, the comprehensive judgment was unacceptable.

  As described above, by using four types of (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoyl benzoylmethane, and (D) high-density oxidized polyethylene wax in the above-described appropriate amount range. The present inventors have found that low-temperature and long-term discoloration can be suppressed in the presence of a basic compound of a vinyl chloride resin. Furthermore, it discovered that the said discoloration suppression and favorable extrusion molding (good appearance) can be made compatible. In addition, in a two-core parallel insulated wire using a bare soft copper wire as a conductor and using a vinyl chloride resin composition according to an embodiment of the present invention as an insulating layer, the conductor length uniformity after peeling of the insulating layer is excellent. I found.

  In addition, this invention is not limited to the said embodiment and Example, A various deformation | transformation implementation is possible.

10, 20, 40: Insulated wire, 30: Cables 1, 21, 41: Conductor, 2, 22, 42: Insulating layer 3: Sheath, 4: Interposition, 5: Press-wrapping tape

Claims (14)

A conductor, and an insulating layer made of a vinyl chloride resin composition coated on the outer periphery of the conductor;
The conductor is a bare annealed copper wire;
The vinyl chloride resin composition comprises (A) a fatty acid metal salt, (B) a cyanuric acid derivative or an isocyanuric acid derivative, (C) stearoylbenzoylmethane, and (D) a high-density oxidized polyethylene wax. The total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin is 1 to 4.5 parts by mass, and the (B) the cyanuric acid derivative or the isocyanuric acid derivative is (C) The insulated wire whose content mass ratio (C / B) of stearoyl benzoylmethane is 0.25-6.   The insulated wire according to claim 1, wherein the vinyl chloride resin composition contains 25 to 70 parts by mass of a plasticizer with respect to 100 parts by mass of the vinyl chloride resin.   The insulated wire according to claim 2, wherein the plasticizer is trimellitic acid ester.   The (A) fatty acid metal salt is a fatty acid metal salt other than (A1) fatty acid zinc salt and (A2) fatty acid zinc salt, and (A1) fatty acid zinc salt relative to a fatty acid metal salt other than (A2) fatty acid zinc salt. The insulated wire according to any one of claims 1 to 3, wherein the mass ratio (A1 / A2) is 4 to 9.   The insulated wire according to claim 4, wherein the fatty acid metal salt other than the (A2) fatty acid zinc salt is one or more selected from a fatty acid calcium salt, a fatty acid magnesium salt, and a fatty acid aluminum salt.   The (D) high-density oxidized polyethylene wax has a viscosity within a range of 2500 to 85000 cps at 150 ° C, and is contained in an amount of 0.01 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. The insulated wire of any one of -5.   The (A) fatty acid metal salt, the (B) cyanuric acid derivative or isocyanuric acid derivative, the (C) stearoylbenzoylmethane, and the (D) high density oxidized polyethylene wax with respect to the total content of the (A) fatty acid metal salt. Content rate is 35 mass% or more, The insulated wire of any one of Claims 1-6.   The insulated wire according to any one of claims 1 to 7, further comprising hydrotalcite, aluminum hydroxide, calcined clay, and titanium oxide. The base polymer containing vinyl chloride resin contains (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, (D) high-density oxidized polyethylene wax, and plasticizer. ,
The total content of (A) to (D) is 1 to 4.5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and the plasticizer content is 25 to 70 parts by mass, and the (B) The vinyl chloride resin composition whose content mass ratio (C / B) of the said (C) stearoyl benzoyl methane with respect to a cyanuric acid derivative or an isocyanuric acid derivative is 0.25-6.   The insulated wire provided with the insulating layer which consists of a vinyl chloride resin composition of Claim 9.   It is a multi-core parallel insulated wire, The insulated wire of any one of Claims 1-8 and 10. A plurality of conductors, and an insulating layer made of a vinyl chloride resin composition coated on the outer periphery of the plurality of conductors,
The plurality of conductors are tin-plated annealed copper wires having a tin plating thickness of 0.05 to 0.2 μm,
The vinyl chloride resin composition comprises (A) a fatty acid metal salt, (B) a cyanuric acid derivative or an isocyanuric acid derivative, (C) stearoylbenzoylmethane, (D) a high density oxidized polyethylene wax, And a plasticizer is contained, and the total content of (A) to (D) is 1 to 4.5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and the content of the plasticizer is 25 to 70 parts by mass. A multi-core parallel insulated wire in which the (C) stearoylbenzoylmethane content mass ratio (C / B) to the (B) cyanuric acid derivative or isocyanuric acid derivative is 0.25 to 6.   The base polymer containing vinyl chloride resin contains (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, (D) high-density oxidized polyethylene wax, and plasticizer. The total content of (A) to (D) with respect to 100 parts by mass of the vinyl chloride resin is 1 to 4.5 parts by mass, and the content of the plasticizer is 25 to 70 parts by mass. The cable provided with the sheath which consists of a vinyl chloride resin composition whose content mass ratio (C / B) of the said (C) stearoyl benzoyl methane with respect to a cyanuric acid derivative or an isocyanuric acid derivative is 0.25-6.   The cable of Claim 13 provided with the insulated wire of any one of Claims 1-8 and 10-12.

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