CN1566189A - Heat-resistant weather-resistant excellent insulating resin composition and insulated wire - Google Patents

Abstract

Flame-retardant, heat-resistant, and weather-resistant insulating resin composition and its covered insulated wire. The composition contains 100 parts by mass of resin (A) mainly composed of polyolefin resin and/or vinyl copolymer and/or styrene block copolymer; 60-300 parts by mass of metal hydrate treated with silane coupling agent ; Selected from: (i) 1-8 parts by mass of hindered phenol antioxidants, 0.4-8 parts by mass of benzophenone-based and/or benzotriazole-based ultraviolet absorbers, 1-7 parts by mass of hindered amine light stabilizers (ii) 1 to 8 parts by mass of hindered phenol antioxidant, 0.8 to 8 parts by mass of benzophenone-based ultraviolet absorber, 1 to 7 parts by mass of hindered amine light stabilizer; (iii) 1 to 7 parts by mass of hindered phenol antioxidant 8 parts by mass, 0.8-8 parts by mass of thioether antioxidant, 0.4-8 parts by mass of benzophenone-based and/or benzotriazole-based ultraviolet absorbers, 1-7 parts by mass of hindered amine light stabilizers (g) 0.01-1.0 parts by mass of organic peroxide; (h) 0.03-1.8 parts by mass of methacrylate-based and/or allyl-based cross-linking aids. Then, heating and kneading are carried out at a temperature equal to or higher than the melting temperature of the thermoplastic resin (A).

Description

Insulating resin composition excellent in heat resistance and weather resistance, and insulated wire

technical field

The present invention relates to an insulating resin composition that does not generate metal compound elution, a large amount of smoke, and corrosive gas during waste disposal such as landfill and incineration. In addition, the present invention relates to insulated wires used for internal and external wiring of electric and electronic equipment.

current technology

Insulated wires used for internal and external wiring of electric and electronic equipment are required to have various properties such as flame retardancy, tensile properties, and heat resistance. Therefore, as the coating material of these insulated wires, it is known that a polyvinyl chloride (PVC) compound or an ethylenic copolymer containing a halogen flame retardant containing a bromine atom or a chlorine atom in the molecule can be used as a main component. thing.

In recent years, various problems have arisen when insulated electric wires using this covering material are discarded without proper disposal. For example, plasticizers and heavy metal stabilizers blended in coating materials are eluted when disposed of in landfills, and large amounts of corrosive gases and dioxins are generated when incinerated.

Therefore, the technology of coating electric wires with non-halogen flame retardants that do not generate harmful heavy metals, halogen gases, etc. is being actively studied.

The existing non-halogen flame retardant material is a material that exhibits flame retardancy by blending a halogen-free flame retardant into the resin. As the flame retardant of the coating material, for example, magnesium hydroxide, hydroxide Metal hydrates such as aluminum, and as resins, polyethylene, ethylene-1-butene copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene - Diene terpolymers, etc.

Solve the problem of the invention

For electronic wiring used in electronic instruments, from the aspect of safety, it is required to have high flame retardancy, and must strictly meet the very strict flame retardancy standard UL1581 (Reference Standard for Electrical Wires, Cables, and Flexible Cords) and other regulations The VW-1 standard of the vertical flame test (Vertical Flame Test), the horizontal flame retardant standard, and the 60-degree inclined flame retardancy specified in JIS C3005. In addition, regarding properties other than flame retardancy, UL and electrical appliance management standards are adopted, and high mechanical properties such as elongation at break of 100% and tensile strength at break of 10 MPa or more are required.

In the non-halogen flame retardant material, in order to ensure the above flame retardancy, it is possible to maintain the flame retardancy by adding metal hydrate in an equivalent amount or more to the above resin component.

However, a resin composition to which a large amount of metal hydrate has been added and an electric wire using the composition have remarkably poor weather resistance and cannot be used for outdoor or lighting wiring.

Previously, when using wires and cables coated with non-halogen flame-retardant materials outdoors, the weather resistance can be improved by adding carbon powder, but when performing various wiring such as lighting system wiring, multi-colored wires are essential Therefore, there are problems such as that non-halogen wires cannot be used in this field.

The object of the present invention is to solve these problems and provide an insulating resin composition having the following characteristics and an insulated wire using the composition as a coating material: high flame retardancy and excellent heat resistance, Weatherability and mechanical properties, can be colored into any color, maintain electrical properties such as electrical insulation, maintain oil resistance, and do not produce heavy metal compounds and phosphorus compounds when they are discarded by landfill, and do not produce a lot of smoke when incinerated. Corrosive gases, etc.

Measures to solve this problem

As a result of careful research, the present inventors have found that metal hydrates treated with a crosslinkable silane treatment agent are used as metal hydrates, and a specific amount of hindered phenolic antioxidants (if necessary, mixed with thioether antioxidants) agent in combination), benzophenone-based and/or benzotriazole-based ultraviolet absorbers, and hindered amine-based light stabilizers, whereby a non-halogen insulating resin composition with excellent weather resistance and heat resistance can be obtained, And an insulated wire using the composition as a coating material. The present invention was accomplished based on this finding.

That is, the present invention provides,

(1) An insulating resin composition characterized in that it is a mixture containing the following composition, which is produced by heating and kneading at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A), that is,

Contains:

60-300 parts by mass of metal hydrates that have been surface-treated with a crosslinkable silane coupling agent;

Any one of the following (i), (ii) or (iii):

(i) 1-8 parts by mass of a hindered phenolic antioxidant, 0.4-8 parts by mass of a benzophenone-based and/or benzotriazole-based ultraviolet absorber, and 1-7 parts by mass of a hindered amine-based light stabilizer,

(ii) 1-8 parts by mass of hindered phenolic antioxidant, 0.8-8 parts by mass of benzophenone-based ultraviolet absorber, and 1-7 parts by mass of hindered amine-based light stabilizer, or

(iii) 1 to 8 parts by mass of hindered phenolic antioxidants, 0.8 to 8 parts by mass of thioether antioxidants represented by the structure of the following formula (1), benzophenone-based and/or benzotriazole-based 0.4-8 parts by mass of ultraviolet absorber, and 1-7 parts by mass of hindered amine light stabilizer;

[chemical formula 2]

(In formula (1), R ¹ represents an alkyl group)

(g) 0.01 to 1.0 parts by mass of organic peroxide; and

(h) 0.03-1.8 parts by mass of (meth)acrylate-based and/or allyl-based crosslinking aids;

(2) The insulating resin composition described in item (1), which is characterized in that, relative to 100 parts by mass of the above-mentioned resin component (A), 1 to 8 parts by mass of the above-mentioned (i) hindered phenolic antioxidant, two 0.4-8 parts by mass of benzophenone-based and/or benzotriazole-based ultraviolet absorbers, and 1-7 parts by mass of hindered amine-based light stabilizers;

(3) The insulating resin composition described in item (1), which is characterized in that, with respect to 100 parts by mass of the above-mentioned resin component (A), 1 to 8 parts by mass of the aforementioned (ii) hindered phenolic antioxidant, two 0.8-8 parts by mass of a benzophenone-based ultraviolet absorber, and 1-7 parts by mass of a hindered amine-based light stabilizer;

(4) The insulating resin composition described in item (1), which is characterized by containing 1 to 8 parts by mass of the above-mentioned (iii) hindered phenolic antioxidant with respect to 100 parts by mass of the above-mentioned resin component (A). 0.8-8 parts by mass of thioether-based antioxidant represented by the structure of the above formula (1), 0.4-8 parts by mass of benzophenone-based and/or benzotriazole-based ultraviolet absorber, and hindered amine-based light stabilizer 1 to 7 parts by mass;

(5) An insulated wire characterized in that it is formed by coating the insulating resin composition described in any one of (1) to (4) around a conductor or an optical fiber;

(6) An insulated electric wire, characterized in that the insulating resin composition described in any one of (1) to (4) is coated around a conductor and/or an optical fiber, and the coating resin composition is crosslinked And constitute.

