CN111909468B - Vinyl chloride resin composition, insulated wire, cable, method for producing insulated wire, and method for producing cable - Google Patents

Vinyl chloride resin composition, insulated wire, cable, method for producing insulated wire, and method for producing cable Download PDF

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Publication number
CN111909468B
CN111909468B CN202010351580.4A CN202010351580A CN111909468B CN 111909468 B CN111909468 B CN 111909468B CN 202010351580 A CN202010351580 A CN 202010351580A CN 111909468 B CN111909468 B CN 111909468B
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mass
parts
vinyl chloride
chloride resin
base polymer
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CN111909468A (en
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菊池龙太郎
三浦刚
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Bomeilicheng Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K3/2279—Oxides; Hydroxides of metals of antimony
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Insulated Conductors (AREA)
  • Manufacturing Of Electric Cables (AREA)
  • Organic Insulating Materials (AREA)
  • Processes Specially Adapted For Manufacturing Cables (AREA)

Abstract

The invention provides a vinyl chloride resin composition which can prevent discoloration caused by electron beam irradiation and has excellent heat resistance and flame retardance, an insulated wire and cable using the same, and a method for manufacturing the insulated wire and cable. The vinyl chloride resin composition of the present invention comprises: a base polymer containing a vinyl chloride resin having a K value of 75 to 86, a flame retardant comprising aluminum hydroxide and hydrotalcite, a stabilizer comprising zinc stearate, an isocyanuric acid derivative, stearoyl benzoyl methane and a dibenzoyl methane metal salt, a covering agent containing rutile-type titanium dioxide, and a plasticizer. The total content of the stabilizer is 2 parts by mass or more, the content of the rutile titanium dioxide is 2 parts by mass or more, and the total content of the flame retardant is 12 parts by mass or more and 16 parts by mass or less, based on 100 parts by mass of the base polymer.

Description

Vinyl chloride resin composition, insulated wire, cable, method for producing insulated wire, and method for producing cable
Technical Field
The present invention relates to a vinyl chloride resin composition, an insulated wire, a cable, a method for producing an insulated wire, and a method for producing a cable.
Background
An electric wire (insulated electric wire) has a conductor and an insulating layer as a coating material provided around the conductor. The cable includes the electric wire and a sheath (outer coating) as a coating material provided around the electric wire. The sheath is arranged around the insulating layer.
The insulating layer of the electric wire and the coating material such as the sheath of the cable are made of an electrically insulating material mainly composed of rubber or resin. The insulating layer of the electric wire is formed of an electrically insulating material containing rubber or resin as a main material. The characteristics required of such an electric wire vary depending on the purpose thereof. For example, high flame retardancy, tensile characteristics, heat resistance, and the like are required for electric wires for automobiles. In particular, the flame retardancy requirements are acceptable in the vertical flame retardant test VW-1 specified in flame retardancy standard UL 1581.
As an example of such an electric wire, patent document 1 describes an insulated electric wire comprising a conductor and a coating layer (insulating layer) coated around the conductor, wherein the coating layer is composed of a vinyl chloride resin composition to which a metal hydrate (metal hydroxide) is added.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2011-26427
Disclosure of Invention
Problems to be solved by the application
The present inventors have studied on improvement of heat resistance and flame retardancy of a vinyl chloride resin composition. However, it was confirmed that when the heat resistance and flame retardancy were improved, discoloration called irradiation burn occurred in the vinyl chloride resin composition crosslinked by irradiation with electron beams, the insulated wire having the vinyl chloride resin composition as an insulating layer, or the cable having the vinyl chloride resin composition as a sheath. If such discoloration occurs, there is a problem that it is difficult to distinguish the hue of the insulating layer and the sheath.
The present application has been made in view of the above problems, and an object thereof is to provide a vinyl chloride resin composition which can prevent discoloration due to electron beam irradiation and is excellent in heat resistance and flame retardancy, and an insulated wire and cable using the same.
Means for solving the problems
An outline of a representative embodiment of the application disclosed in the present application will be briefly described below.
[1] A vinyl chloride resin composition contains a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent and a plasticizer. The base polymer contains a vinyl chloride resin having a K value of 75 to 86, the covering agent contains rutile-type titanium dioxide, and the fatty acid metal salt contains zinc stearate. The total content of the zinc stearate, the cyanuric acid derivative, the isocyanuric acid derivative, the stearoyl benzoyl methane, the dibenzoyl methane and the dibenzoyl methane metal salt is 2 parts by mass or more per 100 parts by mass of the base polymer. The content of the rutile titanium dioxide is 2 parts by mass or more relative to 100 parts by mass of the base polymer, and the total content of the aluminum hydroxide and the hydrotalcite is 12 parts by mass or more and 16 parts by mass or less relative to 100 parts by mass of the base polymer.
[2] A vinyl chloride resin composition contains a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent and a plasticizer. The base polymer contains a vinyl chloride resin having a K value of 75 to 86, the covering agent contains rutile titanium dioxide and antimony trioxide, and the fatty acid metal salt contains zinc stearate. The total content of the zinc stearate, the cyanuric acid derivative, the isocyanuric acid derivative, the stearoyl benzoyl methane, the dibenzoyl methane and the dibenzoyl methane metal salt is 2 parts by mass or more per 100 parts by mass of the base polymer. The content of antimony trioxide is less than 3.5 parts by mass per 100 parts by mass of the base polymer, and the total content of the aluminum hydroxide, the hydrotalcite and the antimony trioxide is 12 parts by mass to 16 parts by mass relative to 100 parts by mass of the base polymer.
[3] The vinyl chloride resin composition according to [2], wherein the rutile titanium dioxide is contained in an amount of 0.94 parts by mass or more based on 100 parts by mass of the base polymer; the antimony trioxide is contained in an amount of 1.8 parts by mass or more and less than 3.5 parts by mass relative to 100 parts by mass of the base polymer.
[4] The vinyl chloride resin composition according to any one of [1] to [3], wherein the fatty acid metal salt further comprises calcium stearate, and the mass ratio of the zinc stearate to the calcium stearate is 12 to 13.
[5] The vinyl chloride resin composition according to any one of [1] to [4], wherein the base polymer contains a vinyl chloride resin having a K value of 71 to 73 and a vinyl chloride resin having a K value of 84 to 86.
[6] An insulated wire comprising an insulating layer formed of the vinyl chloride resin composition of any one of [1] to [5], wherein the vinyl chloride resin composition is crosslinked in the insulating layer.
[7] A cable comprising a sheath formed of the vinyl chloride resin composition according to any one of [1] to [5], wherein the vinyl chloride resin composition is crosslinked.
[8] A method of manufacturing an insulated wire, comprising: (a) Mixing a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent, and a plasticizer to form a vinyl chloride resin composition; (b) Extruding the vinyl chloride resin composition so as to surround the coated conductor to form an insulating layer; (c) And a step of irradiating the insulating layer with an electron beam to crosslink the vinyl chloride resin composition. The base polymer contains a vinyl chloride resin having a K value of 75 to 86, the covering agent contains rutile-type titanium dioxide, and the fatty acid metal salt contains zinc stearate. The total content of the zinc stearate, the cyanuric acid derivative, the isocyanuric acid derivative, the stearoyl benzoyl methane, the dibenzoyl methane and the dibenzoyl methane metal salt is 2 parts by mass or more per 100 parts by mass of the base polymer. The content of the rutile titanium dioxide is 2 parts by mass or more relative to 100 parts by mass of the base polymer, and the total content of the aluminum hydroxide and the hydrotalcite is 12 parts by mass or more and 16 parts by mass or less relative to 100 parts by mass of the base polymer.
