JP2005336252A - Flame-retardant resin composition and molded component using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a highly flame-retardant resin composition emitting no toxic substances when discarded. <P>SOLUTION: The flame-retardant resin composition comprises 100 pts. mass of the thermoplastic resin component(A) described below, (e) 0.001-1 pt. mass of an organic peroxide, (f) 0.03-2.5 pt(s). mass of a crosslinking auxiliary and 50-300 pts. mass of a metal hydrate(B). This composition is obtained by partially crosslinking by heating/kneading the above components at a temperature higher than the melting temperature of the component(A). The thermoplastic resin component(A) comprises (a) 20-96.5 mass% of at least one polymer selected from the group consisting of copolymer rubbers of (a1) an ethylene-α-olefin, (a2) ethylene-vinyl acetate and an ethylene-(meth)acrylic acid (ester) and (a3) ethylene propylene, respectively, (b) 0-36.5 mass% of a hydrogenated product of a copolymer of an aromatic vinyl compound and conjugated diene compound, (c) 3-50 mass% of a polypropylene resin and (d) 0.5-25 mass% of a hydrogenated product of a copolymer of an unsaturated carboxylic acid-modified aromatic vinyl compound and conjugated diene compound. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention does not require a crosslinking facility during processing, and is particularly excellent in flexibility and weather resistance, excellent in mechanical properties and heat resistance, and has excellent flame retardancy and the flame retardant resin composition. The present invention relates to a wiring material having a composition as a covering material, an optical fiber cord and other molded parts.
More specifically, the present invention relates to an insulated wire, an electric cable, an electric cord, an optical fiber core, an optical fiber cord or the like used for an internal or external wiring of an electric / electronic device, or a mold such as a power cord. With regard to flame retardant resin compositions suitable as materials, tubes and sheets, and wiring materials and other molded parts using them, heat resistance, flexibility, and trauma resistance without the need for special equipment such as crosslinking equipment after processing It is a flame retardant resin composition with excellent pressure contact processability, and does not generate volatile substances even when kept at high temperature for a long time, especially in landfills that are not treated properly, burning under inappropriate conditions, etc. A flame-retardant resin composition that is suitable for recycling after use and has no elution of heavy metal compounds, generation of a large amount of smoke or harmful gas at the time of disposal, and an environmental problem. It relates wiring material other molded parts which are.

Insulated wires / cables / cords, optical fiber cores, optical fiber cords, etc. used for internal and external wiring of electrical / electronic equipment are flame retardant, heat resistant, mechanical properties (eg tensile properties, wear resistance) ) And other characteristics are required.
For this reason, as the coating material used for these wiring materials, polyvinyl chloride (PVC) compound and polyolefin compound containing halogen flame retardant containing bromine atom or chlorine atom in the molecule are mainly used. It was.
However, if these are disposed of without proper treatment and landfilled, plasticizers and heavy metal stabilizers blended in the coating material will elute, or if burned under inappropriate conditions, In some cases, harmful gases may be generated from halogen compounds contained in the coating material, and this problem has been discussed in recent years.
For this reason, it is a non-halogen flame retardant material that does not cause the generation of harmful plasticizers and heavy metals, which are concerned about having an impact on the environment, or the generation of halogenated gases when burned in equipment without an exhaust gas treatment facility. Investigation of coated wiring materials is underway.

Insulation using thermoplastic elastomers based on ethylene copolymers and styrene block copolymers as non-halogen materials with moderate flexibility and a balance between flame retardancy and heat resistance. Electric wires have been used.
In the past, polyolefin resins modified with unsaturated carboxylic acids or their derivatives have been generally used in order to maintain the strength and trauma resistance of these coating materials.
However, when a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof is added, there are problems that flexibility is poor and weather resistance is lowered.
In Patent Document 2, a hydrogenated product of a copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or a derivative thereof and a conjugated diene compound and a hydrogenated product of a copolymer of an aromatic vinyl compound and a conjugated diene compound are disclosed. Since a large amount of the product is contained, there are disadvantages that it is hard, has low tensile elongation, and has poor fluidity.
JP 2000-143935 A Japanese Patent No. 3047911

  The present invention solves the above-mentioned problems, particularly excellent in flexibility and weather resistance, and has excellent flame retardancy, heat deformability, mechanical properties, and landfill, combustion under inappropriate conditions and Providing flame retardant resin compositions and molded articles that respond to recent environmental problems without elution of heavy metal compounds, generation of a large amount of smoke and harmful gases at the time of disposal such as combustion without exhaust treatment facilities For the purpose.

  The inventors of the present invention have proposed that hydrogen of a copolymer of an aromatic vinyl compound modified with a specific amount of an ethylene copolymer, a specific amount of a polypropylene resin, a specific amount of an unsaturated carboxylic acid or a derivative thereof and a conjugated diene compound. Additives, specific amounts of organic peroxides, specific amounts of (meth) acrylate and / or allylic crosslinking aids, specific amounts of metal hydrates and, if necessary, specific amounts of aromatic vinyl compounds and conjugated diene compounds It has been found that a composition comprising a hydrogenated product of a copolymer with the above becomes an insulating resin composition and a molded part having excellent flexibility, weather resistance, mechanical strength, and flame retardancy. . The present invention has been completed based on this finding.

That is, the present invention
(1) (a1) ethylene / α-olefin copolymer, (a2) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer, (A3) 20 to 96.5% by mass of at least one polymer selected from (a1) to (a3) of ethylene / propylene copolymer rubber, (b) a copolymer of an aromatic vinyl compound and a conjugated diene compound 0 to 36.5% by mass of hydrogenated product, (c) 3 to 50% by mass of polypropylene resin, and (d) Copolymerization of aromatic vinyl compound modified with unsaturated carboxylic acid or derivative thereof and conjugated diene compound For 100 parts by mass of the thermoplastic resin component (A) containing 0.5 to 25% by mass of the combined hydrogenated product (provided that component (b) + component (d) is 37% by mass or less), ) Organic peroxide 0.001-1 part by mass, (f) (meth) acrylate-based and / or allylic crosslinking aid 0.03-2.5 parts by mass, and metal hydrate (B) 50-300 parts by mass Part of the metal hydrate (B),
(I) When the metal hydrate (B) is 50 parts by mass or more and less than 100 parts by mass, the metal hydrate pretreated with a silane coupling agent with respect to 100 parts by mass of the thermoplastic resin component (A) 25 parts by mass or more of the product;
(Ii) When the metal hydrate (B) is 100 parts by mass or more and 300 parts by mass or less, at least 1/4 of the metal hydrate (B) is pre-treated with a silane coupling agent. A flame retardant resin composition, which is a mixture of a composition, which is heated and kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A) and partially crosslinked in the presence of an organic peroxide. Stuff,
(2) The crosslinking aid (f) has the general formula

