JP2000315424A - Insulating resin composition, and insulated electric wire and insulating member using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide insulating resin composition and an electric wire using the same having heat resistance, excellent flexibility, and recyclability, without being whitened when bending the electric wire. SOLUTION: This insulating resin composition contains 50-300 pts.wt. metal hydrate to (a) block co-polymer containing polymer block A mainly containing a vinyl aromatic compound and polymer block B mainly containing a conjugate diene compound 100 pts.wt. and/or hydrogenated block co-polymer, (b) 50-150 pts.wt. softener for non aromatic rubber, (c) 40-600 pts.wt polypropylene resin, and (d) 100 pts.wt. vinyl aromatic thermoplastic elastomer composition (A). When (i) 50-100 pts.wt. metal hydrate is contained, not less than 50 pts.wt. metal hydrate is pretreated with silane coupling agent. When (ii) 100-300 pts.wt. metal hydrate is contained, at least a half amount of the metal hydrate is prepared with silane coupling agent to form the insulating resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an insulating resin composition for covering electric wires or forming an insulating member, which is suitable as a covering material for electric wires used for internal and external wiring of electric and electronic equipment, and using the same. It is related to insulated wires and insulating members.More specifically, it does not dissolve heavy metal compounds, generates a large amount of smoke or corrosive gas during disposal such as landfill, combustion, etc., and has excellent heat resistance and flexibility. The present invention relates to an insulating resin composition that does not whiten when a wire is bent and an insulated wire and an insulating member using the same.

[0002]

2. Description of the Related Art Polyvinyl chloride (PVC) compounds and halogen-based flame retardants containing bromine atoms and chlorine atoms in the molecule are used as covering materials for insulated wires used for internal and external wiring of electric / electronic devices. It is well known to use a resin composition containing a blended ethylene copolymer as a main component. However, if these materials are disposed of without proper treatment, the plasticizers and heavy metal stabilizers contained in the coating materials will elute, and if they are burned, corrosive gases will be generated from the halogen compounds contained in the coating materials. May occur, and this problem has been discussed in recent years. For this reason, a technique for coating an electric wire with a non-halogen flame-retardant material that is not likely to elute harmful heavy metals or generate a halogen-based gas has begun to be studied. Non-halogen flame-retardant materials exhibit flame retardancy by blending a flame retardant containing no halogen into the resin. Examples of the flame retardant include metal hydrates such as magnesium hydroxide and aluminum hydroxide. Further, as the resin, an ethylene / 1-butene copolymer, an ethylene / propylene copolymer, an ethylene / propylene copolymer,
A vinyl acetate copolymer, an ethylene / ethyl acrylate copolymer, an ethylene / propylene / diene terpolymer and the like are used. When imparting a high degree of flame retardancy to such a non-halogen flame-retardant material, it is necessary to mix a large amount of metal hydrate (for example, more than 120 parts by weight of metal hydrate with respect to 100 parts by weight of resin). As a result, there is a problem that the mechanical properties of the flame-retardant material deteriorate.
To solve this problem, a small amount of the metal hydrate (for example, 100 parts by weight of the resin,
(Less than 0 parts by weight) and blending red phosphorus, and non-halogen flame-retardant materials having both high flame retardancy and mechanical properties are being studied. Incidentally, insulated wires for electric / electronic devices that require a high degree of flame retardancy include, for example, UL1581 (Reference Standard for Wires, Cables, and Flexible Cords (Reference Sta.)).
ndard for Electric Wire
s, Cables, and Flexible C
ords)), etc. (Vert combustion test)
(flame retardancy) that passes the I.C.I. Flame Test.

[0003] Furthermore, a wire covering material having a high heat resistance of usually 105 ° C or higher has improved heat resistance by adopting a crosslinked structure, but the crosslinked wire has a problem in recyclability. That is, in the case of a cross-linked electric wire, it is difficult to recycle the material because the covering material does not re-melt and must be burned when discarded or landfilled. On the other hand, in order to realize high heat resistance of about 105 ° C. with a non-crosslinked electric wire, use of a resin having a high melting point such as a polypropylene resin as a base material is being studied. However, although such resins have heat resistance,
The flexibility of the electric wire obtained by coating the resin is poor, and when the electric wire is bent, the surface of the electric wire becomes whitish, causing a whitening phenomenon, which does not satisfy the characteristics required for the insulated electric wire. The current use area of PVC wires is about 105 ° C. at UL heat resistance temperature. Therefore, a non-halogen electric wire replacing this PVC electric wire needs to have heat resistance of at least UL 105 ° C. In order to ensure the heat resistance of UL 105 ° C, it is required that the resin does not melt at 136 ° C. Therefore, in order to manufacture non-halogen electric wires required as a substitute for PVC, 1
It is indispensable to develop a coating material for electric wires that does not melt at a temperature of about 36 ° C., has excellent flexibility, particularly excellent bending properties, hardly whitens when bent, and can be reshaped. On the other hand, insulation materials such as power plugs are also required to have heat resistance and flame retardancy, and it is necessary to develop recyclable and re-moldable insulation members that have heat resistance, flexibility and flame retardancy. Have been.

Japanese Unexamined Patent Publication (Kokai) No. 61-171006 discloses an insulated wire in which an insulator made of an SBS block copolymer, a polyolefin polymer, a softener, and a fatty acid metal salt is provided around the conductor. ing. In this case, it is possible to provide an insulated wire having excellent heat aging characteristics and excellent flexibility, extrusion processability, heat deformation resistance, and dispersibility without crosslinking the insulator. However, in order to obtain a halogen-free, flame-retardant insulated wire, it is not possible to achieve both mechanical properties and flame retardancy simply by adding a flame retardant such as a metal hydrate to the insulator composition. JP 58
JP-A-132032 discloses a crosslinkable composition for modifying a composition comprising a hydrogenated derivative of a block copolymer, a hydrocarbon oil, an olefin resin and / or a styrene resin, and an inorganic filler with an unsaturated silane compound. A manufacturing method is disclosed. In this case, the unsaturated group of the silane compound reacts with the resin at the time of kneading the resin composition, so that crosslinking eventually proceeds. In this case, it is difficult to keep the degree of cross-linking at a relatively low stage, and it is impossible to re-extrude after forming the molded body.In addition, a large amount of a water-containing filler such as metal hydrate is used. When added, the water crosslinking reaction further progressed, and it was found that a phenomenon such as bumps, rough appearance, and difficulties in extrusion occurred during molding of the molded article. JP 5
JP-A-9-131613 discloses that a composition comprising a hydrogenated derivative of a block copolymer, a softener for a non-aromatic rubber, and a peroxide-decomposable olefin resin is kneaded in advance, and then an organic peroxide and a crosslinking aid are used. And a method for producing a molded article which is partially crosslinked and melt-molded.
In this case, although partial crosslinking proceeds well, this alone retains mechanical strength and the molded article's resistance to scratching,
It has proven difficult to improve the wear resistance.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above problems, has heat resistance, is excellent in flexibility, does not whiten when bending an electric wire or an insulating member, and has a recyclable electric wire. An object of the present invention is to provide an insulating resin composition for coating or forming an insulating member, and an insulated wire and an insulating member using the same. Furthermore, the present invention, while having high flame retardancy and excellent mechanical properties, is excellent in flexibility, does not whiten when bending cables and formed members, landfill, at the time of disposal such as combustion,
Another object of the present invention is to provide a heat-resistant insulated wire and an insulative member that are free from elution of heavy metal compounds, generate a large amount of smoke and corrosive gas, and are recyclable.