[9] A method of manufacturing an insulated wire, comprising: (a) Mixing a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent, and a plasticizer to form a vinyl chloride resin composition; (b) Extruding the vinyl chloride resin composition so as to surround the coated conductor to form an insulating layer; (c) And a step of irradiating the insulating layer with an electron beam to crosslink the vinyl chloride resin composition. The base polymer contains a vinyl chloride resin having a K value of 75 to 86, the covering agent contains rutile titanium dioxide and antimony trioxide, and the fatty acid metal salt contains zinc stearate. The total content of the zinc stearate, the cyanuric acid derivative, the isocyanuric acid derivative, the stearoyl benzoyl methane, the dibenzoyl methane and the dibenzoyl methane metal salt is 2 parts by mass or more per 100 parts by mass of the base polymer. The content of antimony trioxide is less than 3.5 parts by mass per 100 parts by mass of the base polymer, and the total content of the aluminum hydroxide, the hydrotalcite and the antimony trioxide is 12 parts by mass to 16 parts by mass relative to 100 parts by mass of the base polymer.
[10] The method of producing an insulated wire according to [9], wherein the rutile-type titanium dioxide is contained in an amount of 0.94 parts by mass or more based on 100 parts by mass of the base polymer; the antimony trioxide is contained in an amount of 1.8 parts by mass or more and less than 3.5 parts by mass relative to 100 parts by mass of the base polymer.
[11] The method for producing an insulated wire according to any one of [8] to [10], wherein the base polymer contains a vinyl chloride resin having a K value of 71 to 73 and a vinyl chloride resin having a K value of 84 to 86.
[12] A method of manufacturing a cable comprising: (a) Mixing a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent, and a plasticizer to form a vinyl chloride resin composition; (b) Extruding the vinyl chloride resin composition so as to cover the circumference of an insulated wire having a conductor and an insulating layer covering the circumference of the conductor, thereby forming a sheath; (c) And a step of irradiating the sheath with an electron beam to crosslink the vinyl chloride resin composition. The base polymer contains a vinyl chloride resin having a K value of 75 to 86, the covering agent contains rutile-type titanium dioxide, and the fatty acid metal salt contains zinc stearate. The total content of the zinc stearate, the cyanuric acid derivative, the isocyanuric acid derivative, the stearoyl benzoyl methane, the dibenzoyl methane and the dibenzoyl methane metal salt is 2 parts by mass or more per 100 parts by mass of the base polymer. The content of the rutile titanium dioxide is 2 parts by mass or more relative to 100 parts by mass of the base polymer, and the total content of the aluminum hydroxide and the hydrotalcite is 12 parts by mass or more and 16 parts by mass or less relative to 100 parts by mass of the base polymer.
[13] A method of manufacturing a cable comprising: (a) Mixing a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent, and a plasticizer to form a vinyl chloride resin composition; (b) Extruding the vinyl chloride resin composition so as to cover the circumference of an insulated wire having a conductor and an insulating layer covering the circumference of the conductor, thereby forming a sheath; (c) And a step of irradiating the sheath with an electron beam to crosslink the vinyl chloride resin composition. The base polymer contains a vinyl chloride resin having a K value of 75 to 86, the covering agent contains rutile titanium dioxide and antimony trioxide, and the fatty acid metal salt contains zinc stearate. The total content of the zinc stearate, the cyanuric acid derivative, the isocyanuric acid derivative, the stearoyl benzoyl methane, the dibenzoyl methane and the dibenzoyl methane metal salt is 2 parts by mass or more per 100 parts by mass of the base polymer. The content of antimony trioxide is less than 3.5 parts by mass per 100 parts by mass of the base polymer, and the total content of the aluminum hydroxide, the hydrotalcite and the antimony trioxide is 12 parts by mass to 16 parts by mass relative to 100 parts by mass of the base polymer.
[14] The method for producing a cable according to [13], wherein the rutile titanium dioxide is contained in an amount of 0.94 parts by mass or more based on 100 parts by mass of the base polymer; the antimony trioxide is contained in an amount of 1.8 parts by mass or more and less than 3.5 parts by mass relative to 100 parts by mass of the base polymer.
[15] The method for producing a cable according to any one of [12] to [14], wherein the base polymer contains a vinyl chloride resin having a K value of 71 to 73 and a vinyl chloride resin having a K value of 84 to 86.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a vinyl chloride resin composition which can prevent discoloration due to electron beam irradiation and is excellent in heat resistance and flame retardancy, and an insulated wire and cable using the same can be provided.
Drawings
Fig. 1 is a cross-sectional view showing a structure of an insulated wire according to an embodiment.
Fig. 2 is a cross-sectional view showing the structure of a cable according to an embodiment.
Symbol description
1: a conductor; 2: an insulating layer; 3: is arranged between; 4: a sheath; 10: an insulated wire; 11: and (3) a cable.
Detailed Description
(study item)
Before describing the embodiments, first, the matters studied by the present inventors will be described.
The present inventors have studied improvement of heat resistance and flame retardancy of a vinyl chloride resin composition (hereinafter referred to as a vinyl chloride resin composition of a study example).
Since vinyl chloride resin contains halogen and is excellent in flame retardancy, it is hard, and therefore, in order to be used for an insulating layer for insulating an electric wire or a sheath for a cable, a large amount of plasticizer needs to be added to the vinyl chloride resin to be used as a vinyl chloride resin composition. On the other hand, since the flame retardancy of the vinyl chloride resin composition is lowered by the addition of a plasticizer, it has been studied to add aluminum hydroxide or the like as a metal hydroxide to the vinyl chloride resin composition as a flame retardant.
However, it was confirmed that when flame retardancy and heat resistance were improved, discoloration, so-called irradiation burn, was caused by the vinyl chloride resin composition crosslinked by electron beam irradiation, an insulated wire having the vinyl chloride resin composition as an insulating layer, or a cable having the vinyl chloride resin composition as a sheath.
The following two factors are mainly considered as the reasons for this. First: the dehydrochlorination reaction of the vinyl chloride resin is promoted in the presence of aluminum hydroxide as a base to produce a polyene containing allyl chloride (-ch=ch-CHCl-) (hereinafter referred to as an allyl chloride compound) which develops color. Second,: since (2) aluminum chloride formed by neutralization of hydrogen chloride with aluminum hydroxide forms pi complex with allyl chloride compound, the pi complex undergoes color development.
In general, since a vinyl chloride resin undergoes decomposition reaction in which hydrogen chloride is released by heat, ultraviolet rays, oxygen, or the like during production, processing, or use, and thus changes in color, a stabilizer is added to a vinyl chloride resin composition in order to capture and neutralize hydrogen chloride generated by a dehydrochlorination reaction of the vinyl chloride resin or in order to stabilize an allyl chloride compound. However, since the energy of the electron beam is far greater than that of heat, ultraviolet rays, etc., it is considered that it is difficult to prevent discoloration due to electron beam irradiation only by the addition of a stabilizer. Even if discoloration due to electron beam irradiation can be prevented, the stabilizer is consumed at this time, and therefore there is a concern that heat resistance may be lowered.