(Here, R is H or CH ₃ , and n is an integer of 1 to 9.)
A flame retardant resin composition according to item (1), which is a (meth) acrylate-based crosslinking aid represented by
(3) The flame retardant resin composition according to (1) or (2), wherein the metal hydrate (B) is magnesium hydroxide,
(4) The silane coupling agent is a silane compound having one type selected from the group consisting of a vinyl group, a (meth) acryloyl group, an amino group, and an epoxy group at the terminal. The flame retardant resin composition according to any one of (3),
(5) The flame-retardant resin composition according to any one of (1) to (4) is provided as a coating layer on the outside of a conductor, an optical fiber, or / and an optical fiber. Molded articles,
(6) A molded part formed by molding the flame-retardant resin composition according to any one of (1) to (4),
(7) (a1) ethylene / α-olefin copolymer, (a2) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer ( a3) at least one polymer selected from the group consisting of (a1) to (a3) of ethylene / propylene copolymer rubber, (b) a hydrogenated product of a copolymer of an aromatic vinyl compound and a conjugated diene compound, (C) a polypropylene resin, (d) a hydrogenated product of a copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or a derivative thereof and a conjugated diene compound, (e) an organic peroxide, (f) (meta ) Acrylic and / or allylic crosslinking aid and metal hydrate (B) are simultaneously heated and kneaded at a temperature equal to or higher than the melting temperature of the resin components (a) to (f). Method for producing a flame-retardant resin composition according to any one of which comprises treating (1) to (4), and,
(8) As a first step, (b) hydrogenated copolymer of aromatic vinyl compound and conjugated diene compound, (c) polypropylene resin, (a1) ethylene / α-olefin copolymer, (a2) ethylene -From (a1) to (a3) of vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer, (a3) ethylene / propylene copolymer rubber At least one polymer selected from the group consisting of (d) a hydrogenated product of a copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or a derivative thereof and a conjugated diene compound, After obtaining the plastic resin component (A), in the second step, the resin component (A) and (e) an organic peroxide, (f) a (meth) acrylate-based and / or allyl-based crosslink Any one of (1) to (4), wherein the agent and the metal hydrate (B) are heated and kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A) and partially crosslinked. A method for producing the flame retardant resin composition according to Item,
Is to provide.

  The flame-retardant resin composition of the present invention and a molded article using the flame-retardant resin composition are particularly excellent in flexibility and weather resistance, have excellent flame retardancy and mechanical properties, and are used for landfill and in inappropriate conditions. At the time of disposal such as combustion or combustion without exhaust treatment facilities, there is no elution of heavy metal compounds, large amounts of smoke, and no harmful gases.

Hereinafter, the present invention will be described in detail.
First, each component of the flame retardant resin composition of the present invention will be described.
(A) Thermoplastic resin component The thermoplastic resin component (A) is: (a1) ethylene / α-olefin copolymer, (a2) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer Or ethylene- (meth) acrylic acid ester copolymer, (a3) at least one polymer selected from the group consisting of ethylene / propylene copolymer rubbers, and (b) a copolymer of an aromatic vinyl compound and a conjugated diene compound. A hydrogenated product of a polymer, (c) a polypropylene resin, and (d) a hydrogenated product of a copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or a derivative thereof and a conjugated diene compound. However, the said (b) component can be not included as needed.

(A1) Component Ethylene / α-Olefin Copolymer As the (a1) component of the present invention, an ethylene / α-olefin copolymer is used. The ethylene / α-olefin copolymer (a1) is preferably a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms. Specific examples of the α-olefin include 1-butene, 1- Examples include hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and 1-dodecene.
Examples of ethylene / α-olefin copolymers include LLDPE (linear low density polyethylene), LDPE (low density polyethylene), VLDPE (very low density polyethylene), EBR (ethylene 1-butene rubber), and metallocene catalysts. And an ethylene / α-olefin copolymer synthesized in the above. Among these, an ethylene / α-olefin copolymer synthesized in the presence of a metallocene catalyst is preferable.

The density of the ethylene · alpha-olefin copolymer (a1) is preferably 925 kg / ^{m 3} or less, more preferably 915 kg / ^{m 3} or less, particularly preferably 905 kg / ^{m 3} or less. This is because when the density is high, it becomes difficult to fill the metal hydrate with a high degree, resulting in a problem that the flexibility of the resin composition and the wiring material covering the resin composition is lowered. There is no particular limitation on the lower limit of the density, but usually the lower limit is about 850 kg / m ³ .
The ethylene / α-olefin copolymer (a1) preferably has a melt flow rate (hereinafter referred to as MFR) (ASTM D-1238) of 0.5 to 30 dg / min.

Examples of the ethylene / α-olefin copolymer in the present invention include those synthesized in the presence of a metallocene catalyst, ordinary linear low-density polyethylene, and ultra-low-density polyethylene. Among them, in the presence of a metallocene catalyst. What is synthesized is preferable, and a known method described in JP-A-6-306121, JP-A-7-500622 or the like can be used as the production method.
The metallocene catalyst is also called a Kaminsky catalyst from the name of the inventor and a single site catalyst because of its single polymerization active site, and one having a high polymerization activity is commercialized. An ethylene / α-olefin copolymer synthesized using a single-site metallocene catalyst has a narrow molecular weight distribution and composition distribution.

Since the ethylene / α-olefin copolymer synthesized in the presence of such a metallocene catalyst has high tensile strength, tear strength, impact strength, etc., it is a non-halogen flame retardant that requires high filling of metal hydrates When used as a material (a covering material for a wiring material), there is an advantage that a decrease in mechanical properties due to a highly filled metal hydrate can be reduced.
On the other hand, when an ethylene / α-olefin copolymer synthesized using a metallocene catalyst is used, compared to the case of using a normal ethylene / α-olefin copolymer, an increase in melt viscosity or a decrease in melt tension occurs, Problems arise in moldability. In this regard, long chain branching is introduced using an asymmetric catalyst as a metallocene catalyst (Constrained Geometry Catalytic Technology), or two polymerization vessels are connected during synthesis to form two peaks in the molecular weight distribution (Advnced). Some have improved the molding processability by (PerformanceTerpolymer).

  As the ethylene / α-olefin copolymer (a1) used in the present invention, an ethylene / α-olefin copolymer synthesized in the presence of a metallocene catalyst is preferable, and among them, those having improved moldability are preferable. . Examples of such products include “Kernel” (trade name) and Mitsui Chemicals “Evolue” (trade name) from Nippon Polyethylene.

Component (a2) At least one of ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer As component (a2) of the present invention, ethylene -Vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer (for example, ethylene-butyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene -Methyl acrylate copolymer, ethylene-methyl methacrylate copolymer, etc.) are used. Among these, in order to further improve the flame retardancy, it is preferable to use an ethylene-vinyl acetate copolymer.

  In order to further improve the flame retardancy, the content of copolymerization components other than ethylene is preferably 23% by mass or more, more preferably 25% by mass or more, and further preferably 28% by mass or more. For example, in the case of an ethylene-vinyl acetate copolymer, a vinyl acetate (VA) component content of 23% by mass or more is preferable. The MFR is preferably 0.3 dg / min or more from the viewpoint of fluidity and 30 dg / min or less from the viewpoint of strength retention.