When 60 parts by mass or more of a metal hydrate such as magnesium hydroxide is added to a polyolefin resin or an ethylene-based copolymer, the weather resistance is remarkably lowered. Usually, as a weather-resistant formulation, 0.2 to 0.4 parts by mass of a benzotriazole-based ultraviolet absorber and about 0.4 parts by mass of a hindered amine-based light stabilizer are added to 100 parts by mass of a polymer.

However, when 60 parts by mass of the above-mentioned metal hydrate was added to this weather resistance formulation, there was no effect at all and deterioration occurred. This is because the surface treatment agent of the polymer and the metal hydrate deteriorates under the action of light such as ultraviolet rays, and a defect occurs between the metal hydrate and the polymer, which causes a decrease in elongation and stress fracture.

In the present invention, a metal hydrate treated with a crosslinkable silane treatment agent is used as the metal hydrate, and the metal hydrate and the polymer are bonded with a silane coupling agent. Usually, it is used as an anti-aging agent with respect to 100 parts by mass of the resin component. When using about 0.1 parts by mass, add at least 1 part by mass of hindered phenolic antioxidants, 0.4 parts by mass or more of benzophenone and/or benzotriazole-based ultraviolet absorbers, hindered amine-based light stabilizers More than 1 part by mass, the bond can be repaired even if it deteriorates under the long-term action of light such as ultraviolet rays, so the defects between the metal hydrate and the polymer can be suppressed to the minimum, so that no elongation and stress failure. In particular, weather resistance can be further improved by adding a benzophenone-based ultraviolet absorber. In addition, at least 0.8 parts by mass of thioether-based antioxidants represented by formula (1) are added, and 0.8 parts by mass of benzophenone-based and/or benzotriazole-based ultraviolet absorbers are added. A non-halogen compound that is thermally resistant and has excellent weather resistance.

Embodiment of the invention

The present invention will be described in detail below.

First, components and functions contained in the resin composition of the present invention will be described.

(A) thermoplastic resin

The thermoplastic resin (A) used as the main component in the resin composition of the present invention is a polyolefin resin and/or an ethylene-based copolymer and/or a styrene block copolymer.

(A-1) Polyolefin resin

Examples of polyolefin resins include polypropylene resins, ethylene-α-olefin resins, polyethylene, and the like.

Examples of polypropylene-based resins that can be used in the present invention include homopolypropylene, ethylene-propylene random copolymers, ethylene-propylene block copolymers, and propylene and other small amounts of α-olefins (for example, 1-butene , 1-hexene, 4-methyl-1-pentene, etc.) copolymers, etc. These polypropylene resins may be used alone or in combination of two or more.

Ethylene-α-olefin copolymers are preferably copolymers of ethylene and α-olefins having 3 to 12 carbon atoms. Specific examples of α-olefins include propylene, 1-butene, 1-hexene, 4- Methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, etc.

As ethylene-α-olefin copolymers, there are LLDPE (linear low-density polyethylene), LDPE (low-density polyethylene), VLDPE (ultra-low-density polyethylene), EPR, EBR, and those synthesized in the presence of single-site catalysts. Ethylene·α-olefin copolymer, etc. Among them, an ethylene·α-olefin copolymer synthesized in the presence of a single-site catalyst is preferable.

The ethylene-α-olefin copolymer synthesized in the presence of the single-site catalyst in the present invention can be produced by a known method described in JP-A No. 6-306121 and JP-A-7-500622. .

The characteristic of single-site catalyst is that the polymerization active point is single and has high polymerization activity. It is also called metallocene catalyst, chemical (kaminsky) catalyst, ethylene-α-olefin copolymer synthesized by catalyst, molecular weight The distribution and composition distribution are narrow.

The ethylene·α-olefin copolymer synthesized in the presence of such a single-site catalyst has high tensile strength, tear strength, impact strength, etc. When used as a coating material for wire materials), there is an advantage that the reduction in mechanical properties is small due to the use of a large amount of filled metal hydrate.

As the ethylene-α-olefin copolymer synthesized in the presence of a single-site catalyst used in the present invention, there are commercially available: "AFFINITY" and "ENGAGE" (trade name) manufactured by Dow Chemical Co., Ltd., Exxon Chemical Co., Ltd. "EXACT" (trade name) manufactured by Nippon Polychem "Ka-Nel" (trade name).

(A-2) Ethylene Copolymer

Specific examples of ethylene-based copolymers that can be used in the present invention include, for example, ethylene-vinyl acetate copolymer (EVA), ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, (EEA), ethylene-methacrylate copolymer (EMA), etc. These may be used alone or in combination of two or more. In addition, among ethylene-based copolymers, it is preferable to use ethylene-vinyl acetate copolymer (EVA) from the viewpoint of improving flame retardancy and weather resistance.

In particular, when an ethylene-based copolymer having an acid content of 20 to 50% by mass is used, improvement in weather resistance can be confirmed. When using ethylene copolymers or polyolefin resins with an acid content of less than 20 mass%, when exposed to stress for a long time, the material is prone to cracking, but when using ethylene copolymers with an acid content of 20 to 50 mass%, When it is a copolymer, the occurrence of cracks can be greatly suppressed. The acid content of a preferable ethylene-type copolymer is 22-45 mass %, More preferably, it is 25-45 mass %, Especially preferably, it is 25-40 mass %.

(A-3) Styrenic block copolymer

The styrene-based block copolymers of the present invention include at least two polymer blocks A mainly composed of vinyl aromatic compounds, and at least two polymer blocks A mainly composed of conjugated diene compounds. A block copolymer composed of one polymer block B, or a product obtained by hydrogenating it, or a mixture thereof, such as a vinyl aromatic compound-conjugated diene compound having a structure such as A-B-A, B-A-B-A, A-B-A-B-A, etc. Block copolymers, or, their hydrogenated products, etc. The above-mentioned (hydrogenated) block copolymers (hereinafter, the so-called (hydrogenated) block copolymers refer to block copolymers and/or hydrogenated block copolymers) usually contain 5 to 60 mass of vinyl aromatic compounds %, preferably 20 to 50% by mass.