Further, it is known that if aluminum hydroxide is added in a large amount to a vinyl chloride resin in order to improve flame retardancy, heat resistance is lowered, and it is difficult to achieve both flame retardancy and heat resistance.
In view of the above, when aluminum hydroxide is added as a flame retardant to a vinyl chloride resin composition, it is desired to obtain a vinyl chloride resin composition which is excellent in heat resistance and flame retardancy while preventing discoloration due to electron beam irradiation by grinding its composition. Further, it is desired to provide an insulated wire and cable which can prevent discoloration due to electron beam irradiation and which is excellent in heat resistance and flame retardancy, using the vinyl chloride resin composition.
(embodiment)
Features and effects of vinyl chloride resin composition
The vinyl chloride resin composition according to the present embodiment will be described in detail below. The vinyl chloride resin composition according to the present embodiment contains (a) a vinyl chloride resin, (B) aluminum hydroxide, (C) hydrotalcite, (D) a fatty acid metal salt, (E) a cyanuric acid derivative (isocyanuric acid derivative), (F) stearylbenzoylmethane, (G) dibenzoylmethane (dibenzoylmethane metal salt), (H) a covering agent, and (I) a plasticizer. Here, (E) a cyanuric acid derivative (isocyanuric acid derivative) means either one of the cyanuric acid derivative alone, the isocyanuric acid derivative alone or both. Similarly, (G) dibenzoylmethane (dibenzoylmethane metal salt) means dibenzoylmethane alone, dibenzoylmethane metal salt alone or in combination.
The vinyl chloride resin (a) according to the present embodiment contains a resin having a K value of 75 to 86. Here, the K value is a value showing the specific viscosity of the vinyl chloride resin as measured by a test method prescribed in JIS K7367-2 or ISO 1628-2, and is related to the degree of polymerization. More specifically, the vinyl chloride resin (a) according to the present embodiment uses any one of (A2) a resin having a K value of 75 to 78, (A3) a resin having a K value of 79 to 82, and (A4) a resin having a K value of 83 to 86, alone. Alternatively, the vinyl chloride resin (a) according to the present embodiment may be used in combination with any two of a resin having a K value (A1) of 71 to 74, a resin having a K value (A2) of 75 to 78, a resin having a K value (A3) of 79 to 82, and a resin having a K value (A4) of 83 to 86.
In addition, in the (H) covering agent according to the present embodiment, (H1) rutile titanium dioxide is used alone or (H1) rutile titanium dioxide and (H2) antimony trioxide are used in combination.
Hereinafter, the vinyl chloride resin (a) constituting the vinyl chloride resin composition is described as a base polymer. In this embodiment, for convenience, the aluminum hydroxide (B) and the hydrotalcite (C) are sometimes collectively referred to as a flame retardant. Likewise, for convenience, the (D) fatty acid metal salt, (E) cyanuric acid derivative (isocyanuric acid derivative), (F) stearoyl benzoyl methane, and (G) dibenzoyl methane (dibenzoyl methane metal salt) are sometimes collectively referred to as a stabilizer. In this embodiment, the (H2) antimony trioxide also functions as a flame retardant, but is conveniently classified as (H) a covering agent.
The vinyl chloride resin composition according to the present embodiment has the above-described characteristics, whereby discoloration due to electron beam irradiation can be prevented, and heat resistance and flame retardancy can be improved. The reason for this will be specifically described below.
First, the vinyl chloride resin composition according to the present embodiment contains (a) a vinyl chloride resin having a K value of 75 to 86. In this way, in the present embodiment, since a vinyl chloride resin having a relatively high polymerization degree and a large molecular weight is used as the base polymer, dehydrochlorination reaction is less likely to occur, and heat resistance can be improved.
The vinyl chloride resin composition according to the present embodiment contains (B) aluminum hydroxide and (C) hydrotalcite. By doing so, flame retardancy can be improved. However, as described above, if (B) aluminum hydroxide is added in a large amount, heat resistance is lowered. Therefore, the use of hydrotalcite (C) in combination, which functions as both a flame retardant and a hydrogen chloride scavenger, can achieve both heat resistance and flame retardancy.
On the other hand, in the vinyl chloride resin composition, (B) aluminum hydroxide and (C) hydrotalcite promote dehydrochlorination reaction, and thus cause discoloration due to electron beam irradiation. Therefore, in the vinyl chloride resin composition according to the present embodiment, (D) a fatty acid metal salt, (E) a cyanuric acid derivative (isocyanuric acid derivative), (F) stearoyl benzoyl methane, and (G) dibenzoyl methane (dibenzoyl methane metal salt) are used in combination as a stabilizer. By doing so, discoloration due to electron beam irradiation can be prevented in the vinyl chloride resin composition, and heat resistance can be improved.
However, according to the studies by the present inventors, it was confirmed that the discoloration of the vinyl chloride resin composition due to the electron beam irradiation cannot be completely prevented by the stabilizer alone. Therefore, the discoloration due to the irradiation of the electron beam can be prevented reliably by further adding (H) the masking agent to the vinyl chloride resin composition according to the present embodiment.
As described above, the vinyl chloride resin composition according to the present embodiment can prevent discoloration due to electron beam irradiation and can improve heat resistance and flame retardancy.
Detailed constitution of vinyl chloride resin composition
Hereinafter, the raw materials used in the vinyl chloride resin composition according to the present embodiment will be described in more detail, and the amount of the raw materials and the like necessary for the establishment of the present invention will be included.
[ base Polymer ]
The vinyl chloride resin (a) according to the present embodiment constitutes the base polymer of the vinyl chloride resin composition according to the present embodiment. As described above, the K value is a value indicating the specific viscosity of the vinyl chloride resin and is related to the degree of polymerization. Specifically, the average degree of polymerization of the vinyl chloride resin having a K value of 71 or more and 74 or less is about 1300, the average degree of polymerization of the vinyl chloride resin having a K value of 75 or more and 78 or less is about 1700, the average degree of polymerization of the vinyl chloride resin having a K value of 79 or more and 82 or less is about 2000, and the average degree of polymerization of the vinyl chloride resin having a K value of 83 or more and 86 or less is about 2500.
In the vinyl chloride resin, if the polymerization degree is lowered, moldability is improved but heat resistance is lowered. On the other hand, if the polymerization degree is increased, the heat resistance is improved but the moldability is lowered. Specifically, when the polymerization degree of the vinyl chloride resin is increased, the molecular weight becomes large, and thus dehydrochlorination reaction is less likely to occur, and heat resistance is improved. On the other hand, when the polymerization degree of the vinyl chloride resin is increased, the molecular weight becomes large, so that the affinity with the plasticizer is lowered, and the processability is lowered. However, if the polymerization degree of the vinyl chloride resin is increased, it is necessary to increase the processing temperature, and as a result, dehydrochlorination reaction may be promoted.
In this embodiment, any one of (a) a vinyl chloride resin, (A2) a resin having a K value of 75 to 78, (A3) a resin having a K value of 79 to 82, or (A4) a resin having a K value of 83 to 86 is used alone. In the present embodiment, the heat resistance and moldability can be achieved by setting the K value of the vinyl chloride resin to 75 to 86 (average polymerization degree 1300 to 2500).
