JP6684053B2 - Vinyl chloride resin composition, and insulated wire and cable using the same - Google Patents

Description

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

  BACKGROUND ART Insulated electric wires used for internal wiring of electronic devices are required to be flame-retardant so that a fire does not spread along the electric wires in case of a fire accident of devices.

  The flame-retardant standard of the internal wiring material is defined by, for example, UL758 standard in the United States. The vertical combustion test (hereinafter referred to as "VW-1 test") is provided as an option for the items required by UL758, but most insulated wires have passed this test and have been certified by UL, so it is an option. However, the VW-1 test is a near-essential item.

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

  Antimony trioxide has generally been used as the flame retardant. However, since antimony trioxide is a powerful drug, strict control is required in manufacturing, and it is a material that should be avoided. Moreover, they are rare metals, and their prices have recently been rising.

  Therefore, a metal hydroxide such as aluminum hydroxide or magnesium hydroxide is 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 lead-free stabilizer. Disclosed is a vinyl chloride resin composition in which the content of magnesium is 8 to 22 parts by mass with respect to the content of vinyl chloride resin of 100 parts by mass, the content of antimony is less than 1000 ppm, and which is crosslinked after molding. There is.

  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, so that the tensile elongation is lowered and the withstand voltage characteristic in a high temperature environment is also remarkably lowered. In order to prevent this, lead and lead compound-based stabilizers, which have long-term heat resistance effects, have been conventionally used, but these are environmentally hazardous substances designated as prohibited substances by 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 depending on the application, barium zinc-based, calcium hydroxide-based, calcium zinc-based, hydrotalcite-based, metal octylate, etc. The non-lead-based stabilizers are properly used (for example, see Patent Documents 2 and 3).

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

  However, in the above-mentioned conventional technique, when a basic hydrate such as aluminum hydroxide or magnesium hydroxide is contained, for example, when the accelerated test is performed at 100 ° C. for about 20 days, discoloration due to the base occurs. However, there is a problem that it is difficult to distinguish the hue when the wire is formed. In addition, there is a problem in that the surface becomes rough and uneven, which deteriorates the appearance.

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

  Then, the objective of this invention is the vinyl chloride resin composition which can suppress the discoloration by the base origin of an insulating layer or a sheath, and can suppress generation | occurrence | production of the roughening and unevenness of the surface of an insulating layer or a sheath, and the insulated wire using this. And to provide a cable.