The polymer block A mainly composed of vinyl aromatic compounds is preferably composed of only vinyl aromatic compounds, or more than 50% by mass, preferably 70% by mass or more of vinyl aromatic compounds and (through A copolymer block of a hydrogenated) conjugated diene compound (hereinafter, a (hydrogenated) conjugated diene compound means a conjugated diene compound and/or a hydrogenated conjugated diene compound). The polymer block B mainly composed of a (hydrogenated) conjugated diene compound is preferably composed only of a (hydrogenated) conjugated diene compound, or more than 50% by mass, preferably 70% by mass A copolymer block of the above (hydrogenated) conjugated diene compound and a vinyl aromatic compound. In each of the polymer block A mainly composed of these vinyl aromatic compounds and the polymer block B mainly composed of (hydrogenated) conjugated diene compounds, the The distribution of repeating units of vinyl aromatic compounds or (hydrogenated) conjugated diene compounds can also be random, wedge-shaped (increase or decrease of monomer components along the molecular chain), a part of block shape or their any combination of . When there are two or more polymer block A mainly composed of a vinyl aromatic compound or block B mainly composed of a (hydrogenated) conjugated diene compound, each may have the same structure or a different structure.

As the vinyl aromatic compound constituting the (hydrogenated) block copolymer, for example, one or two kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Of the above, styrene is preferred. In addition, as the conjugated diene compound, for example, one selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc. Or two or more kinds, among them, butadiene, isoprene and a combination thereof are preferable.

The microstructure in the polymer block B mainly composed of a conjugated diene compound can be selected arbitrarily. For example, in a polybutadiene block, a 1,2-microstructure of 20 to 50%, especially 25 to 45%, is preferred, and at least 90% hydrogenation of aliphatic double bonds based on butadiene is preferred. In the polyisobutadiene block, 70 to 100% by mass of the isobutadiene compound has a 1,4-microstructure, and at least 90% of the aliphatic double bonds of the isobutadiene compound are hydrogenated Got is preferred.

The weight average molecular weight of the (hydrogenated) block copolymer used in the present invention having the above structure is preferably 5,000 to 1,500,000, more preferably 10,000 to 550,000, particularly preferably 100,000 to 550,000, particularly preferably 100,000 to 400,000. The molecular weight distribution (ratio (Mw/Mn) of weight-average molecular weight (Mw) to number-average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, particularly preferably 2 or less. The molecular structure of the (hydrogenated) block copolymer may be linear, branched, radial, or any combination thereof.

Various methods have been proposed as methods for producing these (hydrogenated) block copolymers, but as a representative method, for example, according to the method described in JP-A-40-23798, a lithium catalyst or a Ziegler-type A catalyst is a method of performing block polymerization in an inert solvent to obtain a block copolymer. In addition, for example, the block copolymer obtained by the above method can be hydrogenated in the presence of a hydrogenation catalyst in an inert solvent to obtain a hydrogenated block copolymer.

Specific examples of the above (hydrogenated) block copolymers include SBS (styrene-butadiene block copolymer), SIS (styrene-isoprene block copolymer), SEBS (hydrogenated SBS), SEPS (hydrogenated SIS), etc. In the present invention, a particularly preferable (hydrogenated) block copolymer is a polymer block A having styrene as its main constituent, and isoprene as its main constituent and isoprene 70 to 100% by mass of isoprene has a 1,4-microstructure, and based on the aliphatic double bond of the isoprene hydrogenated at least 90% of the obtained polymer block B is a hydrogenated block with a weight average molecular weight of 50,000 to 550,000 segment copolymers. More preferably, 90 to 100% by mass of isobutadiene is the above hydrogenated block copolymer having a 1,4-microstructure.

(A-4) Softener for non-aromatic rubber

When using a styrenic block copolymer in the resin component of the present invention, a non-aromatic mineral oil, or a liquid or low molecular weight synthetic softener can be used.

The mineral oil softener used for rubber is a mixture of aromatic rings, naphthenic rings and paraffinic hydrocarbon chains, and the difference in its name is that paraffin refers to the number of carbon atoms in the paraffinic hydrocarbon chain Paraffinic hydrocarbons accounting for more than 50% of the total carbon atoms, and naphthenic refers to cycloalkanes with 30-50% of the cycloalkane ring carbon atoms, and aromatic refers to aromatic carbon atoms accounting for 30% above aromatic hydrocarbons.

The mineral oil-based rubber softener used as the component (A-4) of the present invention is a paraffinic hydrocarbon-based and naphthene-based softener classified as described above. Aromatic softeners are not preferable because their use makes the component (a) soluble, hinders the crosslinking reaction, and cannot improve the physical properties of the resulting composition. As the component (A-4), a paraffin type is preferable, and a paraffin type having few aromatic components is particularly preferable.

The properties of these non-aromatic rubber softeners are preferably a dynamic viscosity at 37.8°C of 20 to 500 cSt, a pour point of -10 to -15°C, and a fire point (COC) of 170 to 300°C.

As other resin components other than polyolefin resins and ethylene-based copolymers, polyolefin resins modified with carboxylic anhydrides, styrene-based elastomers, and acrylic rubbers can be added to impart strength, impart flame retardancy, and impart flexibility. and other resin or rubber components.

The so-called resin component (A) in the present invention refers to polyolefin resin (A-1), ethylene-based copolymer (A-2), styrene-based block copolymer (A-3) and non-aromatic rubber In addition to the softener (A-4), the sum of all resin components including resins and rubber components other than the above-mentioned (A-1), (A-2), and (A-3) is used. In addition, 100 parts by mass of the resin component (A) means that the total usage-amount of each resin component mentioned above is 100 parts by mass. The so-called polyolefin resin (A-1) and/or ethylene-based copolymer (A-2) and/or styrene-based block copolymer (A-3) as the main component means that the resin component (A) 100 In mass %, the total amount of (A-1), (A-2) and (A-3) used is usually 60 mass % or more, preferably 75 mass % or more, more preferably 90 mass % or more and 100 mass % or less . In addition, at least 1 sort(s) selected from the said (A-1), (A-2) and (A-3) can be used as a main component of a resin component (A).

(B) metal hydrate

In the present invention, a predetermined amount of metal hydrate (B) is blended into the thermoplastic resin composition (A) in order to impart flame retardancy to the resin composition and the wiring material.

The metal hydrate used in the present invention is not particularly limited. For example, compounds having hydroxyl groups or crystal water such as aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, and hydrotalcite, These can be used individually or in combination of 2 or more types. Magnesium hydroxide is preferable as the metal hydrate, and among magnesium hydroxides, for example, commercially available "Kisma 5 series" (trade name, manufactured by Kyowa Chemical Co., Ltd.) and the like are preferable.

As the metal hydrate used in the present invention, it is necessary to use a metal hydrate treated with a crosslinkable silane coupling agent.