In the present embodiment, any two of (a) a vinyl chloride resin, (A1) a resin having a K value of 71 or more and 74 or less, (A2) a resin having a K value of 75 or more and 78 or less, (A3) a resin having a K value of 79 or more and 82 or less, and (A4) a resin having a K value of 83 or more and 86 or less are used in combination. In this way, in the present embodiment, by using two types of vinyl chloride resins having different K values (degrees of polymerization) in combination, heat resistance and moldability can be further improved.
The base polymer may further contain a vinyl chloride-vinyl acetate copolymer, an ethylene-vinyl acetate copolymer, a chlorinated polyethylene, or the like as a resin component other than the vinyl chloride resin (a). In this case, from the viewpoint of avoiding a decrease in heat resistance of the vinyl chloride resin composition according to the present embodiment, the content of the resin component other than (a) the vinyl chloride resin is preferably 5 parts by mass or more and less than 20 parts by mass in 100 parts by mass of the base polymer.
[ flame retardant ]
The aluminum hydroxide (B) according to the present embodiment functions as a flame retardant. Specifically, (B) aluminum hydroxide causes dissociation reaction of crystal water (hydration water) which is an endothermic reaction at a temperature of 200 ℃ or higher, and thus contributes to flame retardancy.
The hydrotalcite (C) according to the present embodiment functions as a flame retardant and a stabilizer. Specifically, (C) hydrotalcite has the following effects: the aluminum hydroxide contributes to flame retardancy by an endothermic reaction at the time of decomposition and also contributes to discoloration resistance by hydrogen chloride capturing ability, similarly to the aluminum hydroxide (B).
[ stabilizer ]
The fatty acid metal salt (D) according to the present embodiment is also referred to as a metal soap and functions as a stabilizer. Specifically, the fatty acid metal salt contributes to the discoloration resistance against irradiation through the hydrogen chloride capturing ability.
Examples of the fatty acid constituting the fatty acid metal salt (D) include saturated fatty acids having 8 to 22 carbon atoms and unsaturated fatty acids having 8 to 22 carbon atoms, and stearic acid having 17 carbon atoms is preferable from the viewpoint of affinity with vinyl chloride resin.
In the present embodiment, zinc stearate (D1) is preferably contained as the fatty acid metal salt (D) from the viewpoint of high hydrogen chloride capturing ability.
Further, in the present embodiment, as the (D) fatty acid metal salt, (D1) zinc stearate and (D2) calcium stearate are further preferably used in combination. First, (D1) zinc stearate traps hydrogen chloride to produce zinc chloride, but this zinc chloride has a disadvantage of promoting dehydrochlorination of (a) vinyl chloride resin. Therefore, the above disadvantage can be eliminated by using (D2) calcium stearate in combination, whereby (D2) calcium stearate reacts with zinc chloride to be captured.
(D) The fatty acid metal salt also functions as a lubricant, and therefore has a high affinity with (a) a vinyl chloride resin, but (E) a cyanuric acid derivative (isocyanuric acid derivative), (F) stearoyl benzoyl methane and (G) dibenzoyl methane (dibenzoyl methane metal salt) have a low affinity with (a) a vinyl chloride resin, and therefore, the content of (D) a fatty acid metal salt relative to 100 parts by mass of the base polymer is preferably 60% to 95% relative to the total content of (D) a fatty acid metal salt, (E) a cyanuric acid derivative (isocyanuric acid derivative), (F) stearoyl benzoyl methane and (G) dibenzoyl methane (dibenzoyl methane metal salt).
The cyanuric acid derivative (isocyanuric acid derivative) of (E) according to the present embodiment functions as a stabilizer. Specifically, (E) a cyanuric acid derivative (isocyanuric acid derivative) forms a colorless chelate compound with the zinc chloride generated by capturing hydrogen chloride with the zinc stearate (D1) and is stabilized, whereby zinc chloride can be prevented from promoting the dehydrochlorination reaction of the vinyl chloride resin (a).
As the cyanuric acid derivative (isocyanuric acid derivative), an isocyanuric acid derivative is preferably used, and tris (2-hydroxyethyl) isocyanurate (tris (2-hydroxyethyl) isocyanurate) is more preferably used. The cyanuric acid derivative or the isocyanuric acid derivative (e.g., tris (2-hydroxyethyl) isocyanurate) serves to inhibit dehydrochlorination from vinyl chloride resin by chelation of metal salt.
The stearoyl benzoyl methane (F) according to the present embodiment functions as a stabilizer. Specifically, an allyl chloride compound is stabilized in the presence of a metal salt (e.g., zinc chloride) to contribute to the resistance to discoloration by irradiation.
The dibenzoylmethane (dibenzoylmethane metal salt) according to the present embodiment functions as a stabilizer. Specifically, (G) dibenzoylmethane reacts with a fatty acid metal salt (e.g., zinc stearate) to form a dibenzoylmethane metal salt (e.g., zinc dibenzoylmethane salt) that stabilizes the allyl chloride compound, thereby contributing to the resistance to discoloration by irradiation.
In this embodiment, (G) dibenzoylmethane is preferably added because (G) dibenzoylmethane functions by the 2-step reaction, and (G) dibenzoylmethane metal salt functions as a stabilizer by the 1-step reaction if (G) dibenzoylmethane metal salt is added in advance.
Heretofore, (F) stearylbenzoylmethane has been used as a stabilizer in place of (G) dibenzoylmethane (dibenzoylmethane metal salt), but it has been found in the present embodiment that discoloration due to electron beam irradiation can be effectively prevented by using (F) stearylbenzoylmethane and (G) dibenzoylmethane (dibenzoylmethane metal salt) in combination.
As shown in examples described later, the vinyl chloride resin composition according to the present embodiment contains (D1) zinc stearate as (D) a fatty acid metal salt, and the total content of (D1) zinc stearate, (E) a cyanuric acid derivative (isocyanuric acid derivative), (F) stearylbenzoylmethane, and (G) dibenzoylmethane (dibenzoylmethane metal salt) is 2 parts by mass or more per 100 parts by mass of the base polymer. If the total content of these stabilizers is less than 2 parts by mass relative to 100 parts by mass of the base polymer, the discoloration resistance against irradiation decreases. The upper limit of the total content of these stabilizers is not particularly limited, but from the viewpoint of improving the mechanical properties of the vinyl chloride resin composition, the total content of these stabilizers is preferably 5 parts by mass or less relative to 100 parts by mass of the base polymer.
As shown in examples described later, the vinyl chloride resin composition according to the present embodiment preferably further contains (D2) calcium stearate as the (D) fatty acid metal salt, and the mass ratio of (D1) zinc stearate to (D2) calcium stearate is preferably 12 to 13. As will be described in detail below, the hydrogen chloride trapping ability by zinc stearate (D1) and the zinc chloride trapping ability by calcium stearate (D2) can be balanced, and the irradiation discoloration resistance can be improved.
[ masking agent ]
The (H1) rutile titanium dioxide and the (H2) antimony trioxide used as the (H) covering agent according to the present embodiment each function as a white pigment. (H1) Rutile titanium dioxide is preferred as a pigment among titanium dioxide because of its low activity as a catalyst and excellent thermal stability. Among them, (H2) antimony trioxide also functions as a flame retardant, and thus (H1) rutile titanium dioxide and (H2) antimony trioxide are preferably used in combination from the viewpoint of improving flame retardancy.