Component (a3) Ethylene-propylene copolymer rubber The ethylene-propylene copolymer rubber (EPM) used for the base resin in the flame-retardant thermoplastic resin composition of the present invention is a rubber-like copolymer of ethylene and propylene. It is. Here, the ethylene / propylene copolymer rubber is one having an ethylene component content of usually about 40 to 75% by mass. There is an ethylene-propylene terpolymer (EPDM) in which a repeating unit having an unsaturated group is added to a polymer as a third component other than ethylene and propylene, but in the present invention, it is necessary to use an EPM having no double bond. . This is because when EPDM is used, the excellent flexibility and elongation, which are the objects of the present invention, are impaired. EPM may be used alone or in combination of two or more.

The ethylene component content in the ethylene-propylene copolymer rubber is suitably 85 to 40% by mass. Preferably it is 80-45 mass%, More preferably, it is 75-50 mass%. If the ethylene component content is too small, the resulting resin composition is insufficiently flexible, and if it is too much, the mechanical strength is lowered.
The Mooney viscosity, ML _{1 + 4} (100 ° C.) of the ethylene-propylene copolymer rubber is preferably 10 to 120, more preferably 40 to 100. When the Mooney viscosity is less than 10, the rubber elasticity of the resulting elastomer composition may be inferior. Moreover, when a product exceeding 120 is used, the moldability may be deteriorated, and the appearance of the molded product is deteriorated.

The weight average molecular weight of the ethylene-propylene copolymer rubber used is preferably 50,000 to 1,000,000, more preferably 70,000 to 500,000. When the weight average molecular weight is less than 50,000, the resulting composition may be inferior in rubber elasticity. In addition, when a polymer having a weight average molecular weight exceeding 1,000,000 is used, the molding processability is deteriorated and the appearance of the molded product may be deteriorated.
0-50 mass% is preferable in a thermoplastic resin component (A), and, as for the compounding quantity of ethylene-propylene copolymer rubber ((a3) component), More preferably, it is 5-35 mass%. When the upper limit is exceeded, the mechanical strength is reduced.

In the flame-retardant resin composition of the present invention, at least one of the components (a1) to (a3) is used, and these may be used alone or in combination.
However, the sum total of (a1)-(a3) component is 20-96.5 mass% in a thermoplastic resin component (A), Preferably, it is 30-90 mass%, More preferably, it is 40-85 mass%.

Component (b) Hydrogenated product of copolymer of aromatic vinyl compound and conjugated diene compound Component (b) of the present invention is a hydrogenated product of a copolymer of conjugated diene compound and aromatic vinyl compound. Examples of the aromatic vinyl compound include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-p-aminoethylstyrene, vinyl. There are toluene, p-tert-butylstyrene, etc., among which styrene is preferable.

Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and one or more types are selected. Among them, butadiene, isoprene, and these The combination of is preferable.
Moreover, the thing in which at least 90% of the aliphatic double bond based on a conjugated diene compound was hydrogenated is preferable.
The content of the aromatic vinyl compound is preferably 60% by mass or less, more preferably 45% by mass or less in the component (b). If this amount is too large, the flexibility is significantly reduced.

  The weight average molecular weight of the (hydrogenated) 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, and still more preferably 100,000. ˜550,000, particularly preferably in the range of 10,000 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, and more preferably 3 or less. The molecular structure of the (hydrogenated) copolymer may be linear, branched, radial, or any combination thereof.

When the component (b) + (d) exceeds 37% by mass in the thermoplastic resin component (A), the resulting composition becomes hard and the fluidity also deteriorates. At that time, it is necessary that the component (b) is 0 to 36.5% by mass and the component (d) is 0.5 to 25% by mass in the thermoplastic resin component (A).
In this invention, the compounding quantity of (b) component is 0-36.5 mass% in a thermoplastic resin component (A), Preferably it is 0.5-36 mass parts, More preferably, it is 1-36 mass parts. When the component (b) exceeds the upper limit, it becomes hard or has low fluidity.

(C) Polypropylene resin Examples of the polypropylene resin that can be used in the present invention include homopolypropylene, propylene / ethylene random copolymer, propylene / ethylene block copolymer, propylene and other small amounts of α-olefin (for example, 1- Butene, 1-hexene, 4-methyl-1-pentene, etc.).
Among these, the random copolymer is a copolymer obtained by randomly copolymerizing monomers such as propylene and ethylene, and is generally 0.5 to 10% by mass in terms of mass%. The block copolymer is a mixture of a crystalline polypropylene component and a polyolefin copolymer rubber, and a product of 0.5 to 50% by mass in terms of mass% is common. Among them, the one with a lot of rubber is also called a reactor TPO.

When the thermoplastic resin component (A) is heat-kneaded and produced as a partially crosslinked product in the present invention, a part of the polypropylene resin as the component (c) can be blended after heat-kneading.
The polypropylene resin blended in (A) before heat-kneading is thermally decomposed by the presence of component (e) and moderately reduced in molecular weight by subsequent heat-kneading.

As the polypropylene resin to be blended before heating and kneading, MFR (ASTM-D-1238, L condition, 230 ° C.) is preferably 0.1 to 10 dg / min, more preferably 0.1 to 5 dg / min, further preferably 0.1-3 dg / min is used.
When the MFR of the polypropylene resin is less than 0.1 dg / min, the molecular weight of the polypropylene resin is not sufficiently lowered even after the heat treatment, and the moldability of the resulting resin composition may be deteriorated, while the MFR is 10 dg / min. If it exceeds, the molecular weight becomes too low and the rubber elasticity of the resulting resin composition may deteriorate.

The polypropylene resin to be blended after heating and kneading only needs to meet the extrusion conditions for forming the coating layer, and the MFR is preferably 5 to 200 dg / min, more preferably 8 to 150 dg / min, Preferably, 10 to 100 dg / min is used.
When blended after heating and kneading, if the MFR of the polypropylene resin is less than 5 dg / min, the moldability of the resulting resin composition may be deteriorated. If the MFR exceeds 200 dg / min, the rubber elasticity of the obtained resin composition may be deteriorated. May get worse.

  (C) The compounding quantity of a component is 3-50 mass% in (A), Preferably it is 5-45 mass%, More preferably, it is 10-45 mass%. If the amount of component (c) is too large, the wire will be extremely hard and secondary processing will be difficult, and elongation will be significantly reduced. If it is too small, the stress cracking property will be reduced, and the heat resistance will be reduced. To do.

Component (d) Hydrogenated product of copolymer of aromatic vinyl compound modified with unsaturated carboxylic acid or derivative thereof and conjugated diene compound Aromatic vinyl compound modified with unsaturated carboxylic acid or derivative thereof and conjugated diene The hydrogenated product of the copolymer with the compound includes a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, and an unsaturated carboxylic acid or derivative thereof (hereinafter referred to as a hydrogenated product of a random copolymer). These are combined and referred to as unsaturated carboxylic acid etc.). Here, in the copolymer, the aromatic vinyl compound component and the conjugated diene compound component are 60% by mass or more, preferably 90% by mass or more of the whole.