[0006]

Means for Solving the Problems We have used a vinyl aromatic resin obtained by using a block copolymer such as a styrene-isoprene block copolymer and polypropylene as a base resin and adding a softener for a non-aromatic rubber as a softener. High strength, excellent abrasion resistance, and flame retardancy by making the thermoplastic elastomer composition partially cross-linked by using an organic peroxide through a metal hydrate treated with a silane surface. A resin composition was obtained, and it was further found that this resin composition was extrudable after molding. The present invention has been completed based on this finding. In order to achieve the above object, in the present invention, (1) (a) at least two polymer blocks A containing a vinyl aromatic compound as a main component and a conjugated diene compound as a main component At least one
Copolymer block B and / or 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the same, and (b) 50 to 150 parts by weight of a softener for non-aromatic rubber Part, (c) polypropylene resin 40 ~
600 parts by weight, and (d) organic peroxide 0.1
３3 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A) is the main resin component, and 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A) is mixed with metal water. 50 to 300 parts by weight of a hydrate, and (i) when the metal hydrate is 50 parts by weight or more and less than 100 parts by weight, a vinyl aromatic thermoplastic elastomer composition (A) 50 parts by weight or more based on 100 parts by weight, and (ii) 100 parts by weight of metal hydrate
In the case of not less than 300 parts by weight and not more than 300 parts by weight, at least half thereof is a pretreated metal hydrate pretreated with a silane coupling agent, (2)
The vinyl aromatic thermoplastic elastomer composition (A) according to item (1) is a main resin component, and further, 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A) is mixed with red phosphorus 2 0.5 to 16 parts by weight and metal hydrate 5
0-180 parts by weight, as the metal hydrate,
(I) when the metal hydrate is 50 parts by weight or more and less than 100 parts by weight, 50 parts by weight or more based on 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A); When the hydrate is 100 parts by weight or more and 180 parts by weight or less, at least half thereof is a pretreated metal hydrate pretreated with a silane coupling agent, (3) (1) The vinyl aromatic thermoplastic elastomer composition (A) according to the item (1) is a main resin component, and furthermore, ammonium polyphosphate 25 to 100 parts by weight based on 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A). (4) Insulating resin composition characterized by containing by weight, (4) The metal hydrate pretreated with a silane coupling agent is reactive with the resin component (1), (2) ) Or 3) the insulating resin composition according to claim,
(5) The insulating resin composition according to (1), (2), (3) or (4), wherein the silane coupling agent has a vinyl group and / or an epoxy group. 6) An insulated wire characterized by covering a conductor with the insulating resin composition according to any one of (1) to (5), and any of (7) (1) to (5) An insulating member comprising the insulating resin composition according to item 1 is provided. In the present invention, the metal hydrate pretreated with the silane coupling agent has reactivity with the resin component. Here, the term "reactive" means that a reaction is generated to improve the strength, abrasion resistance and scratch resistance.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, each component of the insulating resin composition of the present invention will be described. (A) Vinyl Aromatic Thermoplastic Elastomer Composition The vinyl aromatic thermoplastic elastomer composition (A) is defined as (a) at least two polymer blocks A whose main component is a vinyl aromatic compound. And at least one polymer block B whose main component is a conjugated diene compound, and / or
Or (b) 50 to 150 parts by weight of a softener for non-aromatic rubber, and (c) polypropylene resin 40 with respect to 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the same.
To 600 parts by weight and (d) an organic peroxide.
It is a composition containing 1 to 3 parts by weight. The vinyl aromatic thermoplastic elastomer composition (A) in the present invention comprises:
When kneaded and heat-treated, the component (a) is crosslinked by the presence of the component (d), while the component (c) is thermally decomposed and appropriately reduced in molecular weight, so that the composition as a whole has excellent extrudability. Resulting in a partially crosslinked product.

(A) Component Block Copolymer Component (a) of the present invention comprises at least two polymer blocks A mainly composed of a vinyl aromatic compound.
And a block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound, a block copolymer obtained by hydrogenating the block copolymer, or a mixture thereof. BA, BAB
Examples thereof include a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as —A, ABBABA, or a hydrogenated product thereof. The above (hydrogenated) block copolymer (hereinafter, the (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer) is obtained by adding a vinyl aromatic compound to 5 to 60 parts. % By weight, preferably 20 to 50% by weight. The polymer block A whose main component is a vinyl aromatic compound preferably consists of only the vinyl aromatic compound or more than 50% by weight, preferably 7% by weight.
0% by weight or more of a vinyl aromatic compound and a (hydrogenated) conjugated diene compound (hereinafter, the (hydrogenated) conjugated diene compound means a conjugated diene compound and / or a hydrogenated conjugated diene compound. ). The polymer block B whose main component is a (hydrogenated) conjugated diene compound preferably consists of only the (hydrogenated) conjugated diene compound or comprises more than 50% by weight, preferably 70% by weight %
This is a copolymer block of the above (hydrogenated) conjugated diene compound and vinyl aromatic. In each of the polymer block A whose main component is a vinyl aromatic compound and the polymer block B whose main component is a (hydrogenated) conjugated diene compound,
The distribution of repeating units derived from a vinyl aromatic compound or (hydrogenated) conjugated diene compound in the molecular chain is random, tapered (one in which the monomer component increases or decreases along the molecular chain), partially block-like, or May be any combination. In the case where there are two or more polymer blocks A mainly composed of a vinyl aromatic compound or a polymer block B mainly composed of a (hydrogenated) conjugated diene compound,
Each may have the same structure or different structures.

As the vinyl aromatic compound constituting the (hydrogenated) block copolymer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like are selected. Of which styrene is preferred. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
Isoprene and combinations thereof are preferred. Polymer block B whose main component is a conjugated diene compound
Can be arbitrarily selected. For example, a polybutadiene block preferably has a 1,2-microstructure of 20 to 50%, particularly 25 to 45%, and preferably has at least 90% of a butadiene-based aliphatic double bond hydrogenated. In the polyisoprene block, 70 to 1 of the isoprene compound
00% by weight has a 1,4-microstructure and at least 90% of aliphatic double bonds based on the isoprene compound
Is preferably hydrogenated. 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, and still more preferably 100,000. To 550,000, particularly preferably in the range of 100,000 to 400,000. Molecular weight distribution (weight average molecular weight (Mw) and number average molecular weight (M
The ratio (Mw / Mn) of n) is preferably 10 or less, more preferably 5 or less, and more preferably 2 or less. The molecular structure of the (hydrogenated) block copolymer is linear, branched,
It may be either radial or any combination of these.