  Further, in addition to the above objects, an object of the present invention is to maintain uniform length of each exposed conductor after peeling an insulating layer in a multi-core parallel insulated wire, and to improve work efficiency during connection processing. Another object of the present invention 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, the conductor being a bare annealed copper wire, and the vinyl chloride resin composition containing a vinyl chloride resin. The base polymer containing contains (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 1 part is 1 to 4.5 parts by mass, and the content mass ratio (C) of stearoylbenzoylmethane (C) to the (B) cyanuric acid derivative or isocyanuric acid derivative is (C). / B) is Ri der 0.25, wherein (B) cyanuric acid derivatives or isocyanuric acid derivatives, isocyanuric acid tris (2-hydroxy-et Insulated wire consisting Le).
[2] The insulated wire according to [1], wherein the vinyl chloride resin composition contains a plasticizer in an amount of 25 to 70 parts by mass based on 100 parts by mass of the vinyl chloride resin.
[3] The insulated wire according to the above [2], wherein the plasticizer is a trimellitic acid ester.
[4] The (A) fatty acid metal salt is a fatty acid metal salt other than the (A1) fatty acid zinc salt and the (A2) fatty acid zinc salt, and the (A1) with respect to the (A2) fatty acid metal salt other than the fatty acid zinc salt. The insulated wire according to any one of [1] to [3], wherein the content 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 fatty acid calcium salt, fatty acid magnesium salt, and fatty acid aluminum salt.
[6] The high-density oxidized polyethylene wax (D) has a viscosity in the 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 according to any one of [1] to [5].
[7] The (A) fatty acid relative to the total content of 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 The insulated wire according to any one of the above [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 containing 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 content of the plasticizer is 25 to 70 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, wherein (B) the relative cyanuric acid derivatives or isocyanuric acid derivative (C) containing the mass ratio of stearoylbenzoylmethane (C / B) is Ri der 0.25, wherein (B) cyanuric acid derivatives or isocyanuric acid derivative A vinyl chloride resin composition comprising tris (2-hydroxyethyl) isocyanurate .
[10] An insulated wire provided with an insulating layer made of the vinyl chloride resin composition according to [9].
[11] The insulated electric wire according to any one of [1] to [8] and [10], which is a multicore parallel insulated electric wire.
[12] A plurality of conductors and an insulating layer made of a vinyl chloride resin composition, which is coated on the outer circumference of the plurality of conductors, and has a tin plating thickness of 0.05 to 0. A tin-plated annealed copper wire having a thickness of 0.2 μm, wherein the vinyl chloride resin composition comprises a base polymer containing a vinyl chloride resin, (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, and (C) stearoylbenzoyl. Methane, (D) high-density oxidized polyethylene wax, and a plasticizer are 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, and the content ratio by mass of the (C) stearoylbenzoylmethane to the (B) cyanuric acid derivative or the isocyanuric acid derivative ( / B) is Ri der 0.25, wherein (B) cyanuric acid derivatives or isocyanuric acid derivatives, multi-core parallel insulated wire consisting of isocyanuric acid tris (2-hydroxyethyl).
[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 content of the plasticizer is 25 to 70 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, wherein (B) the relative cyanuric acid derivatives or isocyanuric acid derivative (C) containing the mass ratio of stearoylbenzoylmethane (C / B) is Ri der 0.25, wherein (B) cyanuric acid derivatives or isocyanuric acid derivative A cable having a sheath made of a vinyl chloride resin composition made of tris (2-hydroxyethyl) isocyanurate .
[14] The cable according to [13], which comprises 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 discoloration by the base origin of an insulating layer or a sheath, and can suppress generation | occurrence | production of the roughening of the surface of an insulating layer or a sheath, and an insulated wire and cable using this. Can be provided.

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

It is a transverse cross section showing an example of an insulated wire concerning an embodiment of the invention. It is a transverse cross section showing an example of an insulated wire concerning an embodiment of the 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 showing an example of a conventional insulated wire.

[Vinyl chloride resin composition]
A vinyl chloride resin composition according to an 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) is 1 to 4.5 parts by mass relative to 100 parts by mass of the vinyl chloride resin, and (B) cyanuric acid. The content mass ratio (C / B) of the (C) stearoylbenzoylmethane to the derivative or the isocyanuric acid derivative is 0.25 to 6.

(Base polymer containing 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 a homopolymer of vinyl chloride (that is, polyvinyl chloride), a copolymer of vinyl chloride and another copolymerizable monomer, and a mixture 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 polymerization degree of 1000 to 2500. Those having an average degree of polymerization of 1000 to 2000 are more preferable in terms of heat resistance, cold resistance and moldability. When the degree of polymerization is low, moldability is improved but heat resistance and cold resistance are decreased. On the contrary, when the degree of polymerization is high, heat resistance and cold resistance are improved, but moldability is deteriorated.

  As the vinyl chloride resin, two or more kinds of vinyl chloride resins having different polymerization degrees may be blended and used. Further, 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, if 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)
A vinyl chloride resin composition according to an 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) Contains high density oxidized polyethylene wax. 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 of these 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. , 1.3 to 2.5 parts by mass is more preferable.

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

  The content ratio of the fatty acid metal salt (A) is preferably 35% by mass or more based on the total content of (A) to (D).

The role of the fatty acid metal salt will be described below by taking calcium salts and zinc salts 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 or light, and forms a metal salt. When fatty acid zinc and fatty acid calcium are compared, zinc chloride is first formed because fatty acid zinc has a higher scavenging power. The presence of zinc chloride in the vinyl chloride resin admixture results in short wavelength shades and improved coloration. However, zinc chloride promotes dehydrochlorination of vinyl chloride resin and the addition of a large amount of fatty acid zinc requires an appropriate amount of zinc chloride because the mixture system becomes excessively slippery. On the other hand, in addition to trapping hydrogen chloride, fatty acid calcium also acts as an inhibitor of dehydrochlorination because it undergoes an exchange reaction with zinc chloride as shown in the above formula.