  Examples of the unsaturated carboxylic acid used for modification include maleic acid, itaconic acid, fumaric acid, (meth) acrylic acid and the like, and examples of the unsaturated carboxylic acid derivative include maleic acid monoester, maleic acid diester, Mention may be made of maleic anhydride, itaconic acid monoester, itaconic acid diester, itaconic anhydride, fumaric acid monoester, fumaric acid diester, fumaric anhydride and the like. These modifications can be performed by, for example, heating and kneading a hydrogenated copolymer of an aromatic vinyl compound and a conjugated diene compound, an unsaturated carboxylic acid, and the like in the presence of an organic peroxide. The amount of modification with maleic acid is usually about 0.1 to 15% by mass.

  In the flame-retardant resin composition of the present invention, the hydrogenated product of a copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or derivative thereof and a conjugated diene compound has an elongation of the resulting resin composition. As well as increasing the strength, the strength can be maintained, and the volume resistivity can be kept high. In the case of a polyolefin resin modified with an unsaturated carboxylic acid or derivative thereof by using a hydrogenated product of a copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or derivative thereof and a conjugated diene compound. Unlike the above, the strength can be improved while maintaining flexibility. In addition, when a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof is used, the weather resistance is lowered. However, a copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or a derivative thereof and a conjugated diene compound is used. If a combined hydrogenated product is used, it is possible to improve strength and elongation while maintaining weather resistance.

  In addition, hydrogenated products of copolymers of aromatic vinyl compounds and conjugated diene compounds modified with unsaturated carboxylic acids or their derivatives prevent the deterioration of mechanical properties caused by metal hydrates and prevent whitening of wires. There is also an effect.

When the component (b) + (d) exceeds 37 mass% in the thermoplastic resin component (A), the fluidity of the resulting composition is deteriorated and hardened. At that time, it is necessary that the component (b) is 0 to 36.5% by mass and the component (d) is 0.5 to 25% by mass in the thermoplastic resin component (A).
In (A), the amount of component (d) is 0.5 to 25% by mass, preferably 1% by mass or more and less than 15% by mass, more preferably 1% by mass or more and 12% by mass or less. If the blending amount of component (d) exceeds the upper limit, the tensile elongation and flexibility may be lowered, and further, the extrusion characteristics of the electric wire may be significantly lowered.

(E) Component Organic peroxide Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butyl peroxide). Oxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylper) Oxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxy Isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and the like tert- butyl cumyl peroxide.

Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di- in terms of odor, colorability, and scorch stability. (Tert-Butylperoxy) hexyne-3 is most preferred.
The compounding quantity of organic peroxide (e) is the range of 0.001-1.0 mass part with respect to 100 mass parts of thermoplastic resin components (A), Preferably 0.01-0.5 mass part It is. By selecting the organic peroxide within this range, the crosslinking does not proceed excessively, so that a partially crosslinked composition excellent in extrudability can be obtained without generating scum.

(F) Component (Meth) acrylate-based and / or allyl-based crosslinking aid In the production of the flame-retardant resin composition of the present invention or the thermoplastic resin component (A) used therein, crosslinking aid is present in the presence of an organic peroxide. A partially crosslinked structure is formed between components (a-1), (a-2), (a-3), (b), and (d) through the agent. As the crosslinking aid used at that time, the general formula

(Here, R is H or CH ₃ , and n is an integer of 1 to 9.)
The (meth) acrylate type crosslinking adjuvant represented by these is mentioned. Here, the (meth) acrylate-based crosslinking aid refers to an acrylate-based and methacrylate-based crosslinking aid. Specific examples include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate.
In addition, those having an allyl group at the terminal such as diallyl fumarate, diallyl phthalate, tetraallyloxyethane, and triallyl cyanurate can be used.

  Among these, a (meth) acrylate-based crosslinking assistant having n of 1 to 6 is particularly preferable, and examples thereof include ethylene glycol diacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate.

  In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle, has good compatibility with other components, has a peroxide solubilizing action, and acts as a dispersion aid for peroxide. The cross-linking effect at the time of kneading is most preferable because it provides a uniform and effective cross-linking thermoplastic resin having a balance between hardness and rubber elasticity. By using such a compound, it is possible to expect a uniform and efficient partial crosslinking reaction at the time of heating and kneading without being insufficiently crosslinked or excessively crosslinked.

  The amount of the crosslinking aid used in the present invention is preferably in the range of 0.03 to 2.5 parts by mass, more preferably 0.05 to 1.1, with respect to 100 parts by mass of the thermoplastic resin component (A). 6 parts by mass. By selecting the crosslinking aid within this range, a partially crosslinked structure having a low crosslinking density is obtained without excessive crosslinking, and a composition excellent in extrudability is obtained without generation of blisters. The blending amount of the crosslinking aid is preferably about 1.5 to 4.0 times the addition amount of the organic peroxide by mass ratio.

  By adding the peroxide of component (e) and the crosslinking aid of component (f), partial crosslinking occurs during kneading, and heat resistance comparable to PVC can be maintained. Furthermore, by producing a direct bond between the component (a) and the component (b) and a bond via the crosslinkable silane coupling agent of the component (B), high strength and trauma resistance are obtained. The terminal processability can be maintained. In particular, when the component (b) is added to the cross-linking component, excellent terminal processability can be obtained in the case of, for example, a cord or an electric wire for equipment, while obtaining the same appearance as PVC. (B) By mix | blending a component, it can have the same slipperiness as a PVC electric wire, and also in an automatic processing machine, processing becomes possible by the process prescription equivalent to PVC.

(B) Metal Hydrate The metal hydrate used in the present invention is not particularly limited. For example, aluminum hydroxide, magnesium hydroxide, hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, A compound having a hydroxyl group or crystal water such as hydrotalcite can be used alone or in combination of two or more. Of these metal hydrates, aluminum hydroxide and magnesium hydroxide are preferred. Metal hydrate must be at least partially treated with a silane coupling agent, but is not surface-treated untreated metal hydrate or metal water treated with other surface treatment agents such as fatty acids A Japanese thing can be used together suitably.

  Examples of the silane coupling agent used for the surface treatment of the metal hydrate include vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, and glycidoxypropylmethyl. Silane coupling agents terminated with vinyl or epoxy groups such as dimethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane Silane coupling agent having a terminal mercapto group such as aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-amino A crosslinkable silane coupling agent such as a silane coupling agent having an amino group such as propyltripropyltrimethoxysilane and N- (β-aminoethyl) -γ-aminopropyltripropylmethyldimethoxysilane is preferred. Two or more of these silane coupling agents may be used in combination.

  Among such silane coupling agents, silane coupling agents having an epoxy group and / or vinyl group, (meth) acryloyl group, and amino group at the terminal are preferable, and an epoxy group and / or vinyl group at the terminal (meta) ) Those having an acroyl group are preferred. These may be used alone or in combination of two or more.