Here, the so-called silane coupling agent is cross-linking, which means, for example, the terminal group of the amino group, vinyl group, epoxy group, etc. of the silane coupling agent reacts with the metal hydrate, and the silane coupling agent is attached to the surface of the metal hydrate. mixture. In addition, vinyl groups having reactive double bonds such as acryloyl and methacryloyl groups are also included in the vinyl group.

As a crosslinkable silane coupling agent, the silane coupling agent which has a double bond, such as a vinyl group, an acryloyl group, and a methacryloyl group, and the silane coupling agent which has an epoxy group, a mercapto group, or an amino group at a terminal, etc. are mentioned. These silane coupling agents may be used in combination with other silane coupling agents, or two or more silane coupling agents having these vinyl groups, epoxy groups, mercapto groups, or amino groups at their terminals may be used in combination. In addition, these silane coupling agents may be used in combination with aliphatic surface treatment agents such as stearic acid.

Specific examples of silane coupling agents having a vinyl group, epoxy group, mercapto group or amino group at the end include vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, Glycidoxypropyltriethoxysilane, glycidoxypropylmethyldimethoxysilane, methacryloyloxypropyltrimethoxysilane, methacryloxy Propyltriethoxysilane, Methacryloxypropylmethyldimethoxysilane, Mercaptopropyltrimethoxysilane, Mercaptopropyltriethoxysilane, Aminopropyltriethoxysilane, Aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropyltripropylmethyl Dimethoxysilane, etc.

When the metal hydrate is treated with a silane coupling agent, it is necessary to mix the metal hydrate with the silane coupling agent in advance. At this time, it is appropriate to add a silane coupling agent in an amount sufficient for surface treatment, and specifically, it is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, based on the metal hydrate. The stock solution of silane coupling agent can be used, and it can also be used after diluting with solvent.

When metal hydrate treated with a crosslinkable silane coupling agent is used as a flame retardant, for example, compared with the case of using metal hydrate treated only with stearic acid or oleic acid, it can be confirmed that the weather resistance is greatly improved. Sexual improvement. The improved process is not clear, but a metal hydrate of a crosslinkable silane coupling agent is used, and the silane coupling agent can be bonded to the polymer. When the bond between the silane coupling agent and the polymer is damaged under the action of light such as ultraviolet rays, the hindered phenolic antioxidant or hindered amine light stabilizer captures its free radicals, and the thioether antioxidant shown in formula (1) Oxygen repairs, making it difficult to generate cracks and decrease in elongation when the resin component is under stress.

On the other hand, metal hydrates that have been surface-treated with stearic acid or oleic acid or non-cross-linked metal hydrates do not bond to the polymer, and under the action of light such as ultraviolet light, the polymer or surface A phenomenon in which the treatment agent deteriorates, causing defects between the polymer and the metal hydrate. Of course, although the defect can be repaired by the same method, since there is no bonding between the polymer and the metal hydrate, even the repair is incomplete. Therefore, it is considered that the resin composition exposed for a long period of time in a stress-applied state may generate cracks or decrease in elongation.

In addition, the thioether-based antioxidant or benzophenone-based and/or benzotriazole-based ultraviolet absorber represented by the formula (1) is either decomposed by the alkalinity of the metal hydrate or adsorbed on the metal hydrate . By using a metal hydrate treated with a crosslinkable silane coupling agent, since the metal hydrate and the polymer have a bonded structure, it is possible to inhibit the thioether-based antioxidant or benzophenone-based antioxidant represented by the above formula (1) and / or adsorption or decomposition of benzotriazole-based ultraviolet absorbers.

As part of the metal hydrate treated with a cross-linkable silane coupling agent, for example, a metal hydrate surface-treated with a non-cross-linkable silane coupling agent, a metal hydrate treated with a fatty acid, etc., an untreated metal hydrate can be used. Hydrates, but must be controlled at most below 1/3 of metal hydrates.

The quantity of a metal hydrate is 60-300 mass parts with respect to 100 mass parts of resin components (A), Preferably it is 70-250 mass parts, More preferably, it is 70-200 mass parts. When it is less than 60 parts by mass, a problem arises in flame retardancy, and when it is more than 300 parts by mass, not only the mechanical strength deteriorates but also the weather resistance remarkably decreases. Therefore, in order to maintain weather resistance, the upper limit thereof is preferably 250 parts by mass or less, more preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less.

(C) Hindered phenolic antioxidant

Specific examples of hindered phenolic antioxidants used in the present invention include pentaerythritol-tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 1,6- Hexylene glycol-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3 , 5-di-tert-butylanilino)-1,3,5-triazine, 2,2-thio-diethylene-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl ) propionate), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tri (3,5-di-tert-butyl-4-hydroxybenzyl)benzene and the like.

In conventional resin compositions, the hindered phenolic antioxidant is usually used in an amount of 0.5 parts by mass or less with respect to 100 parts by mass of the resin component. On the contrary, in the resin composition of the present invention, the hindered phenolic antioxidant is used in an amount of at least 1 part by mass in 100 parts by mass of the resin component (A), preferably 1.3 parts by mass or more, more preferably 1.5 parts by mass or more.

In addition, the amount of the hindered phenolic antioxidant must be 8 parts by mass or less with respect to 100 parts by mass of the resin component (A). When it is more than 8 parts by mass, not only the strength is significantly lowered, but also the effect of addition is almost lost.

The hindered phenolic antioxidant not only maintains the heat resistance of the present resin composition, but also has the function of capturing free radicals generated by photodegradation. In addition, by capturing free radicals generated between the metal hydrate bonded with a silane coupling agent and the polymer due to photodegradation, and repairing it, it is possible to suppress defects between the polymer and the metal hydrate, Also, the reduction in elongation or stress fracture of the resin composition after irradiation with light such as ultraviolet rays can be suppressed.

(D) Sulfide-based antioxidant

The thioether-based antioxidant preferably used in the present invention can be represented by the following formula (1).

[chemical formula 3]

In formula (1), R ¹ represents an alkyl group, preferably an alkyl group having 1 to 30 carbon atoms.

The amount of the thioether-based antioxidant represented by formula (1) is usually about 0.3 parts by mass relative to the conventional resin composition. On the contrary, in the present invention, the thioether antioxidant represented by formula (1) is preferably used in an amount of 0.8 to 8 parts by mass, more preferably in a range of 1.0 to 6 parts by mass, and particularly preferably in 100 parts by mass of the resin component (A). 1.5 to 5 parts by mass are used.

The addition of 0.8 parts by mass or more of the thioether-based antioxidant is preferable since heat resistance can be dramatically improved. However, when a thioether-based antioxidant represented by formula (1) is added, weather resistance tends to decrease. Therefore, especially by adding 0.8 parts by mass or more of a benzophenone-based or benzotriazole-based ultraviolet absorber, a non-halogen compound and an electric wire further excellent in both heat resistance and weather resistance can be obtained. In particular, by adding a benzophenone-based ultraviolet absorber, high weather resistance can be maintained, and a non-halogen compound and electric wire excellent in both heat resistance and weather resistance can be obtained.