  The fatty acid magnesium salt has a higher hydrogen chloride scavenging ability than the calcium salt, and since the chloride produced in the above-mentioned example of the zinc salt does not further accelerate the dehydrochlorination reaction from the vinyl chloride resin, the fatty acid zinc salt or the fatty acid calcium salt It is preferably used in combination with a salt.

  As the fatty acid constituting the fatty acid metal salt, for example, a C8 to C22 saturated fatty acid or a C8 to C22 unsaturated fatty acid can be used. Particularly, stearic acid metal salt is preferable, but any fatty acid species may be used as long as the metal equivalent is added. The fatty acid species may be used alone or in combination of two or more.

B: Cyanuric Acid Derivative or Isocyanuric Acid Derivative As the cyanuric acid derivative or isocyanuric acid derivative, an isocyanuric acid derivative is preferably used, and for example, tris (2-hydroxyethyl) isocyanuric acid is particularly preferably used. It should be noted that the term “or” as used herein includes the case where the cyanuric acid derivative and the isocyanuric acid derivative are used alone, and the case where the cyanuric acid derivative and the isocyanuric acid derivative are used in combination.

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

  It is known that a metal chloride forms a polyene with a π complex and is colored, but since the present system material forms a colorless chelate compound, an effect is also exhibited in reducing coloring. However, this system material is inferior in compatibility with the vinyl chloride resin, so that it is necessary to adjust the amount appropriately.

C: Stearoylbenzoylmethane The role of stearoylbenzoylmethane will be described below.
Generally, dibenzoylmethane (DBM) has been used as an allyl salt stabilizer for vinyl chloride resins. Works in the following formulas (I) and (II) under fatty acid salts and metal compounds. That is, by stabilizing the allyl salt, it functions as a coloring inhibitor as a result.

Although it is known that DBM has a photosensitizing property, it requires 1/2 mol of metal salt to stabilize allyl salt and the reaction is two-stage. Is. In the present invention, stearoylbenzoylmethane was used as a material for stabilizing the allyl salt earlier in one step. The reaction formula (III) is shown below. The allyl salt is stabilized in one step in the presence of the metal salt.

  The mass ratio (C / B) of the (C) stearoylbenzoylmethane to the (B) cyanuric acid derivative or the isocyanuric acid derivative is 0.25 to 6. The effects of the present invention are achieved by setting the content mass ratio within the above range. The preferable content mass ratio (C / B) is 0.25 to 5, more preferably 0.25 to 4, and further preferably 0.25 to 3.

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

  Further, the high-density oxidized polyethylene wax in the embodiment of the present invention has a viscosity at 150 ° C. within a range of 2500 to 85000 cps, and contains 0.01 to 2 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Preferably. The viscosity at 150 ° C. is in the range of 8500 to 85000 cps, and it is more preferable to contain 0.04 to 0.1 parts by mass with respect to 100 parts by mass of the vinyl chloride resin described above from the viewpoint of improving kneading efficiency.

  Further, as long as the effects of the present invention are exhibited, a polyolefin wax other than the high-density oxidized polyethylene wax may be further added, if 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 trimellitate plasticizers from the viewpoint of adhesion to annealed copper wires and heat resistance, for example, tri-2-ethylhexyl trimellitate, trimermalic acid trimellitate, and triisodecyl trimellitate. The trimellitic acid ester can be mentioned. From the viewpoint of heat resistance and cost, it is more preferable to use tri-2-ethylhexyl trimellitate. It is difficult to obtain sufficient heat resistance with phthalates. Further, the polyester plasticizer may cause hydrolysis. The content of the plasticizer 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 the required 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 legislation to use a lead-free stabilizer that does not contain lead. Examples of the lead-free stabilizer include hydrotalcite-based stabilizers and calcium-zinc-based composite stabilizers. When calcium stearate, zinc stearate, or the like is added as the above-mentioned fatty acid metal salt, these can also function as a stabilizer.