As the silane coupling agent surface-treated magnesium hydroxide that can be used in the present invention, non-surface-treated ones (Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd.), stearic acid, oleic acid, etc. are commercially available. Surface treated with fatty acid (Kisuma 5A (trade name, manufactured by Kyowa Chemical Co., Ltd.)), phosphoric acid ester treated surface treated with the above silane coupling agent, or already with silane coupling agent There are commercially available products of surface-treated magnesium hydroxide (Kisuma 5L, Kisuma 5P (both trade names, manufactured by Kyowa Chemical Co., Ltd.), etc.) and Fine Mag MO-E (trade names, manufactured by TMG).
In addition to the above, a silane coupling having a functional group such as a vinyl group or an epoxy group at its terminal in addition to magnesium hydroxide or aluminum hydroxide whose surface is partially pretreated with a fatty acid or a phosphate ester. It is also possible to use a metal hydrate that has been surface-treated with an agent.

  When treating a metal hydrate with a silane coupling agent, it is necessary to blend the silane coupling agent with the metal hydrate in advance. At this time, the silane coupling agent is appropriately added in an amount sufficient for the surface treatment, and specifically, 0.2 to 2% by mass with respect to the metal hydrate is preferable. The silane coupling agent may be a stock solution or may be diluted with a solvent.

The compounding quantity of a metal hydrate is 50-300 mass parts with respect to 100 mass parts of thermoplastic resin components (A) in the resin composition of this invention. In the present invention, when (i) the metal hydrate is 50 parts by mass or more and less than 100 parts by mass, 25 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin component (A), and (ii) metal hydration When the product is 100 parts by mass or more, it is possible to obtain a material with excellent flexibility while maintaining high strength by making at least 1/4 of the metal hydrate pretreated with a silane coupling agent. become.
Furthermore, although it is 50-300 mass parts with respect to 100 mass parts of thermoplastic resin components (A), More preferably, (i) When a metal hydrate is 50 mass parts or more and less than 100 mass parts, a thermoplastic resin 25 parts by mass or more with respect to 100 parts by mass of component (A), and (ii) when the metal hydrate is 100 parts by mass or more and 300 parts by mass or less, at least 1/2 of the amount is a silane coupling agent. By using a pretreated metal hydrate, it is possible to obtain a material and an electric wire that are also excellent in resistance to trauma, high in strength and excellent in end workability.

  When polyolefin resin such as normal polyethylene resin or polypropylene resin is used as the base resin and a large amount of metal hydrate is added to satisfy the required flame retardancy, the mechanical strength is greatly reduced. . On the other hand, the thermoplastic resin component (A) in the present invention is excellent in filler acceptability because the resin component is in a partially crosslinked state via the component (f) because the crosslinking density is low, and such thermoplasticity. When the resin component (A) is used as a base resin, a large amount of metal hydrate can be blended. Among them, only when a specific amount of a metal hydrate treated with a silane coupling agent is blended, the base resin of component (A) and the metal hydrate of component (B) interact through the silane coupling agent. Therefore, a decrease in mechanical strength is suppressed to a minimum, whitening hardly occurs when bent, and satisfactory characteristics can be obtained as a coating material for a wiring material, a molded part, or the like.

  The details of the reaction mechanism during heating and kneading of the resin composition of the present invention are not yet clear, but are considered as follows. That is, when the thermoplastic resin component (A) in the present invention is heated and kneaded, in the presence of the component (e), the components (a1) to (a3), (b), (d) ) Component is crosslinked. On the other hand, the melt viscosity of the resin composition can be appropriately adjusted by appropriately reducing the molecular weight of the component (c) by the action of the component (e). As a result, the composition as a whole becomes a crosslinked product having excellent extrudability. The crosslinking of the composition of the present invention may be carried out in the presence of a small amount of the component (e), and can be referred to as partial crosslinking because it has fewer crosslinking points than ordinary crosslinking.

The degree of cross-linking of the flame retardant resin composition can be represented by the gel fraction of the thermoplastic resin component (A) as a guide. The gel fraction can be expressed as a ratio of the mass of residual solid to 1 g of sample after wrapping 1 g of sample in a 100 mesh wire net and extracting it in boiling xylene using a Soxhlet extractor for 10 hours.
In the present invention, the degree of crosslinking is preferably 30 to 45% by mass, more preferably 40 to 45% by mass, in terms of gel fraction.

  When filling a thermoplastic resin component (A) with a metal hydrate, when a specific amount of a metal hydrate treated with a silane coupling agent is blended simultaneously with the components (e) and (f) As long as it becomes possible to mix a large amount of metal hydrate without impairing the extrusion processability at the time of molding, it has high heat resistance and mechanical properties while having high flame retardancy and flexibility, A flame-retardant resin composition that can be re-extruded after use and can be recycled can be obtained.

  The details of the mechanism of the action of the metal hydrate treated with the silane coupling agent are not yet clear, but are considered as follows. In other words, the silane coupling agent bonded to the surface of the metal hydrate by treating with the silane coupling agent has one alkoxy group bonded to the metal hydrate and the vinyl group or epoxy group present at the other end. Various reactive sites including the first bond to the uncrosslinked portions of the components (a1) to (a3), the component (b), and the component (d). This makes it possible to blend a large amount of metal hydrate without impairing the extrusion moldability, strengthen the adhesion between the resin and the metal hydrate, and have good mechanical strength and wear resistance. A flame-retardant resin composition that is not easily damaged is obtained.

  When this crosslinking is performed, it is possible to amplify the strength by blending a resin modified with an unsaturated carboxylic acid or a derivative thereof, but the problem is that the weather resistance is lowered or the flexibility is significantly lowered. There is. By blending the base material with a hydrogenated copolymer of an aromatic vinyl compound and a conjugated diene compound modified with a specific amount of the unsaturated carboxylic acid or derivative thereof according to the present invention, the strength is maintained while maintaining elongation. It is possible to amplify and maintain weather resistance and flexibility. Also, by blending a hydrogenated product of a copolymer of an aromatic vinyl compound and a conjugated diene compound modified with this specific amount of unsaturated carboxylic acid or derivative thereof, the function of greatly improving the end cutting property of the electric wire There is. The effect of improving weather resistance is particularly remarkable when polypropylene is used as the base material, and high weather resistance can be maintained.

In the present invention, flame retardancy can be improved by adding melamine cyanurate.
The melamine cyanurate compound used in the present invention preferably has a fine particle size. The average particle size of the melamine cyanurate compound used in the present invention is preferably 10 μm or less, more preferably 7 μm or less, and even more preferably 5 μm or less. Moreover, the melamine cyanurate compound surface-treated from the dispersible surface is used preferably.

Examples of the melamine cyanurate compound that can be used in the present invention include MCA-0 and MCA-1 (both trade names, manufactured by Mitsubishi Chemical Corporation) and those marketed by Chemie Linz Gmbh. Examples of the melamine cyanurate compound surface-treated with fatty acid and the melamine cyanurate compound surface-treated with silane include MC610 and MC640 (both are trade names, manufactured by Nissan Chemical Co., Ltd.).
Examples of the melamine cyanurate compound that can be used in the present invention include melamine cyanurate having the following structure.