[0010] Numerous methods have been proposed for producing these (hydrogenated) block copolymers. Typical methods include, for example, the method described in JP-B-40-23798. It can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or a Ziegler-type catalyst. Further, for example, a hydrogenated block copolymer can be obtained by hydrogenating the block copolymer obtained by the above method in an inert solvent in the presence of a hydrogenation catalyst. Specific examples of the (hydrogenated) block copolymer include SBS (styrene / butadiene block copolymer), SIS (styrene / isoprene block copolymer), SEBS (hydrogenated SBS), SEPS (hydrogenated SIS), and the like. Can be. In the present invention, a particularly preferred (hydrogenated) block copolymer is a polymer block A containing styrene as a main component, and a polymer block A containing isoprene as a main component and
0-100% by weight have a 1,4-microstructure and at least 90% of the aliphatic double bonds based on the isoprene
Is a hydrogenated block copolymer having a weight average molecular weight of 50,000 to 550,000 and a polymer block B obtained by hydrogenation. More preferably, 90 to 100% by weight of isoprene is the above hydrogenated block copolymer having a 1,4-microstructure.

Component (b) Softener for Non-Aromatic Rubber As the component (b) 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 an aromatic ring, a naphthene ring, and a paraffin chain in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms. Those having a naphthene ring carbon number of 30 to 40% are called naphthenics, and those having an aromatic carbon number of 30% or more are called aromatics. The mineral oil-based rubber softener used as the component (b) of the present invention is a paraffin-based or naphthene-based one in the above category. The use of an aromatic softening agent is not preferred because its use makes the component (a) soluble and inhibits the cross-linking reaction, so that the physical properties of the obtained composition cannot be improved. As the component (b), a paraffin-based component is preferable, and a paraffin-based component having less aromatic ring components is particularly preferable. The properties of these softeners for non-aromatic rubbers are such that the dynamic viscosity at 37.8 ° C. is 20 to 500 cS.
t, pour point is -10 to -15 ° C, flash point (COC) is 1
What shows 70-300 degreeC is preferable. The amount of the component (b) is from 50 to 150 per 100 parts by weight of the component (a).
Parts by weight, preferably 80 to 120 parts by weight. 150
If the amount exceeds the weight part, the softener tends to bleed out, may give tackiness to the final product, and also deteriorates the mechanical properties. If the amount is less than 50 parts by weight, the resulting composition loses its flexibility.
Part of the component (b) may be added after heat treatment in the presence of a peroxide, but may cause bleed-out. Component (b) preferably has a weight average molecular weight of 100 to 2,000.

Component (c) Polypropylene resin As the polypropylene resin, homopolypropylene or a copolymer of propylene with a small amount of other α-olefin such as 1-butene, 1-hexene, 4-methyl-1-pentene, etc. Can be used. When the elastomer composition (A) is subjected to heat treatment to produce a partially crosslinked product in the present invention, a part of the polypropylene resin as the component (c) may be blended after heat treatment (crosslinking). The polypropylene resin blended in (A) before the heat (crosslinking) treatment,
Due to the presence of the component (d), the compound is thermally decomposed and appropriately reduced in molecular weight. As a polypropylene resin to be compounded before heat treatment,
MFR (ASTM-D-1238, L condition, 230 ° C)
Is preferably 0.1 to 10 g / 10 min, more preferably 0.1 to 5 g / 10 min, and even more preferably 0.1 to 3 g.
/ 10 min. MFR of polypropylene resin
Is less than 0.1 g / 10 minutes, the molecular weight of the polypropylene resin does not decrease even after heat treatment, and the moldability of the obtained elastomer is poor. On the other hand, if the MFR exceeds 10 g / 10 minutes, the molecular weight becomes too low and the This is not preferable because the rubber elasticity of the resulting elastomer composition is deteriorated. The polypropylene resin to be blended after the heat treatment may be any resin that meets the conditions at the time of extrusion forming the coating layer or at the time of molding the insulating member by injection molding or the like, and preferably has an MFR of 5 to 200 g / 10 min. , More preferably 8 to 1
50 g / 10 min, more preferably 10 to 100 g / 10
Use the one for the minute. When blended after heat treatment, if the MFR of the polypropylene resin is less than 5 g / 10 minutes, the moldability of the obtained elastomer is poor, and the MFR is 200 g / 10 min.
If the amount exceeds the above range, the rubber elasticity of the obtained elastomer composition deteriorates, which is not preferable. The amount of the polypropylene resin (c) is 4 parts per 100 parts by weight of the component (a).
0 to 600 parts by weight, preferably 50 to 500 parts by weight, more preferably 100 to 200 parts by weight. If the amount of the polypropylene is less than 40 parts by weight, the strength is remarkably reduced, and the fluctuation in extrusion is increased. On the other hand, if the amount exceeds 600 parts by weight, the flexibility is remarkably reduced.

(D) Organic peroxide Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di- (te
rt-butylperoxy) 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, benzoyl peroxide, p-
Examples thereof include chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di-, in terms of odor, coloring and scorch stability. (Tert-Butylperoxy) hexyne-3 is most preferred. The amount of peroxide (d) added is in the range of 0.1 to 3 parts by weight, preferably 0.1 part by weight, per 100 parts by weight of component (a).
１．５1.5 parts by weight. If the amount is less than 0.1 part by weight, required crosslinking cannot be obtained. If the amount exceeds 3 parts by weight, crosslinking proceeds excessively, and not only does the dispersion of the partially crosslinked product deteriorate, but also the fluidity of the composition extremely deteriorates.

In the production of the thermoplastic elastomer composition (A) of the present invention, a polyfunctional vinyl monomer such as divinylbenzene, triallyl cyanurate, or ethylene glycol dimethacrylate is used for the partial crosslinking treatment with an organic peroxide. Polyfunctional methacrylate monomers such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate can be blended as a crosslinking aid. With such a compound, a uniform and efficient crosslinking reaction can be expected. In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle, has a peroxide solubilizing effect, and acts as a peroxide dispersing agent. This is most preferable because a partially crosslinked thermoplastic elastomer having a balanced rubber elasticity can be obtained. The amount of the crosslinking aid used in the present invention is preferably in the range of 0.02 to 1.5 parts by weight, more preferably 0.1 to 1.0 part by weight, per 100 parts by weight of the component (a). And more preferably 0.3 to 0.75 parts by weight. The addition amount of the crosslinking aid is about 2 to 2.5 times the weight of the peroxide.
Preferably, it is doubled. If the amount is less than 0.02 parts by weight based on 100 parts by weight of the component (a), the required crosslinking cannot be obtained. On the other hand, if it exceeds 1.5 parts by weight, excessive polymerization of the crosslinking aid proceeds excessively, so that not only a crosslinked gel is easily formed, but also the fluidity of the composition is extremely deteriorated.