As shown in examples described later, in the vinyl chloride resin composition according to the present embodiment, when (H1) rutile titanium dioxide is used alone as the (H) covering agent, 2 parts by mass or more of (H1) rutile titanium dioxide is contained per 100 parts by mass of the base polymer. By doing so, discoloration due to electron beam irradiation can be prevented. Further, the total content of the (B) aluminum hydroxide and the (C) hydrotalcite is 12 parts by mass or more and 16 parts by mass or less with respect to 100 parts by mass of the base polymer. If the total amount of the raw materials functioning as the flame retardant is less than 12 parts by mass relative to 100 parts by mass of the base polymer, flame retardancy satisfactory in the VW-1 test cannot be obtained, and if it is 16 parts by mass or more, discoloration due to electron beam irradiation tends to occur, and the discoloration resistance against irradiation is lowered.
Further, as shown in examples to be described later, in the vinyl chloride resin composition according to the present embodiment, when (H1) rutile titanium dioxide and (H2) antimony trioxide are used in combination as (H) covering agent, the total content of (B) aluminum hydroxide, (C) hydrotalcite and (H2) antimony trioxide is 12 parts by mass or more and 16 parts by mass or less, and the content of (H2) antimony trioxide is less than 3.5 parts by mass, relative to 100 parts by mass of the base polymer. As described above, if the total amount of the raw materials functioning as the flame retardant is less than 12 parts by mass with respect to 100 parts by mass of the base polymer, flame retardancy satisfactory in the VW-1 test cannot be obtained, and if 16 parts by mass or more, discoloration due to electron beam irradiation tends to occur, and the discoloration resistance against irradiation is lowered. Since (H2) antimony trioxide also functions as a flame retardant, when (H1) rutile titanium dioxide and (H2) antimony trioxide are used in combination as (H) covering agents, flame retardancy can be ensured if the total content of (B) aluminum hydroxide and (C) hydrotalcite is 11 parts by mass or more per 100 parts by mass of the base polymer. Further, if the content of (H2) antimony trioxide is 3.5 parts by mass or more with respect to 100 parts by mass of the base polymer, dehydrochlorination reaction is promoted and heat resistance is lowered.
In the vinyl chloride resin composition according to the present embodiment, when (H1) rutile titanium dioxide and (H2) antimony trioxide are used in combination as (H) covering agent, it is preferable that 0.94 parts by mass or more of (H1) rutile titanium dioxide and 1.8 parts by mass or more and less than 3.5 parts by mass of (H2) antimony trioxide be contained per 100 parts by mass of the base polymer. By doing so, the irradiation discoloration resistance can be improved.
Plasticizer (plasticizer)
The plasticizer (I) according to the present embodiment is not particularly limited, and a trimellitate plasticizer is preferably used, and examples thereof include tri (2-ethylhexyl) trimellitate, tri-n-alkyl trimellitate, triisodecyl trimellitate, and the like. In this embodiment, from the viewpoint of preventing the reduction of cold resistance after electron beam irradiation, tri-n-alkyl trimellitate is preferably used. From the viewpoint of improving the mechanical properties of the vinyl chloride resin composition, the content of the plasticizer (I) is preferably 30 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the base polymer.
[ others ]
In addition to (a) the vinyl chloride resin, (B) the aluminum hydroxide, (C) the hydrotalcite, (D) the fatty acid metal salt, (E) the cyanuric acid derivative (isocyanuric acid derivative), (F) stearoyl benzoyl methane, (G) dibenzoyl methane (dibenzoyl methane metal salt), (H) the masking agent, and (I) the plasticizer, the vinyl chloride resin composition of the present embodiment may contain, as other components (J), a lubricant, a processing aid, a filler, an anti-frost agent, an antioxidant, a copper inhibitor, a crosslinking aid, and the like as required.
Examples of the lubricant include magnesium stearate as a metal soap, stearic acid as a fatty acid, silicone, fatty acid amide, hydrocarbon, ester, and alcohol. Among them, the (D) fatty acid metal salt according to the present embodiment also functions as a lubricant.
Examples of the processing aid include wax components such as oxidized polyethylene.
Examples of the filler include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, silicon compound, quartz, talc, calcium carbonate, magnesium carbonate, white carbon, and the like.
As the anti-frost agent, basic metal hydrate such as calcium hydroxide is exemplified.
Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, phenol/sulfur ester-based antioxidants, amine-based antioxidants, and phosphite-based antioxidants. Examples of the phenolic antioxidants include 1,3, 5-tris [ [3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl ] methyl ] -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, pentaerythritol tetrakis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate ], stearyl 3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and 4,4' -butylidenebis- (6-t-butyl-3-methylphenol). Examples of the thio antioxidant include di (dodecyl) 3,3' -thiodipropionate, di (tetradecyl) 3,3' -thiodipropionate, 2-bis [ [3- (dodecylthio) -1-propionyloxy ] methyl ] -1, 3-propanediol ester, and dioctadecyl 3,3' -thiodipropionate.
Examples of the copper inhibitor include hydrazides such as N '1, N ' 12-bis (2-hydroxybenzoyl) dodecanedihydrazide, N ' -bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionyl ] hydrazine, bis (2-phenoxypropionyl) isophthalate, 2-hydroxy-N-1H-1, 2, 4-triazol-3-ylbenzamide, and alcohol carboxylic acid esters.
Examples of the crosslinking aid include trimethylolpropane trimethacrylate (TMPT), triallyl isocyanurate, dipentaerythritol hexaacrylate, triallyl cyanurate, N' -m-phenylene bismaleimide, ethylene glycol dimethacrylate, zinc acrylate and zinc methacrylate. The crosslinking assistant is preferably added in an amount of, for example, 2 to 20 parts by mass per 100 parts by mass of the base polymer. This is because if the crosslinking assistant is less than 2 parts by mass, there is a case where crosslinking is insufficient, and if it exceeds 20 parts by mass, there is a case where crosslinking occurs at the time of molding.
The vinyl chloride resin composition of the present embodiment may be added with materials other than the above-described materials within a range that does not affect the characteristics.
The vinyl chloride resin composition of the present embodiment can be used for all applications and dimensions, and can be used for example for insulating layers of various electric wires for railway vehicles, automobiles, wiring in trays, wiring in facilities, and electric power, and is not limited to the insulated electric wires described below.
< composition of insulated wire >)
Fig. 1 is a cross-sectional view showing an insulated wire according to an embodiment of the present invention. As shown in fig. 1, an insulated wire 10 according to the present embodiment includes a conductor 1 and an insulating layer 2 covering around the conductor 1.
As the conductor 1, an aluminum wire, a gold wire, a silver wire, or the like may be used in addition to a metal wire, such as a copper wire, a copper alloy wire, or the like, which is generally used. As the conductor 1, a conductor plated with a metal such as tin or nickel around a metal wire may be used. Further, as the conductor 1, a twisted conductor obtained by twisting metal wires may be used. The outer diameter of the conductor 1 is not particularly limited, and is preferablyAbove->The following is given.
The insulating layer 2 is formed of the vinyl chloride resin composition according to the embodiment of the present invention. The thickness of the insulating layer 2 is not particularly limited, but is preferably 0.15mm to 2 mm.
The outer diameter of the insulated wire 10 is not particularly limited, and is preferablyAbove->The following is given. The insulated wire 10 can be used for wiring in a high-temperature section in a dryer, an electric cooker, a transformer lead-out section, a lighting device, an air conditioner, or the like.
In the insulated wire 10 according to the present embodiment, since the insulating layer 2 is made of the vinyl chloride resin composition according to the present embodiment, discoloration due to irradiation with electron beams can be prevented, and heat resistance and flame retardancy are excellent.