  In this invention, the compounding quantity of a melamine cyanurate compound is 3-70 mass parts with respect to 100 mass parts of thermoplastic resin components (A), Preferably it is 5-40 mass parts. If the amount of the melamine cyanurate compound is too small, the effect of improving the flame retardancy will not be exhibited. If the amount is too large, the mechanical strength, in particular, the elongation will decrease, and the appearance of the electric wire will deteriorate.

  The flame retardant resin composition of the present invention can be blended with at least one selected from the group consisting of zinc borate, zinc stannate, and zinc hydroxystannate, if necessary, to further improve flame retardancy. be able to. By using these compounds, the speed of shell formation during combustion is increased and the shell formation becomes stronger. Therefore, together with the melamine cyanurate compound that generates gas from the inside during combustion, the flame retardancy can be dramatically improved and a high level of flame retardancy can be imparted.

Zinc borate, zinc stannate, and zinc hydroxystannate used in the present invention preferably have an average particle size of 5 μm or less, more preferably 3 μm or less.
As zinc borate which can be used in the present invention, specifically, for example, alk Nex _{FRC-500 (2ZnO / 3B 2} O 3 · 3.5H 2 O), FRC-600 ( trade names, manufactured by Mizusawa Chemical Co. Etc.). 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 present invention, the compounding amount of zinc borate, zinc stannate or zinc hydroxystannate is 0.5 to 20 parts by mass, preferably 2 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin component (A). . If the amount is too small, the effect of improving the flame retardancy will not be exhibited. If the amount is too large, the mechanical strength, particularly the elongation will be reduced, and the appearance of the electric wire will be deteriorated.

  In the flame-retardant resin composition of the present invention, various additives commonly used in electric wires, cables, cords, tubes, electric wire components, sheets, etc., for example, antioxidants, metal deactivators, Flame retardant (auxiliary) agents, fillers, lubricants, and the like can be appropriately blended within a range that does not impair the object of the present invention.

  Antioxidants include amine-based antioxidants such as 4,4′-dioctyl diphenylamine, N, N′-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline polymer. Agent, pentaerythrityl-tetrakis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate , 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like, bis (2-methyl-4- ( 3-n-alkylthiopropionyloxy) -5-tert-butylphenyl) sulfide, 2-mercaptoben ヅ imidazole and its zinc salt, pentaerythritol Lithol - tetrakis (3-lauryl - thiopropionate) and the like sulfur-based antioxidant such.

  Examples of metal deactivators include N, N′-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1,2,4. -Triazole, 2,2'-oxamidobis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like.

  In addition, flame retardants (auxiliaries) 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 For example, carbon.

In particular, silicone compounds such as silicone rubber and silicone oil not only impart and improve flame retardancy, but also in insulators (coating layers comprising the flame retardant resin composition) and conductors in electric wires and cords. The cable has an effect of reducing trauma by controlling the adhesion force of the cable and imparting lubricity to the cable. Specific examples of the silicone compound used in the present invention include commercially available products such as “SFR-100” (trade name, manufactured by GE) and “CF-9150” (trade name, manufactured by Toray Dow Silicone). Is mentioned.
When added, the silicone compound is preferably blended in an amount of 0.5 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin component (A). If the amount is less than 0.5 parts by mass, there is substantially no effect on the flame retardancy and lubricity, and if it exceeds 5 parts by mass, the appearance of the electric wire, cord, and cable is reduced, and the extrusion speed is reduced, resulting in mass productivity. May get worse.
Examples of the lubricant include hydrocarbons, fatty acids, fatty acid amides, esters, alcohols, and metal soaps.

  In the flame-retardant resin composition of the present invention, the additive and other resins can be blended within a range that does not impair the object of the present invention, but at least the thermoplastic resin component (A) is a main resin component. To do. Here, the main resin component is usually 70% by mass or more, preferably 85% by mass or more, more preferably the total amount of the resin component in the resin component of the flame-retardant resin composition of the present invention. (A) means to occupy. Here, in the thermoplastic resin component (A), the components (a1) to (a3), (b), (c), and (d) each have a use amount within the specified range, and the thermoplastic resin component ( A) is 100% by mass in the total amount of components (a) to (d).

Hereinafter, the manufacturing method of the flame-retardant resin composition of this invention is demonstrated.
Add components (a) to (d), metal hydrate (B), components (e) and (f), and heat knead. The kneading temperature is preferably 160 to 240 ° C. The kneading conditions such as kneading temperature and kneading time are such that the resin components (a) to (d) are melted and the organic peroxide acts to achieve the necessary partial crosslinking. It can be set as appropriate to an extent sufficient. The kneading method can be satisfactorily used as long as it is a method usually used for rubber, plastic and the like. As the apparatus, for example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer or various kneaders are used. By this step, a flame retardant resin composition in which each component is uniformly dispersed can be obtained.

  Of the metal hydrates to be blended, it is important that the metal hydrate treated with the silane coupling agent is previously treated with the silane coupling agent. By using a metal hydrate that has been surface-treated in advance, it becomes possible to formulate a sufficient amount of metal hydrate to ensure flame retardancy, and particularly good mechanical strength and wear resistance. Thus, a flame-retardant resin composition that is hardly damaged is obtained.

  As another method, the components (a) to (d) are first heated and kneaded in the first step to obtain the thermoplastic resin component (A). In the second step, the components (e), (f) and the metal hydrate (B) are added to the thermoplastic resin component (A) obtained in the first step, and the mixture is heated and kneaded. The temperature at this time is preferably 160 to 240 ° C. Also in this case, the kneading conditions such as kneading temperature and kneading time are such that the thermoplastic resin component (A) is melted and the contained organic peroxide is partially crosslinked. It can set suitably so that it may fully be used.

  As described above, the components (a) to (d) may be preliminarily heated and kneaded to be microdispersed, and then the components (e) and (f) may be added and heat kneaded. Also in this case, when the surface-treated metal hydrate is used, it is necessary to finish the surface treatment before blending.

The flame retardant resin composition of the present invention is suitable for coating and manufacturing of wiring parts, optical fiber cores, optical fiber cords and the like used for internal and external wiring of electric / electronic devices.
When the flame-retardant resin composition of the present invention is used as a coating material for a wiring material, it preferably comprises at least one layer of the flame-retardant resin composition of the present invention formed on the outer periphery of a conductor by extrusion coating. There is no restriction | limiting in particular except having a coating layer. For example, as the conductor, any known one such as an annealed copper single wire or stranded wire can be used. In addition to the bare wire, the conductor may be tin-plated or an enamel-covered insulating layer.

When the molded article of the present invention is a wiring material such as an electric wire, the flame retardant resin composition of the present invention is manufactured by extrusion coating around a conductor or an insulated wire using a general-purpose extrusion coating apparatus. be able to. The temperature of the extrusion coating apparatus at this time is preferably about 180 ° C. at the cylinder portion and about 200 ° C. at the crosshead portion.
In the wiring material of the present invention, the thickness of the insulating layer (the coating layer made of the flame-retardant resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 mm to 5 mm.