(B) Metal Hydrate The metal hydrate used in the present invention is not particularly limited. Examples thereof include aluminum hydroxide, magnesium hydroxide, aluminum silicate hydrate, magnesium silicate hydrate, and basic hydrate. Compounds having a hydroxyl group or water of crystallization such as magnesium carbonate and hydrotalcite can be used alone or in combination of two or more. Of these metal hydrates, aluminum hydroxide and magnesium hydroxide are preferred. Further, pre-treated magnesium hydroxide pre-treated (surface treated) with a silane coupling agent is preferred. Examples of the silane coupling agent used for the surface treatment of the metal hydrate include vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, and glycidoxypropylmethyldimethoxy. Silane coupling agents having a vinyl or epoxy group at the terminal such as silane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, etc. A silane coupling agent having a mercapto group at the terminal, aminopropyltriethoxysilane,
Aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltripropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltripropylmethyldimethoxysilane and other silanes having an amino group Crosslinkable silane coupling agents such as coupling agents are preferred. Further, two or more of these silane coupling agents may be used in combination. Among such crosslinkable silane coupling agents, a silane coupling agent having an epoxy group and / or a vinyl group at a terminal is more preferable, and these may be used alone or in combination of two or more. .

As the pretreated aluminum hydroxide which can be used in the present invention, the surface-untreated aluminum hydroxide (such as Heidilite H42M (trade name, manufactured by Showa Denko KK)) can be used as the above vinyl group or Examples thereof include those subjected to a surface treatment with a silane coupling agent having an epoxy group at a terminal. As the pretreated magnesium hydroxide of the silane coupling agent that can be used in the present invention, those having no surface treatment (commercially available products such as Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd.)), stearic acid, olein Silane cups having a vinyl group or epoxy group at the terminal, such as those treated with a fatty acid such as an acid (Kisuma 5A, Kisuma 5B (trade name, manufactured by Kyowa Chemical Co., Ltd.), etc.), and those treated with a phosphoric ester. A commercially available product of magnesium hydroxide which has been surface-treated with a ring agent or has already been surface-treated with a silane coupling agent having a vinyl group or an epoxy group at its terminal (Kisma 5)
LH, Kisuma 5PH (both trade names, manufactured by Kyowa Chemical Co., Ltd.)
and so on. In addition to the above, surface treatment using a silane coupling agent having a vinyl group or an epoxy group at a terminal in addition to magnesium hydroxide or aluminum hydroxide partially surface-treated in advance with a fatty acid, a phosphate ester, or the like. Performed metal hydrates and the like can also be used.

When the metal hydrate is subjected to a surface treatment, the silane coupling agent may be blended with the untreated or partially surface-treated metal hydrate in advance or during kneading. it can. At this time, the silane coupling agent is appropriately added in an amount sufficient for surface treatment, and specifically, preferably 0.3 to 2% by weight based on the metal hydrate.
In the present invention, a metal hydrate surface-treated with a silane coupling agent having a vinyl group or an epoxy group at the end not only maintains a high mechanical strength when used as an insulator, but also forms a shell during combustion. To promote.

In addition, a metal hydrate surface-treated with a silane coupling agent having a vinyl group or an epoxy group at the terminal, and a metal hydrate surface-treated with a compound other than the silane coupling agent having a vinyl group or an epoxy group at the terminal. Or an untreated metal hydrate can be used, but 50% by weight or more, preferably 70% by weight or more of the total metal hydrate is surface-treated with a silane coupling agent having a vinyl group or an epoxy group at the terminal. Metal hydrate.

In the insulating resin composition of the present invention, the molecular (cross-linked) structure formed by the cross-linking reaction in the presence of the organic peroxide of the component (d) is one of the components (a) of the block copolymer. A cross-linking structure (I) between a resin and a resin formed by bonding a cross-linking aid between molecular chains, for example;
Another component (a) is a resin-metal hydrate (resin-filler) formed between a molecular chain in the block copolymer and a pretreated metal hydrate pretreated with a silane coupling agent. It is considered to be a crosslinked structure (II) between them. In particular, with respect to the latter (II), the pretreated metal hydrate pretreated with the silane coupling agent causes the reactive site of the silane coupling agent to be (a) by the organic peroxide of the component (d) during the kneading of the resin composition. It is considered that the compound combines with the block copolymer of component (i) and functions as a reinforcing agent for the resin molded article. Thereby, since the mechanical strength, particularly the micro-deformation strength is improved, the molded article is kept from being damaged and the wear resistance is maintained. Therefore, by adding a pretreated metal hydrate pretreated with a silane coupling agent to a resin in a sufficient amount, a resin composition and a resin molded product having strength, abrasion resistance, and scratch resistance are obtained. If the amount of the pretreated metal hydrate pretreated by this silane coupling is small, desired characteristics cannot be obtained. Furthermore, desired characteristics cannot be obtained even if the amount of the organic peroiside is small. In addition, any cross-linked structure is a partial cross-link for the resin,
That is, since it contains a flowable —CH ₂ — chain, it can be extruded after kneading in the same manner as a usual thermoplastic elastomer, and it is also possible to collect and re-extrude a molded article. Further, by the reaction with the organic peroxide, the heat distortion temperature of the resin composition and the extruded product can be further improved. As a conventionally known composition, there is, for example, a composition described in JP-A-58-133202, which does not require cross-linking with an electron beam, ultraviolet light, water, or the like. Rather, it has a molecular structure different from that of the insulating resin composition of the present invention, which is intended to perform resin-filler crosslinking simultaneously with resin-resin crosslinking. That is, in the case of the composition described in JP-A-58-133202, the role of the unsaturated silane compound is mainly for causing the resins to crosslink with each other. The resin is a water-crosslinked resin admixture in which the resin reacts and the resin molecules are crosslinked with each other by a catalytic action at the time of forming a molded article. In this case, it is impossible to re-extrude after forming the molded body, and it is difficult to scratch,
The effect of maintaining strength is small. Furthermore, in this case, the crosslinking reaction proceeds due to the moisture contained in the filler, and when a large amount of a filler that easily contains water such as a metal hydrate is added, the water crosslinking reaction proceeds. A phenomenon that makes extrusion difficult occurs.

It is preferable to use a metal hydrate in combination with red phosphorus when it is desired to further improve the flame retardancy. When added, the metal hydrate is added in an amount of 50 parts by weight when used together with red phosphorus with respect to 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A) in the resin composition of the present invention. To 180 parts by weight, and 50 to 300 parts by weight when not used together. In particular, when used in combination with red phosphorus, it is particularly preferable to use 90 to 150 parts by weight of metal hydrate together with 8 to 16 parts by weight of red phosphorus, whereby it is possible to adapt to vertical flame retardancy. Becomes When a metal hydrate is used without the use of red phosphorus, the metal hydrate is used in an amount of 50 parts by weight or more. It is applicable to the horizontal flame retardancy specified in 3005. However, if the amount exceeds 300 parts by weight in the system to which red phosphorus is not added, and if the amount exceeds 180 parts by weight in the system to which red phosphorus is added, the strength is greatly reduced. The compounding amount is preferably maintained at 280 parts by weight or less for a system to which red phosphorus is not added, and 150 parts by weight or less for a system to which red phosphorus is added. As for the insulating member such as a power plug, the compounding amount of the metal hydrate is based on 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A) in the resin composition of the present invention in combination with red phosphorus. In this case, the amount is preferably 50 to 180 parts by weight, and when not used together, the amount is preferably 50 to 300 parts by weight. In the present invention, a pretreated metal hydrate is prepared by pretreating a predetermined amount of the metal hydrate to be used with a silane coupling agent. That is, when (i) the metal hydrate is 50 parts by weight or more and less than 100 parts by weight, 50 parts by weight or more based on 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A), and (ii) If the metal hydrate is 100 parts by weight or more, at least half of the metal hydrate is a pretreated metal hydrate pretreated with a silane coupling agent. It is considered that this pretreatment causes the silane coupling agent to cause a grafting reaction to the metal hydrate. When the amount of the pre-treated metal hydrate pre-treated with the silane coupling agent is less than a predetermined amount, the strength is remarkably reduced, and the abrasion resistance and the scratch resistance of the molded product are remarkably reduced. Further, the pretreated metal hydrate pretreated with the silane coupling agent has the reactive site bonded and held with the component (a) component block copolymer at the time of kneading and forming the resin composition.
Even if a large amount of metal hydrate is added, a decrease in strength does not occur, and a large amount of filler can be mixed with the resin. Therefore, if the amount of the metal hydrate obtained by combining the pre-treated and untreated metal hydrates is not more than 180 parts by weight when used in combination with red phosphorus and not more than 300 parts when not used in combination, there is no significant decrease in strength. Does not occur.