Method for manufacturing insulated wire
The insulated wire 10 of the present embodiment shown in fig. 1 is manufactured, for example, as follows. First, a raw material of a vinyl chloride resin composition according to the present embodiment to be described later is melt kneaded. Then, the conductor 1 is prepared, and the vinyl chloride resin composition according to the present embodiment is extruded by an extrusion molding machine so as to cover the circumference of the conductor 1, thereby forming the insulating layer 2 having a predetermined thickness. Then, the vinyl chloride resin composition constituting the insulating layer 2 is crosslinked by an electron beam crosslinking method. At this time, after the vinyl chloride resin composition is molded as the insulating layer 2 of the insulated wire 10, for example, an electron beam of 1 to 30Mrad is irradiated to crosslink the composition. Thereby, the mechanical properties of the vinyl chloride resin composition are improved. The insulated wire 10 according to the present embodiment can be manufactured by the above steps.
In the method for producing the insulated wire 10 according to the present embodiment, the insulated wire 10 having the insulating layer 2 formed of the vinyl chloride resin composition according to the present embodiment, which is crosslinked by the electron beam, is produced through the above steps. In this case, since the insulating layer 2 is composed of the vinyl chloride resin composition according to the present embodiment, discoloration due to electron beam irradiation can be prevented, and heat resistance and flame retardancy are excellent.
The kneading apparatus used for producing the vinyl chloride resin composition according to the present embodiment may be a known kneading apparatus such as a batch kneader such as a roll mill, a Banbury mixer, or a pressure kneader, or a continuous kneader such as a twin screw extruder.
< construction of Cable >
Fig. 2 is a cross-sectional view showing a cable 11 according to an embodiment of the present invention. As shown in fig. 2, the cable 11 according to the present embodiment includes a twisted pair of insulated wires 10, a pair of intermediate members 3 provided around the twisted pair, and a sheath 4 provided around the pair of intermediate members 3. The sheath 4 is made of the vinyl chloride resin composition according to the present embodiment.
In the cable 11 according to the present embodiment, since the sheath 4 is made of the vinyl chloride resin composition according to the present embodiment, discoloration due to irradiation with electron beams can be prevented, and heat resistance and flame retardancy are excellent.
The cable 11 according to the present embodiment has been described as an example in which a twisted double wire having two insulated wires 10 twisted is used as a core wire, but the core wire may be a single core (1) or a multi-core twisted wire other than a double core. The insulating layer 2 of the insulated wire 10 is preferably a vinyl chloride resin composition according to the present embodiment, but is not limited thereto, and may be composed of another resin composition. In the cable 11 according to the present embodiment, the intermediate 3 is not necessarily required, and the intermediate 3 may not be provided. In addition, a multi-layer sheath structure in which another insulating layer (sheath) is formed between the insulated wire 10 and the sheath 4 may be employed.
Method for manufacturing cable
The cable 11 according to the present embodiment is manufactured, for example, as follows. First, two insulated wires 10 are manufactured by the foregoing method. Then, the circumference of the insulated wire 10 is covered with the coating material 3, and then the resin composition is extruded so as to cover the coating material 3, thereby forming the sheath 4 having a predetermined thickness. Then, the vinyl chloride resin composition constituting the sheath 4 is crosslinked by an electron beam crosslinking method. At this time, after the vinyl chloride resin composition is molded as the sheath 4 of the cable 11, for example, an electron beam of 1 to 30Mrad is irradiated to crosslink the composition. Thereby, the mechanical properties of the vinyl chloride resin composition are improved. The cable 11 according to the present embodiment can be manufactured by the above steps.
In the method for producing the cable 11 according to the present embodiment, the cable 11 having the sheath 4 formed of the vinyl chloride resin composition according to the present embodiment, which is electron-beam crosslinked, is produced through the above steps. In this case, since the sheath 4 is made of the vinyl chloride resin composition according to the present embodiment, discoloration due to electron beam irradiation can be prevented, and heat resistance and flame retardancy are excellent.
Example (example)
The present invention will be described in further detail with reference to examples, but the present invention is not limited to these examples.
Summary of examples and comparative examples
The insulated wires of examples 1 to 14 and the insulated wires of comparative examples 1 to 10 are explained below. The insulated wires of examples 1 to 14 correspond to the insulated wire 10 shown in fig. 1. That is, the insulating layer 2 of the insulated wire 10 is formed of the vinyl chloride resin composition according to the present embodiment. The insulated wires of comparative examples 1 to 10 were similar in shape to the insulated wire 10 shown in fig. 1, but the insulating layer 2 was formed of a resin composition having a composition different from that of the vinyl chloride resin composition according to the present embodiment. The respective raw materials for examples and comparative examples are described below.
The insulated wires of examples 1 to 14 were produced as follows. First, the raw materials of examples 1 to 14 shown in table 2 were dry-blended at room temperature, and the mixed raw materials were melt-kneaded by an open roll mixer heated to 170 ℃ and then pelletized to produce a vinyl chloride resin composition. Then, an insulating layer made of a vinyl chloride resin composition was formed around the conductor under conditions of a barrel temperature of 170 ℃, a head temperature of 180 ℃, and a wire speed of 20m/min using an extrusion coating apparatus for wire production. The insulating layer was subjected to electron beam crosslinking treatment (3.5 Mrad) to crosslink the vinyl chloride resin composition constituting the insulating layer, thereby producing the insulated wires of examples 1 to 14. The insulated wires of comparative examples 1 to 10 were produced in the same manner as the flame-retardant insulated wires of examples 1 to 14, and therefore were omitted.
In the insulated wires of examples 1 to 14 and comparative examples 1 to 10, tin-plated stranded conductors (17 core wires, bare wire outer diameter 0.16 mm) having an outer diameter of 0.76mm were used as conductors (corresponding to the conductor 1 shown in fig. 1), and the thickness of the insulating layer (corresponding to the insulating layer 2 shown in fig. 1) was set to 0.5mm.
< raw materials of examples and comparative examples >
First, detailed information of raw materials used in examples and comparative examples is shown in table 1.
TABLE 1
The compositions of examples 1 to 14 are shown in Table 2.
TABLE 2
As shown in table 2, the vinyl chloride resin compositions constituting the insulating layers of the insulated wires of examples 1 to 14 contained (a) a vinyl chloride resin, (B) aluminum hydroxide, (C) hydrotalcite, (D) a fatty acid metal salt, (E) a cyanuric acid derivative (isocyanuric acid derivative), (F) stearylbenzoylmethane, (G) dibenzoylmethane (dibenzoylmethane metal salt), (H) a covering agent, and (I) a plasticizer as raw materials thereof.
The vinyl chloride resin compositions of examples 2 and 5 were obtained by changing the amounts of (B) aluminum hydroxide and (C) hydrotalcite to be added relative to the vinyl chloride resin composition of example 1. The vinyl chloride resin compositions of examples 3 and 4 were obtained by changing the amounts of (B) aluminum hydroxide and (C) hydrotalcite and the amounts of stabilizer added relative to the vinyl chloride resin composition of example 1.
The vinyl chloride resin composition of example 6 was a vinyl chloride resin composition of example 1, in which the amount of antimony (H2) trioxide added was changed.
The vinyl chloride resin composition of example 7 was obtained by changing the amount of aluminum hydroxide (B) added to the vinyl chloride resin composition of example 1.