(Other additives)
In the vinyl chloride resin composition according to the embodiment of the present invention, in addition to the above additives, if necessary, a flame retardant, a filler, a cross-linking agent, a cross-linking aid, an ultraviolet absorber, a light stabilizer, a lubricant, Antioxidants, colorants, processability improvers, other modifiers, etc. 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 method of crosslinking, and the method is not particularly limited, and methods such as chemical crosslinking, silane crosslinking, and radiation crosslinking can be used. The degree of crosslinking is preferably 40 to 65%, and more preferably 49 to 60% in terms of gel fraction.

  As a crosslinking aid, trimethylolpropane trimethacrylate, dipentaerythritol hexaacrylate, etc. can be used, and 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, crosslinking may occur during molding.

[Insulated wire]
An insulated wire according to an embodiment of the present invention is characterized by including a conductor and an insulating layer formed on the outer periphery of the conductor and made of the vinyl chloride resin composition according to the embodiment of the present invention.

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, an insulated wire 10 according to this embodiment includes a conductor 1 and an insulating layer 2 that covers the outer periphery of the conductor 1. As the conductor 1 to be covered, for example, a conductor having an outer diameter of about 0.15 to 7 mmφ can be used. A conductor obtained by twisting tin-plated annealed copper wires can be preferably used, but the present invention is not limited to this. The conductor 1 is not limited to the case where there is one conductor as shown in FIG. 1, and may be a plurality of conductors.

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 conductors 21 arranged in parallel and an insulating layer 22 collectively coated on the outer periphery of the two conductors 21. As the conductor 21, it is preferable to use a non-tinned annealed copper wire, that is, a bare annealed copper wire, from the viewpoint of adhesion to the resin composition forming the insulating layer 22. As the conductor 21, for example, a conductor having an outer diameter of about 0.15 to 7 mmφ can be used. A conductor obtained by twisting a plurality of bare annealed copper wires (7 in FIG. 2) can be preferably used, but the conductor 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.

  The insulating layers 2 and 22 are composed of the above vinyl chloride resin composition according to the embodiment of the present invention. In particular, the insulating layer 22 is preferably made of a vinyl chloride resin composition containing the above plasticizer in the above content ratio. An insulated wire can be obtained by coating as an insulating layer by a molding means such as extrusion coating and then crosslinking the vinyl chloride resin by a method such as electron beam irradiation. Incidentally, the extrusion coating, a vinyl chloride resin composition before crosslinking is kneaded with a roll, Banbury, extruder or the like, the pellet compound obtained and a conductor with a conventionally known wire extruder equipped with a crosshead die. It can be performed by, for example, extrusion-molding an electric wire.

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

〔cable〕
The cable according to the embodiment of the present invention is characterized by using the vinyl chloride resin composition according to the 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 the cable according to the embodiment of the present invention.
As shown in FIG. 3, a cable 30 according to the present embodiment includes an insulated electric wire 10 in which a conductor 1 is covered with an insulating layer 2, and a three-core stranded wire in which three wires are twisted together with an interposer 4 such as paper, The wrapping tape 5 provided on the outer circumference of the stranded wire and the sheath 3 extruded on the outer circumference thereof are provided. The insulated wire is not limited to the three-core stranded wire, and may be one insulated wire (single core) or a multi-core stranded wire other than the three-core stranded wire.

  The sheath 3 is made of the above vinyl chloride resin composition according to the embodiment of the present invention. The insulating layer 2 may also be composed of the above vinyl chloride resin composition. A cable can be obtained by coating an insulating layer or a sheath layer by a molding means such as extrusion coating, and then crosslinking the vinyl chloride resin by a method such as electron beam irradiation.

  In the present embodiment, the sheath may have a single-layer structure or a multi-layer structure. Furthermore, you may give a separator, a braid, 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 its use include wiring at a high temperature portion in a device such as a dryer, a rice cooker, a transformer outlet, a lighting fixture, and an air conditioner.

[Effects 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 the sheath can be suppressed, and the insulating layer or the sheath can be suppressed. It is possible to provide a vinyl chloride resin composition capable of suppressing the occurrence of surface roughening and unevenness (enabling a good appearance), and an insulated wire and cable using the same.