When adding the thioether antioxidant represented by formula (1), the benzophenone or benzotriazole UV absorber is more than 0.8 parts by mass, preferably the benzophenone UV absorber is 0.8 parts by mass or more, more preferably 1.0 parts by mass or more.

In particular, when an ethylene-based copolymer having an acid content of 20% by mass or more is used as a resin component, it has been found that the effect of maintaining the heat resistance of the thioether-based antioxidant dramatically increases. Thereby, the non-halogen compound and electric wire which maintain heat resistance and are very excellent in weather resistance can be obtained.

When the added amount of the thioether-based antioxidant is too large, not only bleeding occurs, but also the weather resistance is greatly reduced.

(E) Benzophenone-based and benzotriazole-based UV absorbers

Specific examples of the benzophenone-based ultraviolet absorber used in the present invention include 2,4-dihydroxybenzophenone, bis(5-benzoyl-4-hydroxy-2-methoxyphenyl ) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, etc.

[chemical formula 4]

In formula (Ea-1), R ² represents an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms. Specific examples of the compound of formula (Ea-1) include 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, and the like.

In addition, specific examples of the benzotriazole-based ultraviolet absorber used in the present invention include 2-(2'-hydroxy-3',5'-bis(α,α-dimethylbenzyl)phenyl )-benzotriazole, 2-(2'-hydroxyl-3', 5'-di-tert-butyl-5'-methylphenyl)benzotriazole, 2-(2'-hydroxyl-3', 5'-di-tert-amyl)benzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole and compounds represented by the following formula:

[chemical formula 5]

These ultraviolet absorbers are decomposed by the alkalinity of the metal hydrate and the alkalinity of the hindered amine light stabilizer. Especially when a large amount of magnesium hydroxide is used as a metal hydrate, the decomposition is severe. When using a resin composition with an acid content of 20% by mass or more of an ethylene-based copolymer as the resin component, since the alkalinity can be suppressed and the decomposition of benzophenone-based and benzotriazole-based ultraviolet absorbers can be suppressed, it is weather-resistant performance can be greatly improved.

The amount of the benzophenone-based and/or benzotriazole-based ultraviolet absorber is 0.4 to 8 parts by mass, preferably 0.8 to 8 parts by mass, more preferably 0.8 to 6 parts by mass, based on 100 parts by mass of the resin component (A) , especially preferably 1.2 to 5 parts by mass, particularly preferably 1.5 to 5 parts by mass.

When it is less than 0.4 parts by mass, there is substantially no effect, and when it is more than 8 parts by mass, not only the mechanical strength but also the heat resistance also decreases.

It is estimated that benzophenone-based or benzotriazole-based ultraviolet absorbers are decomposed by metal hydrates, so adding 0.8 parts by mass or more is preferable.

In particular, very excellent weather resistance can be obtained by adding 0.8 parts by mass or more of a benzophenone-based ultraviolet absorber. In addition, even if the thioether-based antioxidant represented by the formula (1) is added, the weather resistance can be maintained while the heat resistance can be maintained.

(F) HALS

Specific examples of hindered amine light stabilizers used in the present invention include dimethyl-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine succinate Pyridine polycondensate, poly((6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl)((2,2,6, 6-tetramethyl-4-piperidinyl)imino)hexamethylene ((2,2,6,6-tetramethyl-4-piperidinyl)imino)) and compounds represented by the following formula:

【Chemical 6】

In formula (F-3), x represents an integer of 1 or more. In formula (F-4), n represents an integer of 1 or more, preferably 1-20. Specific examples of the compound of formula (F-4) include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate and the like.

The function of this hindered amine light stabilizer is to have a repairing effect when it is cut by light such as ultraviolet rays through the bond between the metal hydrate of the silane coupling agent and the polymer. In particular, the restoration of this bond near the surface of the resin has a great effect. When the amount is less than 1 part by mass with respect to 100 parts by mass of the resin component (A), weather resistance will remarkably decrease. In addition, when more than 7 parts by mass, the aging characteristics are remarkably reduced.

(g) organic peroxide

As the organic peroxide used in the present invention, for example, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl peroxide, ) hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1- Bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl-4,4-bis(tert-butylperoxy)valerate (Barrett), benzene peroxide Formyl, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, diacetyl peroxide substances, lauroyl peroxide, tert-butyl cumyl peroxide, etc.

Among them, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 2,5-dimethyl-2, 5-di(t-butylperoxy)hexyne-3 is most preferred.

The content of the organic peroxide (g) is in the range of 0.01 to 1.0 parts by mass, preferably 0.01 to 0.6 parts by mass, more preferably 0.05 to 0.8 parts by mass, particularly preferably 0.1 to 0.6 parts by mass, relative to 100 parts by mass of the thermoplastic resin component (A). parts by mass. When the organic peroxide is selected from the above-mentioned range, since excessive crosslinking does not occur, a partially crosslinked composition having excellent extrudability can be obtained without generating infusible matter.

(h) (meth)acrylate-based and/or acrylic acid-based crosslinking aids

In the manufacture of the flame retardant resin composition of the present invention or the thermoplastic resin component (A) used therein, in the presence of an organic peroxide, through a crosslinking auxiliary agent, the vinyl aromatic thermoplastic elastomer and ethylene· A partially crosslinked structure is formed between the α-olefin copolymers. As an example of the cross-linking aid used at this time, a (meth)acrylate-based cross-linking aid represented by the following general formula can be mentioned:

[chemical formula 7]

(In the formula, R is H or CH ₃ , and n is an integer of 1 to 9). The (meth)acrylate-based cross-linking auxiliary agent here refers to acrylate-based and methacrylate-based cross-linking auxiliary agents. Specifically, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate Allyl acrylate, allyl methacrylate.

In addition, compounds having an allyl group at the terminal, such as diallyl fumarate, diallyl phthalate, tetraallyloxyethane, and triallyl isocyanurate, can be used.

Among them, especially (meth)acrylate-based crosslinking aids in which n is 1 to 6 are preferable, and examples include ethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethyl Acrylate.

In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle, has good compatibility with other components, and has a peroxide solubilizing effect, and has a role as a peroxide dispersing aid, so heating and mixing The cross-linking effect during refining is uniform and effective, so that a partially cross-linked thermoplastic resin with a balance of hardness and rubber elasticity can be obtained, so it is the most ideal. By using such a compound, neither insufficient cross-linking nor excessive cross-linking can be expected, and a uniform and efficient partial cross-linking reaction at the time of heating and kneading can be expected.

The content of the crosslinking assistant used in the present invention is preferably in the range of 0.03 to 1.8 parts by mass, more preferably 0.03 to 1.2 parts by mass, relative to 100 parts by mass of the thermoplastic resin component (A). By selecting the crosslinking assistant within this range, crosslinking can be achieved slowly without excessive crosslinking, and a composition excellent in extrudability can be obtained without generating infusible matter. It is preferable that the content of the crosslinking aid is about 1.5 to 4.0 times the content of the organic peroxide in terms of mass ratio.