The vinyl chloride resin composition of example 8 was obtained by changing the addition amounts of (H1) rutile titanium dioxide and (H2) antimony trioxide relative to the vinyl chloride resin composition of example 1. More specifically, in the vinyl chloride resin composition of example 8, as the (H) covering agent, (H2) antimony trioxide was not added and only (H1) rutile titanium dioxide was added.
The vinyl chloride resin compositions of examples 9 and 10 were modified in the type and formulation of (a) vinyl chloride resin relative to the vinyl chloride resin composition of example 2. The vinyl chloride resin composition of example 11 was a vinyl chloride resin composition of example 3, and the type and formulation of (a) vinyl chloride resin was changed. The vinyl chloride resin composition of example 12 was a vinyl chloride resin composition of example 4, and the type and formulation of (a) vinyl chloride resin was changed. The vinyl chloride resin composition of example 13 was a vinyl chloride resin composition of example 5, and the type and formulation of (a) vinyl chloride resin was changed. The vinyl chloride resin composition of example 14 was a vinyl chloride resin composition of example 6, and the type and formulation of (a) vinyl chloride resin was changed.
The compositions of comparative examples 1 to 10 are shown in Table 3.
TABLE 3
Comparative examples 1 to 10 shown in table 3 are examples in which the types of raw materials and the blending ratios of the raw materials used in examples 1 to 14 shown in table 2 were changed.
As shown in tables 2 and 3, the vinyl chloride resin compositions of comparative examples 1 to 4 are different from examples 1 to 14 mainly in that they do not contain (E) cyanuric acid derivatives (isocyanuric acid derivatives) and (F) stearoyl benzoylmethane as stabilizers and in that they contain 3.5 parts by mass or more of (H2) antimony trioxide per 100 parts by mass of the base polymer.
The vinyl chloride resin composition of comparative example 5 was different from examples 1 to 14 mainly in that (E) cyanuric acid derivative (isocyanuric acid derivative) and (F) stearoyl benzoylmethane were not contained as stabilizers, and in that (H2) antimony trioxide was contained in an amount of 3.5 parts by mass or more based on 100 parts by mass of the base polymer, and in that (C) hydrotalcite was added in an amount smaller than examples 1 to 14 and in that (B) aluminum hydroxide was not contained.
The vinyl chloride resin compositions of comparative examples 6 and 8 to 10 are different from examples 1 to 14 mainly in that they do not contain (E) cyanuric acid derivatives (isocyanuric acid derivatives) and (F) stearoyl benzoylmethane as stabilizers and in that they do not contain (H2) antimony trioxide.
The vinyl chloride resin composition of comparative example 7 differs from examples 1 to 14 mainly in that it contains 3.5 parts by mass or more of (H2) antimony trioxide relative to 100 parts by mass of the base polymer, and in that the amount of (C) hydrotalcite to be added is smaller than examples 1 to 14 and no (B) aluminum hydroxide is contained.
Evaluation methods of examples and comparative examples
(1) Anti-irradiation discoloration property
The sample obtained by cutting the prepared insulated wire, i.e., the insulated wire irradiated with the electron beam, into a length of 300mm was visually observed, and the sample having no discoloration was "o" and the sample having discoloration was "x". Further, this sample was exposed to a gill aging oven at 136℃for 48 hours, and the sample having little discoloration was regarded as "excellent".
(2) Heat resistance
The insulating layer alone after the conductor was extracted from the insulated wire thus produced was used as a sample, and the sample was exposed to a gill aging oven at 136 ℃ for 1800 hours, and the sample which could ensure 50% or more of elongation after exposure relative to the initial elongation was "o" and the sample below 50% was "x".
(3) Flame retardancy
The vertical flame-retardant test VW-1 defined in the flame-retardant property standard UL1581 was performed three times on the insulated wire thus produced, and the sample that was qualified for 3 times was "o" and "x" was obtained when 1 time of failure was detected.
Detailed and evaluation results of examples 1 to 14
The evaluation results of examples 1 to 14 are shown in table 2. As shown in Table 2, in examples 1 to 14, (1) the discoloration resistance against irradiation, (2) the heat resistance and (3) the flame retardancy were all good. Among them, examples 9, 10 and 14 showed little discoloration even under the heat load after the electron beam irradiation, and showed higher discoloration resistance against irradiation than examples 1 to 8 and 11 to 13.
Evaluation results of comparative examples 1 to 10
The evaluation results of comparative examples 1 to 10 are shown in table 3.
As shown in Table 3, in comparative examples 1 to 4, (3) flame retardancy was good, but (1) resistance to discoloration by irradiation and (2) heat resistance were not good.
In comparative examples 6 and 8 to 10, (2) heat resistance and (3) flame retardancy were good, but (1) discoloration by irradiation was not good.
In comparative example 7, (1) the discoloration resistance against irradiation was good, but (2) the heat resistance and (3) the flame retardancy were not good.
In comparative example 5, (1) the discoloration resistance against irradiation, (2) the heat resistance and (3) the flame retardancy were all poor.
Summary of examples and comparative examples
As shown in examples 1 to 14, the vinyl chloride resin composition and the insulated wire using the same according to the present embodiment can prevent discoloration due to electron beam irradiation and can improve heat resistance and flame retardancy.
In particular, in both cases where (H1) rutile titanium dioxide and (H2) antimony trioxide were used as (H) capping agents in combination as shown in examples 1 to 7 and 9 to 14, and where (H1) rutile titanium dioxide was used alone as (H) capping agent as shown in example 8, discoloration due to electron beam irradiation could be prevented. More specifically, as shown in example 8, in the case of using (H1) rutile type titanium dioxide alone as (H) covering agent, that is, in the case of not containing (H2) antimony trioxide, discoloration due to electron ray irradiation can be prevented by containing 2 parts by mass or more of (H1) rutile type titanium dioxide relative to 100 parts by mass of the base polymer. Further, in the case where (H2) antimony trioxide is not contained, if the addition amount of (B) aluminum hydroxide and (C) hydrotalcite is 12 parts by mass or more with respect to 100 parts by mass of the base polymer, flame retardancy can be ensured.
On the other hand, it is considered that the (1) anti-discoloration property of the vinyl chloride resin compositions of comparative examples 1 to 5 is not good because: since (E) cyanuric acid derivative (isocyanuric acid derivative) and (F) stearoyl benzoylmethane are not contained as stabilizers, coloring due to dehydrochlorination reaction occurs.
The reason why the vinyl chloride resin compositions (1) of comparative examples 6 and 7 to 10 were inferior in discoloration resistance against irradiation is considered to be that: since (E) cyanuric acid derivative (isocyanuric acid derivative) and (F) stearoyl benzoylmethane, and (B) aluminum hydroxide and (C) hydrotalcite are not contained as stabilizers, coloring due to dehydrochlorination reaction occurs, or coloring cannot be reduced since (H) masking agent is added in a small amount.
The reason why the vinyl chloride resin compositions (2) of comparative examples 1 to 5 and 7 were inferior in heat resistance is considered to be that: since (H2) antimony trioxide is added in a large amount, dehydrochlorination reaction is promoted.
The flame retardancy of (3) the vinyl chloride resin composition of comparative example 5 is considered to be poor because: since a particularly large amount of (H2) antimony trioxide is added, dehydrochlorination reaction is promoted, and the vinyl chloride resin is easily thermally decomposed and burned.