Moreover, in the wiring material of the present invention, it is preferable to form the coating layer as it is by extrusion coating the flame retardant resin composition of the present invention which is a partially crosslinked product, but for the purpose of further improving the heat resistance. It is also possible to crosslink the coating layer after extrusion. However, when this crosslinking treatment is performed, it becomes difficult to reuse the coating layer as an extruded material.
As a method for crosslinking, an electron beam irradiation crosslinking method or a chemical crosslinking method can be employed.

In the case of the electron beam crosslinking method, the flame retardant resin composition of the present invention is extruded to form a coating layer, and then crosslinked by irradiating an electron beam by a conventional method. An electron beam dose of 1 to 30 Mrad is appropriate, and in order to efficiently perform crosslinking, a flame retardant resin composition constituting a coating layer, a methacrylate compound such as trimethylolpropane triacrylate, triallyl cyanurate, etc. Polyfunctional compounds such as allyl compounds, maleimide compounds, and divinyl compounds may be added as a crosslinking aid.
In the case of the chemical crosslinking method, an organic peroxide is blended in the flame retardant resin composition as a crosslinking agent, extruded to form a coating layer, and then crosslinked by heat treatment according to a conventional method.

The shape of the molded part of the present invention is not limited, and examples thereof include a power plug, a connector, a sleeve, a box, a tape base material, a tube, and a sheet. The molded part of the present invention is molded from the flame retardant resin composition of the present invention by a molding method such as ordinary injection molding.
Sheets, tubes, and the like can be extruded in the same manner as the wire coating. Moreover, you may bridge | crosslink by a chemical crosslinking method or an electron beam crosslinking method similarly to an electric wire.
Further, when an injection molded product such as an electric wire part is obtained as the molded part of the present invention, it can be injection molded at a cylinder temperature of about 220 ° C. and a head temperature of about 230 ° C. The injection molding apparatus can be molded by using an injection molding machine used for molding a normal PVC resin or the like.

When the molded article of the present invention is an optical fiber core or an optical cord, a general-purpose extrusion coating apparatus is used around the optical fiber strand with the flame retardant resin composition of the present invention as a coating layer. Alternatively, it can be manufactured by extrusion coating around a fiber optic fiber lined or twisted with tensile strength fibers. The temperature of the extrusion coating apparatus at this time is preferably about 180 ° C. at the cylinder portion and about 200 ° C. at the crosshead portion.
The optical fiber core of the present invention is used as it is without providing a coating layer around it depending on the application.

  In addition, the optical fiber core wire or cord of the present invention includes all of the optical fiber strand or the core wire coated on the outer periphery with the flame retardant resin composition of the present invention as a coating layer, and its structure is particularly limited. Not what you want. The thickness of the coating layer and the type and amount of the tensile strength fiber that is vertically attached or twisted to the optical fiber core wire vary depending on the type and use of the optical fiber cord, and can be set as appropriate.

1-3 show an example of the structure of the optical fiber core and cord of the present invention.
FIG. 1 is a cross-sectional view of an example of an optical fiber core wire of the present invention in which a coating layer 2 made of a flame retardant resin composition is provided directly on the outer periphery of an optical fiber strand 1.
FIG. 2 is a cross-sectional view of an example of the optical fiber cord of the present invention in which a coating layer 5 is formed on the outer periphery of one optical fiber core wire 3 in which a plurality of tensile strength fibers 4 are vertically attached.
FIG. 3 shows an optical fiber cord of the present invention (optical fiber two-core cord) in which a plurality of tensile fibers 4 are vertically attached to the outer circumferences of two optical fiber cores 3 and 3, and a coating layer 6 is formed on the outer circumference. Is a cross-sectional view of an example.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these.
In addition, a number shows a mass part unless there is particular description.

Each component shown in Tables 1 to 3 was dry blended at room temperature and melt kneaded at 220 ° C. using a Banbury mixer to prepare a resin composition.
In Example 2, other than organic peroxide was dry blended, melt kneaded at 170 ° C. using a Banbury mixer, pelletized, and then mixed with organic peroxide at 220 ° C. using a biaxial extruder. A resin composition was prepared by kneading.
Using the obtained resin composition, a sheet having a thickness of 1 mm and 3 mm was prepared, and elongation (EL), tensile strength (TS), hardness, and specific gravity were measured based on JIS K 6723.

Next, in Table 1, using an extrusion coating apparatus for manufacturing electric wires, a conductor (conductor diameter: 0.95 mmφ tin-plated annealed copper stranded wire configuration: 30 pieces / 0.18 mmφ) for insulating coating previously melted is used. The resin composition was extrusion coated to produce an insulated wire having an outer diameter of 2.74 mm corresponding to each of the examples and comparative examples.
Also, in Tables 2 and 3, using an extrusion coating apparatus for manufacturing electric wires, a conductor (conductor diameter: 0.95 mmφ tin-plated annealed copper stranded wire configuration: 7 / 0.16 mmφ) is used for insulation coating previously melted. The resin composition was extrusion coated to produce an insulated wire having an outer diameter of 0.98 mm corresponding to each example and comparative example.

About each obtained insulated wire, the result of tensile characteristics, a weather resistance, a flame retardance (horizontal combustion test), a softness | flexibility, and an external appearance was combined with Tables 1-3, and was shown.
Tensile properties were determined by measuring the strength (tensile strength) (MPa) and elongation at break (%) of the insulator (coating layer) of each insulated wire under conditions of a marked line interval of 25 mm and a tensile speed of 500 mm / min. The elongation (EL) is required to be 100% or more, and the strength (TS) is required to be 10 MPa or more.

For the flame retardancy, each insulated wire was subjected to a horizontal combustion test specified in JIS C 3005, and the self-extinguishing within 30 seconds was accepted, and the non-extinguishing one was rejected within 30 seconds.
The weather resistance indicates the elongation residual ratio (EL residual ratio) and the tensile strength residual ratio (TS residual ratio) after 2000 hours exposure in a sunshine weather meter. The black panel temperature was 63 ° C. and no rain was evaluated.
In the flexibility test, the electric wire was cut to 120 mm after removing the conductor, a 20 g weight was attached to the tip, and the amount of deflection of the electric wire portion 100 mm was measured.