In the insulating resin composition of the present invention, at least one compound selected from zinc stannate, zinc hydroxystannate, and zinc borate may be added as needed to further improve the flame retardancy. By using these compounds, the shell formation speed at the time of combustion increases, and the shell formation becomes stronger. The zinc stannate, zinc hydroxystannate, and zinc borate used in the present invention preferably have an average particle size of 5 μm or less, and more preferably 3 μm or less.

Specific examples of the zinc borate used in the present invention include Alkanex FRC-500 (2ZnO/3B ₂ O ₃ ·3.5H ₂ O), FRC-600 (both trade names, manufactured by Mizusawa Chemical Co., Ltd.) and the like. In addition, specific examples of zinc stannate (ZnSnO ₃ ) and zinc hydroxystannate (ZnSn(OH) ₆ ) include Alkanex ZS and Alkanex ZHS (both trade names, manufactured by Mizusawa Chemical Co., Ltd.).

In the insulating resin composition of the present invention, various additives generally used in electric wires and cables, such as metal passivators, flame retardant (auxiliary) agents, fillers, lubricants, etc. .

As specific examples of metal deactivators, N, N'-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hydrazine, 3-(N-salicyloyl ) amino-1,2,4-triazole, 2,2'-oxalamide-bis(ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and the like.

Examples of flame retardant (assistant) agents and fillers include carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compounds, quartz, talc, calcium carbonate, magnesium carbonate, White carbon black etc.

Examples of lubricants include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based, etc. Among them, paraffin wax E, paraffin wax OP (both trade names, manufactured by Hoechst Co., Ltd.) and the like also exhibit internal lubrication. Ester-based lubricants with excellent properties and external lubricity are preferred.

In the insulating resin composition of the present invention, the above-mentioned various components can be mixed with a twin-screw kneading extruder, a Banbury mixer, a kneader, a rolling mill, etc. It is made by melting and kneading with a kneading device. In the present invention, the melting temperature should be higher than the melting temperature of the thermoplastic resin component (A). The temperature varies depending on the specific constitution of the resin component (A), and is not particularly limited, but it is preferably performed at 160 to 250°C.

Next, the insulated electric wire of the present invention will be described.

The electric wire, cable, optical cable, and optical flexible wire of the present invention are products coated with the cross-linked body of the insulating resin composition of the present invention on the outside of conductors and/or optical fibers, and are produced by extrusion molding for ordinary electric wire production. The insulating resin composition of the present invention is extruded and coated around conductors or optical fibers by a machine.

It can be cross-linked after the silane coupling agent and the polymer are bonded, or a part of the resin can be cross-linked when the resin composition is made with a kneader or a Banbury mixer, and the polymer and the metal can be hydrated at the same time The material is bonded by a silane coupling agent.

The cross-linking method after coating is not particularly limited, and electron beam cross-linking or chemical cross-linking can be used.

When using the electron beam crosslinking method, the dose of the electron beam is 1 to 30 Mrad is appropriate. In order to carry out more effective crosslinking, it can be mixed with methacrylate compounds such as trimethylolpropane triacrylate, triallyl Polyfunctional compounds such as allyl compounds such as isocyanuric isocyanate, maleimide compounds, and divinyl compounds are used as crosslinking aids.

When using the chemical crosslinking method, organic peroxides such as hydrogen peroxide, dialkyl peroxide, diacyl peroxide, peroxyester, ketone peroxyester, ketone peroxide and the like are added to the resin composition as A cross-linking agent that cross-links by heat treatment after extrusion molding.

The diameter of the conductor, the diameter of the optical fiber, the material of the conductor or the optical fiber, etc. of the insulated electric wire of the present invention are not particularly limited, and may be appropriately selected according to the application. The thickness of the coating layer of the insulating resin composition formed around the conductor and/or the optical fiber is also not particularly limited, but is preferably 0.15 to 1 mm. In addition, the insulating layer may have a multilayer structure, and may have an intermediate layer or the like in addition to the covering layer formed using the insulating resin composition of the present invention.

Example

The present invention will be described in more detail below based on examples, but the present invention is not limited thereto.

First, various components shown in the table below were dry-blended at room temperature and melt-kneaded with a Banbury mixer to produce various insulating resin compositions. In addition, the melting temperature is performed at or above the melting temperature of the resin component mainly composed of the polyolefin resin and/or the ethylene-based copolymer and/or the styrene block copolymer. Specifically, all examples shown in the table were carried out at 210°C.

Next, using an extrusion coating device for wire manufacturing, the insulating resin composition melted and kneaded in advance is used to coat the conductor (tinned annealed copper stranded wire with a conductor diameter of 1.14mmΦ, composition: 30 wires/0.18mmΦ) On, made of various insulated wires. Its outer diameter is 2.74 mm (coating layer thickness 0.86 mm).

Also, the following products using the various ingredients shown in Tables 1-4 were used. In the table, the numerical values representing the composition are all parts by mass.

(01) Ethylene-vinyl acetate copolymer

VA content 33% by mass

EV-180 (trade name, manufactured by Mitsui DuPont Poly Chemical)

(02) Ethylene-ethyl acrylate copolymer

EA content 25% by mass

A-714 (trade name, manufactured by Mitsui DuPont Poly Chemical)

(03) Ethylene-vinyl acetate copolymer

VA content 17% by mass

V-527-4 (trade name, manufactured by Mitsui DuPont Poly Chemical)

(04) Ethylene-vinyl acetate copolymer

VA content 41% by mass

EV-40LX (trade name, manufactured by Mitsui DuPont Poly Chemical)

(05) Ethylene-alpha olefin copolymer

Density 0.905

ユメリツト0540F (trade name, manufactured by Ube Industries)

(06) Block polypropylene

PN-610S (trade name, manufactured by Tokuyama)

(07) Styrene-based elastomer

Septon 4077 (trade name, manufactured by Kurare)

(08) Rubber softener

Diana Procesus Oil PW-90 (trade name, manufactured by Idemitsu Kosan)

(09)Maleic acid modified PE

Adoma XE070 (trade name, manufactured by Mitsui Chemicals)

(10) Untreated magnesium hydroxide

Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd.)

(11) Magnesium hydroxide surface-treated with a vinyl-terminated silane coupling agent

Kisuma 5LH (trade name, manufactured by Kyowa Chemical Co., Ltd.)

(12) Stearic acid treated magnesium hydroxide

Kisuma 5A (trade name, manufactured by Kyowa Chemical Co., Ltd.)

(13) Silane coupling agent with vinyl (acryloyl) at the end

TSL8370 (trade name, manufactured by Toshiba Sirikon Co., Ltd.)

(14) Silane coupling agent with epoxy group at the end

TSL8350 (trade name, manufactured by Toshiba Sirikon Corporation)

(15) Hindered phenol antioxidants

Ilganox 1010 (trade name, manufactured by Chiba Speciaru Tei-Chemicals Co., Ltd.)