(C) Red phosphorus In the present invention, red phosphorus can be added to the resin composition of the present invention for the purpose of improving the flame retardancy of insulated wires and insulating members. Red phosphorus is particularly preferably used in combination with the metal hydrate to significantly improve the flame retardancy. When added, the amount of red phosphorus is preferably 2.5 to 16 parts by weight, more preferably 8 to 13 parts by weight, per 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A). is there. Red phosphorus is 2.5
If the amount is less than 10 parts by weight, sufficient flame retardancy cannot be obtained. If the amount is more than 16 parts by weight, mechanical properties such as tensile strength and tensile elongation are undesirably reduced. More preferably, by setting the blending amount of red phosphorus to 8 parts by weight or more, not only the inclined flame retardant specified in JIS C 3005 but also the vertical flame retardant specified in UL1581 is maintained. Can be. For red phosphorus, heat,
From the viewpoint of stability against moisture and dispersibility in the resin composition, those having been subjected to surface treatment are preferable. Further, from the viewpoint of suppressing the deterioration of the physical properties of the resin composition and improving the flame retardancy, the average particle diameter is 10 μm. The thickness is more preferably 5 μm or less. These include "Novalet,""NovaExcel," and "Novaquell" (brand names,
Commercial products such as Rin Kagaku Kogyo Co., Ltd.) can be used.

(D) Ammonium polyphosphate In the present invention, an ammonium polyphosphate-based flame retardant may be added to the resin composition of the present invention in order to impart flame retardancy to the insulated wires and insulating members. Ammonium polyphosphate is preferred because it is a colorless phosphorus-based flame retardant and can be easily colored. Examples of the ammonium polyphosphate-based flame retardant include those containing ammonium polyphosphate alone, or those containing isocyanuric acid or a derivative thereof,
Those coated with a formaldehyde resin and the like can be mentioned. When ammonium polyphosphate containing isocyanuric acid or a derivative thereof is used, the flame retardancy of insulated wires and insulating members can be further improved, and among them, tris (2-hydroxyethyl) isocyanurate and polypropylene resin are used. It is preferable in terms of affinity and flame retardancy. When ammonium polyphosphate coated with a melamine / formaldehyde resin or the like is used, the water resistance of the insulated wire and the insulating member can be improved. Such examples include “Hostafram AP422”, “Hostafram AP423”, and “Hostafram AP462”.
"Hostafram AP745" (trade name, Hoechst
And "Sumisafe P" and "Sumisafe PM" (trade name, manufactured by Sumitomo Chemical Co., Ltd.). When added, the amount of ammonium polyphosphate is preferably 25 to 100 parts by weight, more preferably 40 to 70 parts by weight, per 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A). is there. If the amount is less than 25 parts by weight, there is a problem in flame retardancy. If the amount is more than 100 parts by weight, elongation becomes extremely low.

The partially cross-linked molded article of the vinyl aromatic thermoplastic elastomer composition (A) in the present invention has flexibility, not only does not easily cause whitening when bent, but also has red phosphorus and metallic water. Even when a large amount of filler such as Japanese is added, it has the property of not causing whitening when bent. When ordinary polyolefin resins such as polyethylene resin and polypropylene resin are used as the base resin, and red phosphorus and metal hydrate are added in large amounts, the strength is greatly reduced. By using the thermoplastic elastomer composition (A), even if these fillers are added, a decrease in strength is suppressed to a minimum, and satisfactory properties as a material for covering electric wires and a material for forming an insulating member can be obtained. In addition, by using magnesium hydroxide surface-treated with a silane coupling agent as magnesium hydroxide, it is possible to greatly suppress the decrease in strength, and it is also difficult to damage and bends insulating members such as electric wires and power plugs Whitening can be minimized. In particular, when a silane coupling agent whose terminal group is a vinyl group and / or an epoxy group is used, the strength is preferably maintained and the degree of scratch resistance is large, which is preferable.

In the present invention, silicone rubber, silicone oil, and silicone gum are added to the resin to further improve the flame retardancy and to control the adhesion between the conductor and the insulating layer (coating layer containing the resin composition). They may be added to the composition, and examples thereof include linear and ladder-type silicone-containing compounds such as silicone rubber, silicone gum, and silicone oil. Although not particularly limited, silicone oils include polymethyl silicone oils, and silicone gums and silicone oils include polymethyl silicone gums and those having a three-dimensional structure. The material is "SFR-100" (trade name, GE
Co., Ltd.) and "CF-9150" (trade name, manufactured by Toray Silicone Co., Ltd.). When added, preferably this silicone rubber, silicone oil, silicone gum,
Vinyl aromatic thermoplastic elastomer composition (A) 10
0.5 to 6 parts by weight per 0 parts by weight. 0.5
When the amount is less than 6 parts by weight, the effect is substantially lost, and when the amount exceeds 6 parts by weight, the appearance is deteriorated, and the extrusion linear speed is remarkably reduced, so that mass productivity is deteriorated. Further, a silicone powder may be added to the resin composition, and examples of the silicone powder include a silicone-containing compound having a three-dimensional structure. Although it is not particularly limited as the silicone powder,
Trade name "Trefill" (manufactured by Toray Silicone Co., Ltd.) and "Tospearl" (manufactured by Toshiba Silicone Co., Ltd.) are listed. When added, preferably the silicone resin powder is
Vinyl aromatic thermoplastic elastomer composition (A) 10
It is blended in an amount of 2 to 20 parts by weight with respect to 0 parts by weight. If not more than 2 parts by weight, no substantial effect can be obtained, and if it exceeds 20 parts by weight, the mechanical strength and elongation are remarkably reduced, and the extrusion characteristics are further remarkably reduced.