The flame retardancy of (3) the vinyl chloride resin composition of comparative example 7 is considered to be poor because: the total content of (B) aluminum hydroxide, (C) hydrotalcite and (H2) antimony trioxide functioning as flame retardants is less than 12 parts by mass relative to 100 parts by mass of the base polymer.
The present invention is not limited to the foregoing embodiments and examples, and various modifications can be made without departing from the spirit and scope thereof.

Claims (12)

1. A vinyl chloride resin composition comprising a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoylbenzoylmethane, dibenzoylmethane and/or a dibenzoylmethane metal salt, a covering agent and a plasticizer,
the base polymer contains a vinyl chloride resin having a K value of 75 to 86,
the capping agent comprises rutile titanium dioxide,
the fatty acid metal salt contains zinc stearate,
the total content of zinc stearate, cyanuric acid derivative, isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and dibenzoyl methane metal salt is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
the content of the rutile titanium dioxide is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
the total content of the aluminum hydroxide and the hydrotalcite is 12 parts by mass to 16 parts by mass inclusive with respect to 100 parts by mass of the base polymer.
2. A vinyl chloride resin composition comprising a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoylbenzoylmethane, dibenzoylmethane and/or a dibenzoylmethane metal salt, a covering agent and a plasticizer,
the base polymer contains a vinyl chloride resin having a K value of 75 to 86,
the covering agent contains rutile type titanium dioxide and antimonous oxide,
the fatty acid metal salt contains zinc stearate,
the total content of zinc stearate, cyanuric acid derivative, isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and dibenzoyl methane metal salt is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
containing 0.94 parts by mass or more of the rutile titanium dioxide per 100 parts by mass of the base polymer,
the content of the antimony trioxide is 1.8 parts by mass or more and less than 3.5 parts by mass with respect to 100 parts by mass of the base polymer,
the total content of the aluminum hydroxide, the hydrotalcite, and the antimony trioxide is 12 parts by mass to 16 parts by mass inclusive with respect to 100 parts by mass of the base polymer.
3. The vinyl chloride resin composition according to claim 1 or 2, wherein the fatty acid metal salt further contains calcium stearate, and a mass ratio of the zinc stearate to the calcium stearate is 12 to 13.
4. The vinyl chloride resin composition according to claim 1 or 2, wherein the base polymer contains a vinyl chloride resin having a K value of 71 to 73 and a vinyl chloride resin having a K value of 84 to 86.
5. An insulated wire comprising an insulating layer formed of the vinyl chloride resin composition according to any one of claims 1 to 4,
in the insulating layer, the vinyl chloride resin composition is crosslinked.
6. A cable provided with a sheath formed of the vinyl chloride resin composition according to any one of claims 1 to 4, wherein the vinyl chloride resin composition is crosslinked.
7. A method of manufacturing an insulated wire, comprising:
(a) Mixing a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent, and a plasticizer to form a vinyl chloride resin composition;
(b) Extruding the vinyl chloride resin composition so as to surround the coated conductor to form an insulating layer;
(c) A step of irradiating the insulating layer with an electron beam to crosslink the vinyl chloride resin composition,
the base polymer contains a vinyl chloride resin having a K value of 75 to 86,
the capping agent comprises rutile titanium dioxide,
the fatty acid metal salt contains zinc stearate,
the total content of zinc stearate, cyanuric acid derivative, isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and dibenzoyl methane metal salt is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
the content of the rutile titanium dioxide is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
the total content of the aluminum hydroxide and the hydrotalcite is 12 parts by mass to 16 parts by mass inclusive with respect to 100 parts by mass of the base polymer.
8. A method of manufacturing an insulated wire, comprising:
(a) Mixing a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent, and a plasticizer to form a vinyl chloride resin composition;
(b) Extruding the vinyl chloride resin composition so as to surround the coated conductor to form an insulating layer;
(c) A step of irradiating the insulating layer with an electron beam to crosslink the vinyl chloride resin composition,
the base polymer contains a vinyl chloride resin having a K value of 75 to 86,
the covering agent contains rutile type titanium dioxide and antimonous oxide,
the fatty acid metal salt contains zinc stearate,
the total content of zinc stearate, cyanuric acid derivative, isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and dibenzoyl methane metal salt is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
containing 0.94 parts by mass or more of the rutile titanium dioxide per 100 parts by mass of the base polymer,
the content of the antimony trioxide is 1.8 parts by mass or more and less than 3.5 parts by mass with respect to 100 parts by mass of the base polymer,
the total content of the aluminum hydroxide, the hydrotalcite, and the antimony trioxide is 12 parts by mass to 16 parts by mass inclusive with respect to 100 parts by mass of the base polymer.
9. The method for producing an insulated wire according to claim 7 or 8, wherein the base polymer contains a vinyl chloride resin having a K value of 71 to 73 and a vinyl chloride resin having a K value of 84 to 86.
10. A method of manufacturing a cable comprising:
(a) Mixing a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent, and a plasticizer to form a vinyl chloride resin composition;
(b) Extruding the vinyl chloride resin composition so as to cover the circumference of an insulated wire having a conductor and an insulating layer covering the circumference of the conductor, thereby forming a sheath;
(c) A step of irradiating the sheath with an electron beam to crosslink the vinyl chloride resin composition,
the base polymer contains a vinyl chloride resin having a K value of 75 to 86,
the capping agent comprises rutile titanium dioxide,
the fatty acid metal salt contains zinc stearate,
the total content of zinc stearate, cyanuric acid derivative, isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and dibenzoyl methane metal salt is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
the content of the rutile titanium dioxide is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
The total content of the aluminum hydroxide and the hydrotalcite is 12 parts by mass to 16 parts by mass inclusive with respect to 100 parts by mass of the base polymer.
11. A method of manufacturing a cable comprising:
(a) Mixing a base polymer, aluminum hydroxide, hydrotalcite, a fatty acid metal salt, a cyanuric acid derivative and/or an isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and/or a dibenzoyl methane metal salt, a covering agent, and a plasticizer to form a vinyl chloride resin composition;
(b) Extruding the vinyl chloride resin composition so as to cover the circumference of an insulated wire having a conductor and an insulating layer covering the circumference of the conductor, thereby forming a sheath;
(c) A step of irradiating the sheath with an electron beam to crosslink the vinyl chloride resin composition,
the base polymer contains a vinyl chloride resin having a K value of 75 to 86,
the covering agent contains rutile type titanium dioxide and antimonous oxide,
the fatty acid metal salt contains zinc stearate,
the total content of zinc stearate, cyanuric acid derivative, isocyanuric acid derivative, stearoyl benzoyl methane, dibenzoyl methane and dibenzoyl methane metal salt is 2 parts by mass or more relative to 100 parts by mass of the base polymer,
Containing 0.94 parts by mass or more of the rutile titanium dioxide per 100 parts by mass of the base polymer,
the content of antimony trioxide is 1.8 parts by mass or more and less than 3.5 parts by mass relative to 100 parts by mass of the base polymer,
the total content of the aluminum hydroxide, the hydrotalcite, and the antimony trioxide is 12 parts by mass to 16 parts by mass inclusive with respect to 100 parts by mass of the base polymer.
12. The method for manufacturing a cable according to claim 10 or 11, wherein,
the base polymer contains a vinyl chloride resin having a K value of 71 to 73 and a vinyl chloride resin having a K value of 84 to 86.
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