(2) According to the embodiment of the present invention, the content mass ratio (C / B) of (C) stearoylbenzoylmethane to the (B) cyanuric acid derivative or the isocyanuric acid derivative is a low value (for example, 1 or less, further, 0. 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) When the content ratio (A1 / A2) of the fatty acid zinc salt (A1) to the fatty acid metal salt other than the fatty acid zinc salt (A2) is 4 or more, the kneading time tends to be long due to excessive lubricity. However, according to the embodiment of the present invention, the kneading time is shortened even when 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 or more. Thus, it is possible to provide an electric wire coating material having an improved kneading moldability, and an insulated electric wire and a cable using the same.

(4) According to the embodiment of the present invention, in a multicore parallel insulated electric wire using a bare annealed copper wire as a conductor, even if pretreatment such as heat treatment is performed after peeling the insulating layer, one side does not protrude as shown in FIG. Provided are a vinyl chloride resin composition capable of maintaining uniform lengths of exposed conductors as shown in FIG. 4 and improving work efficiency during connection processing, and insulated wires and cables using the same. can do.

  According to the embodiment of the present invention, in which the insulating layer is composed of the vinyl chloride resin composition containing the above-mentioned plasticizer in the above-mentioned content ratio, a multi-core parallel insulated electric wire using a tin-plated annealed copper wire as a conductor. Also in the above, the occurrence rate of one conductor protruding after the insulating layer is peeled off can be suppressed to some extent. In this case, when the tin-plated annealed copper wire has a thinner tin-plated thickness, the above-mentioned occurrence rate can be further reduced. 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.

  An insulated wire 10 having the structure shown in FIG. 1 and an insulated wire 20 having the structure shown in FIG. 2 were manufactured by the following method and evaluated.

(1) Preparation of Vinyl Chloride Resin Composition The materials shown in Tables 1 and 2 were blended at the ratios described, and kneaded and mixed with an open roll mixer heated to 140 ° C. to form pellets. A vinyl chloride resin composition was obtained. The materials used are as shown in Table 3.

As a reference, the kneading property was evaluated by the following method. As a result, Examples 1 to 5, Reference Example 1 and Comparative Example 1 were evaluated as ◯, and Comparative Examples 2 and 3 were evaluated as ×.
When kneading with an open-roll mixer heated to 140 ° C, within 5 minutes, the mixture sheet wrapped around the front roll has a smooth appearance and no slack appears on the sheet, ◯, rough appearance or slack on the sheet occurs. The thing was marked as x. The symbol X is a phenomenon caused by excessive external lubricity, and when mass-produced by a continuous kneader or a batch mixer, a uniformly dispersed kneaded product cannot be obtained.

(2) Production of Insulated Electric Wire (2-1) Production of Insulated Electric Wire 10 having Structure of FIG. 1 (Examples 1 to 5, Reference Example 1 and Comparative Examples 1 to 3)
As the conductor, a 26-strand conductor having an outer diameter of 0.16 mmφ tin-plated annealed copper wire (outer diameter 0.94 mmφ, tin-plated thickness 0.5 μm) was used. The vinyl chloride resin composition prepared on the basis of Table 1 in (1) above was extruded on the conductor by a melt extrusion method to obtain a sample (insulated electric 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 production conditions were a cylinder temperature of 170 ° C., a head temperature of 180 ° C., and a work at a linear velocity of 400 m / min.

(2-2) Production of insulated wire 20 having the structure of FIG. 2 (Examples 6 to 10, Reference Examples 2 to 4 and Comparative Examples 4 to 6)
As a conductor, an outer diameter of 0.16 mmφ annealed copper wire (bare annealed copper wire) is used in Examples 6 to 8 and Reference Example 2 , and an outer diameter of 0 is used in Examples 9 and 10, Reference Examples 3 and 4, and Comparative Examples 4 to 6. .16 mmφ tin-plated annealed copper wire 7-stranded conductor (outer diameter 0.94 mmφ, tin plating thickness 0.5 μm (Example 9, Reference Example 3 and Comparative Examples 4 to 6), tin plating thickness 0.1 μm (Example 10) , Reference Example 4 )) was used. A vinyl chloride resin composition prepared on the basis of Table 2 in (1) above was extruded on the conductor by a melt extrusion method to obtain a sample (2-core parallel insulated wire) in which the conductor was coated with each vinyl chloride resin composition. It was The obtained two-core parallel insulated electric wire had a thickness (X shown in FIG. 2) of 1.3 mm and a width (Y shown in FIG. 2) of 2.6 mm. The electric wire production conditions were a cylinder temperature of 180 ° C., a head temperature of 190 ° C., and a work at a linear velocity of 250 m / min. Examples 9 and 10 and Reference Examples 3 and 4 differ only in the tin-plated thickness of the tin-plated soft copper wire.