The following compounds were used as each compound shown in the table.
(EVA (VA = 33))
Manufacturer: Mitsui DuPont Polychemical Product name: EV-170
Type: ethylene / vinyl acetate copolymer; (a-2) component VA component content: 33% by mass
MFR: 1 dg / min (ME-PE (0.880))
Manufacturer: Japan Polyethylene Product Name: Kernel KF360
Type: metallocene polyethylene MFR: 3.5 dg / min, density: 898 kg / m ³ , comonomer: hexene-1
(B-PP)
Manufacturer: Idemitsu Petrochemicals Trade name: 150GK
Type: Block polypropylene Melting point: 160 ° C
MFR: 0.6 dg / min (MAH-SEBS)
Manufacturer: Kraton Polymer Japan, Inc. Brand name: 1901FX
Type: Maleic acid-modified styrene-ethylene-butene-styrene copolymer Maleic acid modification amount: 1.7% by mass
Styrene content: 28% by mass
MFR 22dg / min (200 ℃ / 5kg)
(MAH-PE)
Manufacturer: Mitsui Chemicals Product name: XE070
Type: Maleic acid-modified polyethylene Melting point: 87 ° C., MFR: 1.0 dg / min, density: 910 kg / m ³
(SEPS)
Manufacturer: Kuraray Product Name: SEPS 4077
Type: SEEPS
Styrene content: 30% by mass
Number average molecular weight: 260,000
Weight average molecular weight: 320,000
(OIL)
Manufacturer: Idemitsu Kosan Product name: Diana Process Oil PW-90
Type: Paraffin oil Weight average molecular weight: 540
Aromatic component content: 0.1% or less Dynamic viscosity (37.8 ° C.): 95 cSt
Pour point: -15 ° C
Flash point (COC): 270 ° C
(PE-WAX)
Manufacturer: Sakai Chemical Co., Ltd. Trade name: LBT-77
Type: Polyethylene wax (B) component (Kisuma 5P)
Manufacturer: Kyowa Chemical Product name: Kimas 5P
Type: Magnesium hydroxide already surface treated with silane coupling agent;
(T-111)
Manufacturer: Ciba Specialty Chemicals Brand name: Tinuvin 111
Type: Hindered amine light stabilizer (P-25B)
Manufacturing company: Japanese fats and oils
Type: 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane; (e) component (NK ester 3G)
Manufacturer: Shin-Nakamura Chemical Product name: NK Ester 3G
Type: Triethylene glycol dimethacrylate; (f) component (EP07P)
Manufacturer: JSR
Product name: EP07P
Type: Ethylene / propylene copolymer rubber (EPM)
Ethylene component content: 73% by mass
Mooney viscosity, ML _{1 + 4} (100 ° C.): 70
(EL-45LX)
Manufacturer: Mitsui DuPont Polychemical Product name: EV45LX
Type: Ethylene vinyl acetate copolymer (VA content 45%)
MFR: 2.5 dg / min

  As can be seen from Tables 1 to 3, the electric wires of Comparative Examples 1, 2, 4 and 5 were inferior in the weather resistance EL residual ratio and flexibility. In Comparative Example 3, it was hard and the EL was inferior. Moreover, in the electric wires of Comparative Examples 6 and 7, the required strength could not be satisfied. On the other hand, it can be seen that the electric wires of the examples are all excellent in tensile properties, weather resistance, flame retardancy, and flexibility.

It is sectional drawing of an example of the optical fiber core wire of this invention. It is sectional drawing of an example of the optical fiber cord of this invention. It is sectional drawing of an example of the optical fiber cord (optical fiber 2 core cord) of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical fiber strand 2 Coating layer 3 Optical fiber core wire 4 Tensile fiber 5 Coating layer 6 Coating layer

Claims (8)

(A1) ethylene / α-olefin copolymer, (a2) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer, (a3) 20 to 96.5% by mass of at least one polymer selected from the group consisting of (a1) to (a3) of ethylene / propylene copolymer rubber, (b) a copolymer of an aromatic vinyl compound and a conjugated diene compound 0 to 36.5% by mass of hydrogenated product, (c) 3 to 50% by mass of polypropylene resin, and (d) Copolymerization of aromatic vinyl compound modified with unsaturated carboxylic acid or derivative thereof and conjugated diene compound To 100 parts by mass of thermoplastic resin component (A) containing 0.5 to 25% by mass of combined hydrogenated product (provided that component (b) + component (d) is 37% by mass or less) (E) 0.001 to 1 part by mass of organic peroxide, (f) 0.03 to 2.5 parts by mass of (meth) acrylate-based and / or allylic crosslinking aid, and metal hydrate (B) 50 ~ 300 parts by mass of the metal hydrate (B),
(I) When the metal hydrate (B) is 50 parts by mass or more and less than 100 parts by mass, the metal hydrate pretreated with a silane coupling agent with respect to 100 parts by mass of the thermoplastic resin component (A) 25 parts by mass or more of the product;
(Ii) When the metal hydrate (B) is 100 parts by mass or more and 300 parts by mass or less, at least 1/4 of the metal hydrate (B) is pre-treated with a silane coupling agent. A flame retardant resin composition, which is a mixture of a composition, which is heated and kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A) and partially crosslinked in the presence of an organic peroxide. Stuff. The crosslinking aid (f) has the general formula

(Here, R is H or CH ₃ , and n is an integer of 1 to 9.)
The flame retardant resin composition according to claim 1, which is a (meth) acrylate-based crosslinking aid represented by   The flame retardant resin composition according to claim 1 or 2, wherein the metal hydrate (B) is magnesium hydroxide.   The silane coupling agent is a silane compound having at least one selected from the group consisting of a vinyl group, a (meth) acryloyl group, an amino group, and an epoxy group at a terminal. The flame-retardant resin composition according to any one of the above.   A molded article comprising the flame retardant resin composition according to any one of claims 1 to 4 as a coating layer on the outside of a conductor, an optical fiber, or / and an optical fiber core.   A molded part formed by molding the flame retardant resin composition according to any one of claims 1 to 4.   (A1) ethylene / α-olefin copolymer, (a2) ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer, (a3) At least one polymer selected from the group consisting of (a1) to (a3) of an ethylene / propylene copolymer rubber, (b) a hydrogenated copolymer of an aromatic vinyl compound and a conjugated diene compound, (c) ) A polypropylene resin, (d) a hydrogenated copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or derivative thereof and a conjugated diene compound, (e) an organic peroxide, (f) (meth) acrylate System and / or allylic crosslinking aid and metal hydrate (B) are simultaneously heated and kneaded at a temperature equal to or higher than the melting temperature of the resin components (a) to (f). Method for producing a flame-retardant resin composition according to any one of claims 1 to 4, characterized in that.   (B) Hydrogenated product of copolymer of aromatic vinyl compound and conjugated diene compound, (c) polypropylene resin, (a1) ethylene / α-olefin copolymer, (a2) ethylene-vinyl acetate Copolymer, ethylene- (meth) acrylic acid copolymer, or ethylene- (meth) acrylic acid ester copolymer, (a3) from the group consisting of (a1) to (a3) of ethylene / propylene copolymer rubber Thermoplastic resin component by heating and kneading at least one polymer selected, and (d) a hydrogenated copolymer of an aromatic vinyl compound modified with an unsaturated carboxylic acid or derivative thereof and a conjugated diene compound After obtaining (A), in the second step, this resin component (A) and (e) an organic peroxide, (f) a (meth) acrylate-based and / or allylic crosslinking aid, The metal hydrate (B) is heated and kneaded at a temperature equal to or higher than the melting temperature of the thermoplastic resin component (A), and partially crosslinked. A method for producing a flame retardant resin composition.

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