Other resins can be introduced into the resin composition for covering electric wires of the present invention as long as the object of the present invention is not impaired. At least the vinyl aromatic thermoplastic elastomer composition (A) is mainly used. Resin component. Here, the term “main resin component” refers to a resin component of the insulating resin composition of the present invention that usually has a content of 70% by weight or more, preferably 85% by weight or more.
More preferably, it means that the total amount of the resin component is occupied by the vinyl aromatic thermoplastic elastomer composition (A). In the present invention, various additives commonly used in electric wires, cables, power plugs, and the like are used in the insulating resin composition for covering electric wires or forming insulating members.
For example, an antioxidant, a metal deactivator, a flame retardant (auxiliary) agent, a filler, a lubricant and the like can be appropriately compounded within a range that does not impair the purpose of the present invention. In particular, since the resin composition containing no metal hydrate and / or ammonium polyphosphate flame retardant without red phosphorus is white, a color batch containing a colorant and a polyolefin resin as a base resin is used. By blending, it can be easily colored to any color. Antioxidants include amine-based antioxidants such as polymers of 4,4'-dioctyldiphenylamine, N, N'-diphenyl-p-phenylenediamine, and 2,2,4-trimethyl-1,2-dihydroquinoline. 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
Phenolic antioxidants such as -hydroxybenzyl) benzene, bis (2-methyl-4- (3-n-alkylthiopropionyloxy) -5-t-butylphenyl) sulfide, 2-mercaptobenzimidazole and zinc salts thereof And sulfur-based antioxidants such as pentaerythritol-tetrakis (3-lauryl-thiopropionate).

Examples of the metal deactivator include N, N'-bis (3- (3,5-di-tert-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. Further, as a flame retardant (auxiliary) agent and filler, carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compound, quartz, talc, calcium carbonate, magnesium carbonate, boric acid Zinc, white carbon and the like. Examples of the lubricant include hydrocarbon type, fatty acid type, fatty acid amide type, ester type, alcohol type, metal soap type (for example, magnesium stearate), and the like.
Above all, "Wax E" and "Wax OP" (brand name,
Ester lubricants exhibiting both internal lubricity and external lubricity at the same time are preferred.

Next, a method for producing the insulating resin composition of the present invention will be described. In the first step, first, the total amount of the components (a) and (b) and at least a part of the component (c) (preferably 5 to 100% by weight, more preferably 30 to 100% by weight of the amount of the component (c) used) 100% by weight), metal hydrate, ammonium polyphosphate, flame retardant such as metal hydrate and red phosphorus, and optionally various additives such as filler, antioxidant, light stabilizer, colorant, etc. Melt and knead in advance. The kneading temperature is preferably from 160 to 240 ° C. As the kneading method, a method usually used for rubber, plastics and the like can be used satisfactorily. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, various kneaders and the like are used. By this step, a composition in which each component is uniformly dispersed can be obtained. In the second step, the organic peroxide (d) and, if desired, a crosslinking aid are added to the composition obtained in the first step, and the mixture is further kneaded under heating to cause partial crosslinking. The temperature at this time is preferably 180 to 240 ° C. As described above, the components (a) to (c) are melt-kneaded in advance to cause micro-dispersion, and then the organic peroxide (d) is added and kneading is performed under heat treatment to form a partially crosslinked product. Gives particularly favorable physical properties. This step is
In general, kneading can be performed by using a twin-screw extruder, a Banbury mixer, or the like. The first and second steps may be a single step, and the respective components may be mixed and melt-kneaded. In the third step, the remaining amount of each component is added to the partially crosslinked composition obtained in the second step and kneaded. The kneading temperature is preferably from 180 to 240 ° C. The kneading can be generally performed using a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, various kneaders, or the like. In this step, the reaction is completed at the same time as the dispersion of each component further proceeds. Further, it is also possible to combine the first, second and third steps into a single step, and to melt-knead the components collectively. In the first step, the whole amount of the component (c) is added, and then the second step
The insulating resin composition of the present invention may be obtained through a step.

When adding a metal hydrate, ammonium polyphosphate, red phosphorus or the like not surface-treated with a silane coupling agent to the insulating resin composition of the present invention, the vinyl aromatic thermoplastic elastomer composition is partially crosslinked. After getting it
Alternatively, it may be added before partial crosslinking. However, when using pre-treated magnesium hydroxide pre-treated with a silane coupling agent, it must be added before or during partial crosslinking. By adding it in a state before partial crosslinking, the silane coupling agent on the surface of the metal hydrate and the resin are bonded to each other, so that a molded article having high strength retention and being hardly damaged can be obtained. In particular, when a silane coupling agent having a vinyl group and / or an epoxy group at a terminal is used, the effect is remarkable. In addition, in order to add a large amount of a filler such as magnesium hydroxide, it is preferable in terms of ease of kneading that even a metal hydrate not surface-treated with a silane coupling agent be added at a stage before partial crosslinking. . The insulated wire of the present invention is not particularly limited, except that it has at least one coating layer made of the resin composition of the present invention formed on the outer periphery of the conductor by extrusion coating. For example, any known conductor such as a single wire or stranded wire can be used as the conductor. The shape of the insulating member of the present invention is not particularly limited, and examples thereof include a power plug, a connector, a sleeve, a box, and a tape base material. The insulating member of the present invention is molded from the resin composition of the present invention by a normal molding method such as injection molding. In the insulated wire of the present invention, the thickness of the insulating layer (the coating layer made of the resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 mm to 3 mm.

In the insulated electric wire of the present invention, it is preferable to form a coating layer by extrusion coating with the resin composition of the present invention, which is a partially crosslinked product, but it is intended to further improve heat resistance. It is also possible to crosslink the coating layer after extrusion. However, when this cross-linking treatment is performed,
The coating layer cannot be reused as an extruded material. As a method for performing crosslinking, a conventionally known electron beam irradiation crosslinking method or chemical crosslinking method can be employed. In the case of the electron beam cross-linking method, the resin composition is extruded to form a coating layer and then irradiated with an electron beam by a conventional method to perform cross-linking. The dose of the electron beam is appropriately 1 to 30 Mrad, and in order to efficiently perform crosslinking, the resin composition constituting the coating layer is formed by adding a methacrylate-based compound such as trimethylolpropane triacrylate or an allyl-based compound such as triallyl cyanurate. A polyfunctional compound such as a compound, a maleimide compound or a divinyl compound may be blended as a crosslinking aid. In the case of the chemical cross-linking method, an organic peroxide is blended in a resin composition as a cross-linking agent, and after extrusion molding to form a coating layer, cross-linking is performed by a heat treatment in a conventional manner.

[0030]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Numerals indicate parts by weight unless otherwise specified. Hydrogenated styrene-isoprene block copolymer (SEPS) as a component (a), paraffin oil as a component (b), homopolypropylene (MFR 8 g / 10 min) as a component (c), dik as a component (d) A vinyl aromatic thermoplastic elastomer composition was produced in three steps using a twin screw extruder with L / D = 44 using milloxide and the respective components at the compounding amounts shown in Table 1. First, the total amount of each of the components (a) and (b) other than the components (c) and (d) shown in Table 1 and the component (c)
Is melt-kneaded (first step), and then component (d) and 2 parts by weight of triethylene glycol dimethacrylate as a crosslinking aid are added and melt-kneaded in the middle of the extruder (second step). ) Further, the remainder of the component (c) was added in the middle of the extruder and melt-kneaded (third step). Using a twin-screw extruder (L / D = 47), melt kneading was performed at a screw rotation speed of 200 rpm, and the melt kneading temperature in each step was as follows: First step: 180 to
200 ° C., second step: 200 to 220 ° C., third step: 2
00-220 ° C.