(3) Evaluation 1 of insulated wire (color change)
Regarding the insulated wire of each of the above examples, the wire cut to a length of 300 mm was exposed to a gear oven (forced circulation air heating aging tester) at 100 ° C. for 500 hours, and the hue change before and after the exposure was confirmed. Regarding the change in hue, a visual comparison test by 5 people was conducted, and all 5 persons judged to have no discoloration before and after the exposure were marked ◎, 4 persons judged that there was no discoloration, and 0 to 3 persons judged that there was no discoloration. Was designated as x. The evaluation results are shown in Tables 1 and 2.

(4) Evaluation 2 of insulated wire (appearance)
The appearance of the insulated wire of each of the above examples was visually evaluated. If the surface was glossy and the surface was smooth, it was marked with ⊚, if the surface was smooth but in a matte state, it was marked with ○, and if the surface was rough or uneven, it was marked with x. The evaluation results are shown in Tables 1 and 2.

(5) Evaluation 3 of insulated wire (uniformity of conductor length after insulation layer peeling)
The two-core parallel insulated electric wire produced in the above (2-2) was cut into a length of 500 mm, and the insulating layer was peeled off by 5 mm from the tip of the electric wire to obtain the state shown in FIG. Then, after heating in a gear oven at 120 ° C. for 3 hours, it was taken out of the gear oven and the length of the two-core conductor was measured. If the length of the two-core conductor after the heat treatment is within the range of 4.5 to 5.5 mm, it is judged as a non-defective product, and one of the two-core conductors has a length of less than 4.5 mm or more than 5.5 mm. It was judged that the product was defective. The test was performed with N = 20. 20 out of 20 were good products, ∘ was 16 to 19 out of 20 was good products, and less than 16 out of 20 was good products.

(6) Comprehensive judgment In the comprehensive judgment, those in which all of the above-mentioned evaluations 1 to 2 or 1 to 3 were ⊚ or ◯ were judged to be acceptable. The results are shown in Tables 1 and 2.

In Examples 1 to 5 and Reference Example 1 , both the hue change and the appearance were good, and the overall evaluation was acceptable.

In Examples 6 to 10 and Reference Examples 2 to 4 , the hue change, the appearance, and the uniformity of the conductor length after the insulating layer was peeled off were good, and the overall judgment was acceptable.

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

  In Comparative Example 2, the polyethylene wax was contained, but (D) the high-density oxidized polyethylene wax was not contained, and the mass ratio of C / B and the mass ratio of A1 / (A2 + A3) were large. The appearance was poor and the overall evaluation was unacceptable.

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

  In Comparative Example 4, (D) the 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 the mass ratio of A1 / (A2 + A3) were small. The result of the change was bad. Further, since a tin-plated annealed copper wire is used as the conductor and the amount of the plasticizer is large, the result of the uniformity of the conductor length after the insulating layer is peeled off is poor. Therefore, the overall judgment was unsuccessful.

  In Comparative Example 5, since the C / B mass ratio and the A1 / (A2 + A3) mass ratio were large, the results were poor in terms of hue change and appearance. Further, since tin-plated annealed copper wire was used as the conductor and the amount of the plasticizer was slightly small, the result of uniformity of the conductor length after peeling off the insulating layer was 10% or more that was not acceptable. Therefore, the overall judgment was unsuccessful.

  In Comparative Example 6, a tin-plated 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, the result of the hue change was poor, and the conductor after the insulating layer was peeled off. 20% or more of the results of the uniformity of length were rejected. Therefore, the overall judgment was unsuccessful.