(16) Sulfide-based antioxidants

ADEKA STAB AO-412S (trade name, manufactured by Asahi Denka)

(17) Benzophenone-based UV absorbers

ADEKA STAB 1413 (trade name, made by Asahi Denka)

(18) Benzotriazole-based UV absorbers

アディカタブ LA-36 (trade name, manufactured by Asahi Denka)

(19)Hindered amine light stabilizer

ADEKA STAB LA-52 (trade name, manufactured by Asahi Denka)

(20) (meth)acrylate crosslinking aid

NK ester 3G (trade name, methylolpropane trimethacrylate made by Shin-Nakamura Chemical Co., Ltd.)

(21)Organic peroxide

Perohexa 25B (trade name, 2,5-dimethyl-2,5-bis(tert-butylpentyloxy)-hexane manufactured by NOF Corporation)

(22) Calcium stearate (manufactured by NOF)

The various insulated wires obtained were subjected to the following tests. The results are shown in Tables 1-4.

1) elongation, tension

The elongation (%) of each insulated wire and the tensile strength (MPa) of the coating layer were measured under the conditions of 20 mm between the marked lines and a tensile speed of 200 mm/min. The required properties of elongation and tensile strength are 100% or more and 10MPa or more, respectively.

2) Heat resistance

After heat treatment at 160° C. for 30 days, the elongation (%) of each insulated wire and the tensile strength (MPa) of the coating layer were measured under the conditions of 20 mm between the marked lines and a tensile speed of 200 mm/min. The elongation residual rate is above 65%, and the tensile residual rate is above 70%, which is qualified.

3) Weather resistance

The weather resistance was irradiated for 300 hours using a super UV tester SUV-1 (manufactured by Dainippon Plastics Co., Ltd.). The elongation residual rate is above 45%, and the tensile residual rate is above 50%.

In addition, samples wound around their inner diameters were made, and the presence or absence of cracks after irradiation was measured. The case where cracks did not occur was rated as ○, and the case where cracks occurred was rated as ×.

4) Exudation

Leave it at 30°C for 10 days, and check whether it seeps out. Those with no leakage or no problem are rated as ○, those with large leakage are rated as △, and those with large bleeding that cannot be tolerated by users are rated as ×. Even △ can sometimes be used.

Table 1 Example 1 2 3 4 5 6 (01) Ethylene-vinyl acetate copolymer 50 50 50 50 (02) Ethylene-ethyl acrylate copolymer 50 (03) Ethylene-vinyl acetate copolymer 50 (04) Ethylene-vinyl acetate copolymer (05) Ethylene-α-olefin copolymer (06) Block polypropylene 15 15 15 15 15 15 (07) Styrene-based elastomer 25 25 25 25 25 25 (08) Rubber softener 5 5 5 5 5 5 (09)Maleic acid modified PE 5 5 5 5 5 5 (10) Untreated magnesium hydroxide (11) Magnesium hydroxide treated with silane coupling agent containing vinyl groups at the end 130 130 100 130 130 130 (12) Stearic acid treated magnesium hydroxide (13) Silane coupling agent with vinyl group at the end (14) Silane coupling agent with epoxy group at the end (15) Hindered phenol antioxidants 3 3 3 2 2 2 (16) Sulfide-based antioxidants 1.5 1.5 1.5 (17) Benzophenone-based UV absorbers 2 2 2 2 2 2 (18) Benzotriazole-based UV absorbers 1 1 (19)Hindered amine light stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 (21)Organic peroxide 0.2 0.2 0.2 0.2 0.2 0.2 (20) (meth)acrylate-based crosslinking agent 0.6 0.6 0.6 0.6 0.6 0.6 (22) Calcium stearate 1 1 1 1 1 1 Elongation (%) 280 280 280 280 290 180 Tension resistance (MPa) 13.3 13.3 13.3 13.3 11.1 17.2 Residual rate of heat resistance elongation (%) Tensile residual rate (%) 67104 68104 67104 92104 83102 77113 Weather Resistance Elongation Residual Rate (%) Tension Residual Rate (%) Crack 7785○ 8285○ 8985○ 6485○ 5983○ 5082○ exudate ○ ○ ○ ○ ○ ○

Table 2 Example 7 8 9 10 11 12 (01) Ethylene-vinyl acetate copolymer 50 50 55 55 (02) Ethylene-ethyl acrylate copolymer (03) Ethylene-vinyl acetate copolymer (04) Ethylene-vinyl acetate copolymer 50 (05) Ethylene-α-olefin copolymer 50 (06) Block polypropylene 15 15 15 15 15 15 (07) Styrene-based elastomer 25 25 25 25 20 20 (08) Rubber softener 5 5 5 5 5 5 (09)Maleic acid modified PE 5 5 5 5 5 5 (10) Untreated magnesium hydroxide (11) Magnesium hydroxide treated with silane coupling agent containing vinyl groups at the end 130 130 130 130 130 130 (12) Stearic acid treated magnesium hydroxide (13) Silane coupling agent with vinyl group at the end (14) Silane coupling agent with epoxy group at the end (15) Hindered phenol antioxidants 2 2 2 2 2 2 (16) Sulfide-based antioxidants 1.5 1.5 0.8 6.5 1.5 1.5 (17) Benzophenone-based UV absorbers 2 2 2 2 0.5 7 (18) Benzotriazole-based UV absorbers (19)Hindered amine light stabilizer 1.5 1.5 1.5 1.5 1.5 1.5 (21)Organic peroxide 0.2 0.2 0.2 0.2 0.2 0.2 (20) (meth)acrylate-based crosslinking agent 0.6 0.6 0.6 0.6 0.6 0.6 (22) Calcium stearate 1 1 1 1 1 1 Elongation (%) 420 380 290 350 260 330 Tension resistance (MPa) 10.5 18.5 14.1 10.9 14.2 10.6 Residual rate of heat resistance elongation (%) Tensile residual rate (%) 8292 6698 74106 85102 87113 77109 Weather Resistance Elongation Residual Rate (%) Tension Residual Rate (%) Crack 6782○ 4675○ 7481○ 5090○ 5385○ 5785○ exudate ○ ○ ○ ○ ○ ○

table 3 Example 13 14 15 16 17 (01) Ethylene-vinyl acetate copolymer 55 55 55 55 55 (02) Ethylene-ethyl acrylate copolymer (03) Ethylene-vinyl acetate copolymer (04) Ethylene-vinyl acetate copolymer (05) Ethylene-α-olefin copolymer (06) Block polypropylene 15 15 15 15 15 (07) Styrene-based elastomer 20 20 20 20 20 (08) Rubber softener 5 5 5 5 5 (09)Maleic acid modified PE 5 5 5 5 5 (10) Untreated magnesium hydroxide 130 (11) Magnesium hydroxide treated with silane coupling agent containing vinyl groups at the end 130 130 100 130 (12) Stearic acid treated magnesium hydroxide 30 (13) Silane coupling agent with vinyl group at the end 1.0 (14) Silane coupling agent with epoxy group at the end 0.3 (15) Hindered phenol antioxidants 2 2 2 2 6 (16) Sulfide-based antioxidants 1.5 1.5 1.5 1.5 1.5 (17) Benzophenone-based UV absorbers 2 2 2 2 (18) Benzotriazole-based UV absorbers 2 (19)Hindered amine light stabilizer 1.5 6 1.5 1.5 1.5 (21)Organic peroxide 0.2 0.2 0.2 0.2 0.2 (20) (meth)acrylate-based crosslinking agent 0.6 0.6 0.6 0.6 0.6 (22) Calcium stearate 1 1 1 1 1 Elongation (%) 260 320 350 210 350 Tension resistance (MPa) 11.8 10.9 10.8 12.7 10.4 Residual rate of heat resistance elongation (%) Tensile residual rate (%) 92112 74109 70112 83116 91114 Weather Resistance Elongation Residual Rate (%) Tension Residual Rate (%) Crack 5785○ 5081○ 4780○ 5684○ 6185○ exudate ○ ○ ○ ○ ○