[0032]

[Table 1]

On the other hand, magnesium hydroxide (trade name, Kisuma 5LH, manufactured by Kyowa Chemical Industry Co., Ltd.) surface-treated with a silane coupling agent having a vinyl group at the terminal or magnesium hydroxide not subjected to a surface treatment is used. Insulation resin compositions were prepared by using compositions that had been surface-treated (pre-treated) with a silane coupling agent having a vinyl group at the terminal and in the formulations shown in Tables 2 to 4. Here, for each composition, each component was dry-blended at room temperature, charged into a kneader, and melt-kneaded. Using a kneader of 20 liter capacity, kneading at a rotor rotation speed of 40 rpm until the temperature of the melt-kneaded product becomes 180 to 220 ° C.
It pelletized by the granulator.

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

(Examples 1 to 22, Comparative Examples 1 to 16) First, the components shown in Table 5 were dry-blended at room temperature and melt-kneaded using a Banbury mixer to prepare a resin composition. From the obtained resin composition, 1 mm sheets corresponding to Examples 1 to 3 were prepared by pressing. Next, a conductor (conductor diameter: 0.
95mmφ tinned soft copper stranded wire Composition: 21 / 0.18
mmφ), an insulating resin layer previously melt-kneaded was coated by an extrusion method so as to have an outer diameter of 2.63 mm to form an insulating coating layer, and insulated wires corresponding to Examples 1 to 3 were manufactured. Separately, each of the components shown in Tables 2 to 4 was melt-kneaded, and then extruded and coated on a conductor in the same manner as described above using each of the insulating resin compositions pelletized to form Examples 4 to 22 and Comparative Example 1. The insulated wires corresponding to Nos. To 16 were manufactured.

The obtained sheets were evaluated for tensile properties (elongation (%) and strength (tensile strength, MPa)) and heat deformation properties, and the results are shown in Tables 5 to 8. Each characteristic was performed based on JIS K 6723, and the heating deformation test was performed at 120 ° C. For each property of the sheet, elongation was 100% or more and strength 10 MPa or more was accepted, and as for heat deformation, deformation rate 30% or less was accepted. on the other hand,
For each of the obtained insulated wires, tensile properties, flame retardancy 1, flame retardancy 2, appearance, flexibility, whitening property when bending the cable,
The heat deformation characteristics were evaluated, and the results are shown in Tables 5 to 8. Tensile properties were measured by measuring the strength (tensile strength) (MPa) and elongation (%) of the coating layer of each insulated wire at a mark distance of 25 mm and a tensile speed of 500 mm / min. It measured on condition of. Growth is 1
50% or more, and the strength of the composition is required to be about 10 MPa or more. Flame retardancy 1 is UL1581 for each insulated wire.
The vertical combustion test (VW-1) was performed, and the result was represented by the number of passed samples / the number of tests. Regarding Flame Retardancy 2, a horizontal flame retardancy test shown in JIS C 3005 was performed on each insulated wire, and the number of passed flames / test number was shown. The appearance was visually checked for roughness of the insulated wire.
A slightly rough thing is indicated by △, and a severely rough thing is indicated by ×. × and △ cannot be put to practical use.
The flexibility was evaluated by the test method shown in FIG. Each insulated wire was cut to a length of 20 cm to obtain a sample (1), one end of which was fixed to a vertically upright wall (2), and the difference between the fixed position and the height of the other end lowered by its own weight. L (cm) was measured. Height difference (L) is 1c
x if less than 1 cm and less than 3 cm
In the case of 3 cm or more, it was indicated by ○. The ones with poor cross-linkability are poor and cannot be put to practical use as insulated wires. The whitening property when the cable was bent was evaluated based on whether or not whitening occurred when the cable was wound around a mandrel having a self-diameter. After 10 windings, the white circle indicates no whitening even once, the white circle indicates the whitening occurs three times or less, and the cross indicates the whitening occurs four or more times. × cannot be put to practical use. Heat deformation characteristics are UL1
581, at 136 ° C. in accordance with the heat deformation test. The results are shown as a ratio (%) of deformation after heating to that before heating.
If this value is 50% or more, it cannot be put to practical use.

The following substances were used. Component (a): hydrogenated block copolymer Kuraray Co., Ltd. Product name: Septon 4077 Styrene content: 30% by weight Isoprene content: 70% by weight Microstructure: 1,4-microstructure Number average molecular weight: 260 Weight average molecular weight: 320,000 Molecular weight distribution: 1.23 Hydrogenation rate: 90% or more Component (b): softener for non-aromatic rubber Idemitsu Kosan Co., Ltd. Product name: Diana Process Oil PW-
90 types: paraffinic oil Weight average molecular weight: 540 Aromatic component content: 0.1% or less-Component (c): polypropylene resin manufactured by Tokuyama Corp. Product name: ME140 Type: homopolymer Melt index (measuring temperature 190 ° C) , Measured load
2.16 kg): 8.5 g / 10 min. Component (d): Organic peroxide Chemicals manufactured by Akzo Co., Ltd. Product name: Kayakumil D Type: Dicumyl peroxide-Crosslinking auxiliary agent: Shin Nakamura Chemical Co., Ltd. Product name: NK Ester 3G Type: Triethylene glycol dimethacrylate

-Magnesium hydroxide Product name: Kisuma 5B (magnesium hydroxide surface-treated with oleic acid) manufactured by Kyowa Chemical Co., Ltd. Product name: Kisuma 5LH (a silane coupling agent having a vinyl group at a terminal) Magnesium hydroxide with surface treatment) Kyowa Kagaku Co., Ltd. Product name: Kisma 5 (non-surface treatment) ・ Silane coupling agent Product name: TSL8370 (Toshiba Silicone Co., Ltd.) Ammonium flame retardant manufactured by Hoechst Company name: Hostaflam AP462 ・ Antioxidant pentaerythrityl-tetrakis (3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate) Ciba-Geigy product name: Irganox 1
010 ・ Lubricant Partially saponified montanic acid ester wax manufactured by Hoechst Company name: Wax OP ・ Red phosphorus manufactured by Rin Kagaku Kogyo Co., Ltd. Product name: Nova Excel F5 ・ Random polypropylene manufactured by Grand Polymer Corporation Product name: F-226B ・ Block polypropylene ground polymer Product name: J703

[0041]

[Table 5]

[0042]

[Table 6]

[0043]

[Table 7]

[0044]

[Table 8]

From the results shown in Tables 5 to 8, (a) it is composed of at least two polymer blocks A mainly containing a vinyl aromatic compound and at least one polymer block B mainly containing a conjugated diene compound. (B) 50-150 parts by weight of a non-aromatic rubber softener, and (c) polypropylene, relative to 100 parts by weight of a block copolymer and / or a hydrogenated block copolymer obtained by hydrogenating the same. Resin 40
To 600 parts by weight, (d) organic peroxide 0.1 to 3
It can be seen that a system using the vinyl aromatic thermoplastic elastomer composition in which parts by weight are blended is excellent in heat resistance, flexibility and strength. Red phosphorus and metal hydrates, metal hydrates,
When a predetermined amount of ammonium polyphosphate is blended and a metal hydrate is used, the predetermined amount is used as a pre-treated metal hydrate pretreated with a silane coupling agent, so that flame retardancy and strength, further heat resistance, It can be seen that a flame-retardant insulated wire having excellent flexibility and not being whitened by bending can be obtained.