  As described above, by using four kinds of (A) fatty acid metal salt, (B) cyanuric acid derivative or isocyanuric acid derivative, (C) stearoylbenzoylmethane, and (D) high-density oxidized polyethylene wax, in the above-mentioned appropriate amount range. It was found that the discoloration of vinyl chloride resin in the presence of a basic compound can be suppressed at low temperature for a long time. Furthermore, they have found that both the above-described suppression of discoloration and good extrusion molding (good appearance) can be achieved. Further, in a two-core parallel insulated electric wire in which a bare annealed copper wire is used as a conductor and the vinyl chloride resin composition according to the embodiment of the present invention is used as an insulating layer, the uniformity of the conductor length after peeling the insulating layer is excellent. Found.

  The present invention is not limited to the above-mentioned embodiment and examples, and can be variously modified.

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

Claims (14)

A conductor and an insulating layer made of a vinyl chloride resin composition, which is coated on the outer periphery of the conductor,
The conductor is a bare annealed copper wire,
The vinyl chloride resin composition comprises a base polymer containing a vinyl chloride resin, (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. 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 (B) the cyanuric acid derivative or the isocyanuric acid derivative described above. (C) containing the mass ratio of stearoylbenzoylmethane (C / B) is 0.25 to 1 der is, the (B) cyanuric acid derivatives or isocyanuric acid derivatives, insulation made of isocyanuric acid tris (2-hydroxyethyl) Electrical wire.   The insulated wire according to claim 1, wherein the vinyl chloride resin composition contains a plasticizer in an amount of 25 to 70 parts by mass 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 the (A1) fatty acid zinc salt and the (A2) fatty acid zinc salt, and the (A1) fatty acid zinc salt relative to the (A2) fatty acid metal salt other than the fatty acid zinc salt The insulated wire according to any one of claims 1 to 3, wherein the content mass ratio (A1 / A2) of 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 high-density oxidized polyethylene wax (D) has a viscosity at 150 ° C. within a 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. Insulated electric wire given in any 1 paragraph of ~ 5.   Of 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, relative to the total content of the (A) fatty acid metal salt. The insulated wire according to any one of claims 1 to 6, wherein the content ratio is 35% by mass or more.   The insulated wire according to any one of claims 1 to 7, which further contains 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 a plasticizer. ,
The total content of (A) to (D) is 1 to 4.5 parts by mass, and the content of the plasticizer is 25 to 70 parts by mass, relative to 100 parts by mass of the vinyl chloride resin, wherein for cyanuric acid derivatives or isocyanuric acid derivative (C) stearoylbenzoylmethane content mass ratio of methane (C / B) is Ri der 0.25, wherein (B) cyanuric acid derivatives or isocyanuric acid derivatives, isocyanuric acid tris A vinyl chloride resin composition comprising (2-hydroxyethyl) .   An insulated wire comprising an insulating layer made of the vinyl chloride resin composition according to claim 9.   The insulated electric wire according to any one of claims 1 to 8, which is a multi-core parallel insulated electric wire. A plurality of conductors, and an insulating layer made of a vinyl chloride resin composition, which is 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,
In the vinyl chloride resin composition, (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 are added to a vinyl chloride resin-containing base polymer. And a plasticizer, and the total content of (A) to (D) is 1 to 4.5 parts by mass, and the content of the plasticizer is 25 to 70 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. a part, the (B) the relative cyanuric acid derivatives or isocyanuric acid derivative (C) containing the mass ratio of stearoylbenzoylmethane (C / B) is Ri der 0.25, wherein (B) cyanuric acid derivatives or isocyanuric acid derivatives, isocyanuric acid tris (2-hydroxyethyl) Tona Ru multicore parallel insulated wire. 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 a plasticizer. The total content of (A) to (D) is 1 to 4.5 parts by mass, and the content of the plasticizer is 25 to 70 parts by mass, relative to 100 parts by mass of the vinyl chloride resin, ) the relative cyanuric acid derivatives or isocyanuric acid derivative (C) stearoylbenzoylmethane content mass ratio of methane (C / B) is Ri der 0.25, wherein (B) cyanuric acid derivatives or isocyanuric acid derivatives, isocyanuric acid A cable having a sheath made of a vinyl chloride resin composition made of tris (2-hydroxyethyl) .   A cable according to claim 13, comprising the insulated wire according to any one of claims 1 to 8 and 10 to 12.

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