Table 4 Example 1 2 3 4 (01) Ethylene-vinyl acetate copolymer 55 55 55 55 (02) Ethylene-ethyl acrylate copolymer (03) Ethylene-vinyl acetate copolymer (04) Ethylene-vinyl acetate copolymer (05) Ethylene-α-olefin copolymer (06) Block polypropylene 15 15 15 15 (07) Styrene-based elastomer 20 20 20 20 (08) Rubber softener 5 5 5 5 (09)Maleic acid modified PE 5 5 5 5 (10) Untreated magnesium hydroxide (11) Magnesium hydroxide treated with silane coupling agent containing vinyl groups at the end 130 130 130 (12) Stearic acid treated magnesium hydroxide 130 (13) Silane coupling agent with vinyl group at the end (14) Silane coupling agent with epoxy group at the end (15) Hindered phenol antioxidants 2 0.5 2 2 (16) Sulfide-based antioxidants 1.5 1 1 10 (17) Benzophenone-based UV absorbers 2 1 0.2 2 (18) Benzotriazole-based UV absorbers (19)Hindered amine light stabilizer 1.5 1 0.2 2 (21)Organic peroxide 0.2 0.2 0.2 0.2 (20) (meth)acrylate-based crosslinking agent 0.6 0.6 0.6 0.6 (22) Calcium stearate 1 1 1 1 Elongation (%) 420 260 250 350 Tension resistance (MPa) 10.8 13.3 13.2 11.0 Residual rate of heat resistance elongation (%) Tensile residual rate (%) 6798 70102 86110 9210 Weather Resistance Elongation Residual Rate (%) Tension Residual Rate (%) Crack 3270○ 3278○ 4372○ 4689○ exudate ○ ○ ○ △

It is clear from the results shown in Tables 1 to 4 that in Comparative Example 1, since the metal hydrate was not treated with a silane coupling agent, defects were generated between the magnesium hydroxide and the polymer, and the extension was confirmed in the weather resistance test. rate decreased. In Comparative Example 2, since the amount of hindered phenolic antioxidant was too small, the elongation decreased in the weather resistance test. In Comparative Example 3, since the amount of the benzophenone-based ultraviolet absorber and the amount of the hindered amine-based light stabilizer were too small, the elongation decreased due to light irradiation.

On the contrary, in Examples 1 to 17 of the present invention, all test evaluations were good, and an insulating resin composition and an insulated wire having the desired performance were obtained. In addition, Comparative Example 4 is a comparative example in which the amount of the sulfide-based antioxidant was too large.

The effect of the invention

According to the present invention, it is possible to provide a wire that has high flame retardancy, excellent heat resistance, weather resistance, and mechanical properties required for insulated wires, can be colored in any color, and maintains electrical properties such as electrical insulation. An insulating resin composition that maintains oil resistance.

In addition, by using this composition as a coating material, it is possible to provide an insulated wire having the following characteristics: no heavy metal compound and phosphorus compound are leached out during landfill, no large amount of smoke is produced during incineration, and there is no problem of corrosive gas generation. Instead, it has excellent heat resistance and weather resistance.

Claims (6)

1. an insualtion resin composition is characterized in that, said composition be with respect to polyolefin resin and/or vinyl copolymer and/or styrene block copolymer as resinous principle (A) 100 mass parts of principal constituent, contain:

Carried out surface-treated metal hydrate 60～300 mass parts through the bridging property silane coupling agent,

Be selected from following (i), (ii) or (iii) any a kind:

(i) hindered phenol is that oxidation inhibitor 1～8 mass parts, benzophenone series and/or benzotriazole are that UV light absorber 0.4～8 mass parts and hindered amine are photostabilizer 1～7 mass parts,

(ii) hindered phenol is that oxidation inhibitor 1～8 mass parts, benzophenone series UV light absorber 0.8～8 mass parts and hindered amine are photostabilizer 1～7 mass parts,

(iii) hindered phenol is oxidation inhibitor 1～8 mass parts and is that oxidation inhibitor 0.8～8 mass parts, benzophenone series and/or benzotriazole are that UV light absorber 0.4～8 mass parts and hindered amine are photostabilizer 1～7 mass parts with the thioether that following formula (1) structure is represented

(Chemical formula 1)

(in the formula, R ¹The expression alkyl)

(g) organo-peroxide 0.01～1.0 mass parts; And

(h) mixture of (methyl) acrylic ester and/or allyl base system crosslinking coagent 0.03～1.8 mass parts, and more than the melt temperature of described thermoplastic resin composition (A), add hot milling and form.

2. according to the insualtion resin composition described in the claim 1, it is characterized in that, with respect to above-mentioned resinous principle (A) 100 mass parts, containing above-mentioned (i) hindered phenol is that oxidation inhibitor 1～8 mass parts, benzophenone series and/or benzotriazole are UV light absorber 0.4～8 mass parts, and hindered amine is photostabilizer 1～7 mass parts.

3. according to the insualtion resin composition described in the claim 1, it is characterized in that, with respect to above-mentioned resinous principle (A) 100 mass parts, containing above-mentioned (ii) hindered phenol is that oxidation inhibitor 1～8 mass parts, benzophenone series UV light absorber 0.8～8 mass parts and hindered amine are photostabilizer 1～7 mass parts.

4. according to the insualtion resin composition described in the claim 1, it is characterized in that, with respect to above-mentioned resinous principle (A) 100 mass parts, contain above-mentioned (iii) hindered phenol and be oxidation inhibitor 1～8 mass parts, be that oxidation inhibitor 0.8～8 mass parts, benzophenone series and/or benzotriazole are that UV light absorber 0.4～8 mass parts and hindered amine are photostabilizer 1～7 mass parts with the thioether of following formula (1) expression structure.

5. an insulated line is characterized in that, with what form around wantonly 1 described insualtion resin composition coated conductor in the claim 1～4 and/or the optical fiber.

6. an insulated line is characterized in that, around wantonly 1 described insualtion resin composition coated conductor in the claim 1～4 and/or optical fiber, and resin combination that should lining portion crosslinked forming in addition.