On the other hand, in particular, Comparative Examples 11, 12, 1
In No. 3, since no pre-treated metal hydrate was used, any of the properties was extremely inferior to the examples of the present invention. Comparative Example 11: After the partial cross-linking reaction of the elastomer composition (A) was completed, the effect (strength and appearance) of the present invention was not recognized because metal hydrate was added. Comparative Example 12: After the silane grafting and the partial crosslinking reaction of the elastomer composition (A) were completed, a metal hydrate (whether pre-treated or untreated, or treated with a material other than the silane coupling agent) It was the same when used.)
Was added, but the effect of the present invention was not recognized as in Comparative Example 11. Comparative Example 13: A compound having the composition of Example 20 was prepared by the following method without mixing magnesium hydroxide and a silane coupling agent in advance. Hydrogenated styrene
Isoprene block copolymer (SEPS), paraffin oil, homopolypropylene (MFR8g / 10min),
The metal hydrate having no surface treatment was first mixed with a Banbury mixer, and then dicumyl peroxide and a silane coupling were charged, kneaded with a Banbury mixer, and discharged. The obtained compound was difficult to re-mold, the sheet surface had many bumps, and extrusion was impossible.

The compositions I, J, and K were evaluated for characteristics after molding into plug terminals in addition to the evaluation for electric wires. Injection molding was performed on each of the power plug terminals to which the two electric wires prepared in Example 4 were connected by using an injection molding machine by using the composition I, J, or K to form a power plug. These power plugs were molded at an injection temperature of 230 ° C. The appearance of each of the obtained molded plugs was good, and no shrinkage due to the material occurred. Furthermore, the flame of the burner used in the flame retardancy test specified in JIS C3005 was applied to the power plug for 15 seconds, and the fire was instantaneously extinguished when the flame was separated.

[0048]

The insulating resin composition of the present invention is composed of a non-halogen flame-retardant material, and does not elute heavy metal compounds or generate a large amount of smoke or corrosive gas at the time of disposal such as landfill or combustion. . Further, the insulated wire and the insulating member of the present invention are excellent in flame retardancy, strength, heat resistance and flexibility, and are not particularly whitened by bending. As described above, in particular, the insulated wire according to the present invention has excellent properties as a halogen-free insulated wire that can achieve both flame retardancy and mechanical properties. Furthermore, the coating layer of the insulated wire of the present invention can be formed of a resin composition that is a partially crosslinked product, and can achieve high heat resistance without crosslinking the entire resin composition. The insulated wire is a wire having high heat resistance and a recyclable covering layer and excellent recyclability. As described above, the insulated wire of the present invention is very useful as a wiring or cord for electric / electronic devices in consideration of environmental issues. Further, the resin composition of the present invention is used as a covering material for such wirings and cords.
It is also suitable as a material for the insulating member, and also as a tube or tape material.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a test method of flexibility.

[Explanation of symbols]

 1 Wire sample 2 Wall L Height difference (cm)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 9/00 C08K 9/00 C08L 23/10 C08L 23/10 53/02 53/02 H01B 3/44 H01B 3/44 K 15/00 15/00 // H01B 7/29 17/56 A 17/56 17/58 F 17/58 7/34 A (72) Inventor Michihisa Tasaka Shimoodanaka, Nakahara-ku, Kawasaki City, Kanagawa Prefecture 3-16-25-405 (72) Inventor: Yoshiyuki Kajiyama 3-20-3, Ryoke, Urawa-shi, Saitama (72) Inventor: Shinzo Saito 1-9-9, Higashi-Kojiya, Ota-ku, Tokyo F-term (reference) 4J002 AE05X BB12Y BB14Y BP01W DA058 DE077 DE147 DE267 DE287 DH058 DJ007 EK036 EK046 EK056 EK086 FB087 FB107 FB137 FB147 FB157 FB237 FD010 FD070 FD137 FD138 GQ01 5G303 AA06 AA06 AA06 AA06 AA08 AB20 BA12 CA09 CA11 5G305 AB02 AB03 CD13 CD17 5G315 CA02 CA03 CB02 CC08 CD01 CD13 CD14 5G333 AA09 AB14 CB12 CB13 DA03 DA21 EA02 EB09

Claims (7)

[Claims] 1. (a) at least two polymer blocks A whose main component is a vinyl aromatic compound,
A block copolymer comprising at least one polymer block B whose main component is a conjugated diene compound and / or 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the same; (b ) A vinyl aromatic thermoplastic elastomer containing 50 to 150 parts by weight of a softening agent for non-aromatic rubber, (c) 40 to 600 parts by weight of a polypropylene resin, and (d) 0.1 to 3 parts by weight of an organic peroxide. The composition (A) is a main resin component, and further, a vinyl aromatic thermoplastic elastomer composition (A)
The metal hydrate is contained in an amount of 50 to 300 parts by weight with respect to 100 parts by weight. As the metal hydrate, (i) when the metal hydrate is 50 parts by weight or more and less than 100 parts by weight, vinyl aromatic is used. 50 parts by weight or more based on 100 parts by weight of the base thermoplastic elastomer composition (A), and (ii) at least half the amount when the metal hydrate is 100 parts by weight or more and 300 parts by weight or less, a silane coupling agent. An insulating resin composition characterized by being a pre-treated metal hydrate pretreated with 2. The vinyl aromatic thermoplastic elastomer composition (A) according to claim 1, which is a main resin component, and further comprising a vinyl aromatic thermoplastic elastomer composition (A).
2.5 to 16 parts by weight of red phosphorus and 50 to 180 parts by weight of metal hydrate with respect to 100 parts by weight, and as the metal hydrate, (i) 50 to 100 parts by weight of metal hydrate When the amount is less than 50 parts by weight, 100 parts by weight or more of the vinyl aromatic thermoplastic elastomer composition (A) is used, and (ii) 100 parts by weight or more of the metal hydrate is used.
In the case where the amount is less than part by weight, at least half of the composition is a pretreated metal hydrate pretreated with a silane coupling agent. 3. The vinyl aromatic thermoplastic elastomer composition (A) according to claim 1, which is a main resin component, further comprising a vinyl aromatic thermoplastic elastomer composition (A).
Ammonium polyphosphate 25 to 1 part by weight
An insulating resin composition containing 00 parts by weight. 4. The insulating resin composition according to claim 1, wherein the metal hydrate pretreated with the silane coupling agent is reactive with the resin component. 5. The insulating resin composition according to claim 1, wherein the silane coupling agent has a vinyl group and / or an epoxy group. 6. An insulated wire comprising a conductor coated with the insulating resin composition according to claim 1. Description: 7. An insulating member comprising the insulating resin composition according to claim 1.