JP3464410B2 - Insulating resin composition and insulated wire and insulating member using the same - Google Patents

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 wire coating or forming an insulating member, which is suitable as a coating material for wires used for internal and external wiring of electric / electronic devices, and the use thereof. More specifically, it relates to insulated wires and insulating members, and more specifically, it has excellent heat resistance and flexibility without elution of heavy metal compounds, generation of large amounts of smoke or corrosive gas, at the time of disposal such as landfill and combustion. The present invention relates to an insulating resin composition that does not whiten when a wire is bent, and an insulated wire or insulating member using the same.

[0002]

2. Description of the Related Art Polyvinyl chloride (PVC) compounds and halogen-based flame retardants containing a bromine atom or a chlorine atom in a molecule are used as coating materials for insulated electric wires used for internal and external wiring of electric and electronic devices. It is well known to use a resin composition containing a blended ethylene-based copolymer as a main component. However, if they are discarded without proper treatment, the plasticizers and heavy metal stabilizers contained in the coating material will elute, and if they are burned, the halogen compounds contained in the coating material will cause corrosive gas. May occur and this issue has been discussed in recent years. Therefore, a technique for coating the electric wire with a non-halogen flame-retardant material that does not cause the elution of harmful heavy metals or the generation of halogen-based gas has begun to be studied. The non-halogen flame-retardant material exhibits flame retardancy by blending a flame-retardant containing no halogen with the resin, and examples of the flame-retardant include metal hydrates such as magnesium hydroxide and aluminum hydroxide. As the resin, ethylene / 1-butene copolymer, ethylene / propylene copolymer, ethylene /
Vinyl acetate copolymer, ethylene / ethyl acrylate copolymer, ethylene / propylene / diene terpolymer and the like are used. When imparting a high degree of flame retardancy to such a halogen-free flame-retardant material, it is necessary to add a large amount of metal hydrate (for example, more than 120 parts by weight of metal hydrate to 100 parts by weight of resin). As a result, there is a problem that the mechanical properties of the flame-retardant material deteriorate.
In order to solve this problem, a small amount of the metal hydrate is used (for example, 100 parts by weight of the resin is mixed with 12 parts of the metal hydrate).
The amount of red phosphorus is adjusted to 0 part by weight or less), and a non-halogen flame-retardant material having both high flame retardancy and mechanical properties has been studied. By the way, for insulated electric wires for electric / electronic devices that require a high degree of flame retardancy, for example, UL1581 (related standards for electric wires, cables, and flexible cords (Reference Sta.
nd for for electrical wire
s, Cables, and Flexible C
vertical combustion test (Vert)) etc.
It is required to have flame retardancy to pass the ICal Flame Test).

Further, a wire covering material having a high heat resistance of 105 ° C. or higher usually has a crosslinked structure to improve heat resistance, but the crosslinked wire has a problem in recyclability. That is, in the case of a crosslinked electric wire, since the coating material does not remelt, it is difficult to recycle the material because it burns or discards it when it is discarded. On the other hand, using a resin having a high melting point such as a polypropylene resin as a base material has been studied in order to realize a high heat resistance of about 105 ° C. in a non-crosslinked electric wire. However, although such a resin has heat resistance,
The electric wire obtained by coating the resin is poor in flexibility, and when the electric wire is bent, a whitening phenomenon occurs in which the electric wire surface becomes whitish, which does not satisfy the properties required for the insulated electric wire. The current usage range of PVC electric wires is about 105 ° C. at the UL heat resistant temperature. Therefore, a non-halogen electric wire that replaces this PVC electric wire needs to have a heat resistance of at least about UL 105 ° C. In order to ensure the heat resistance of UL 105 ° C., it is required that the material does not melt at 136 ° C. Therefore, in order to manufacture a non-halogen electric wire which is required as a PVC substitute, 1
It is indispensable to develop a re-moldable coating material for electric wires which does not melt at a temperature of about 36 ° C., is excellent in flexibility, particularly bending characteristics, hardly whitens when bent, and is re-moldable. On the other hand, insulation materials such as power plugs are also required to have heat resistance and flame retardancy, and since they have heat resistance, flexibility, and flame resistance, the development of recyclable and remoldable insulation materials is required. Has been.

By the way, Japanese Patent Application Laid-Open No. 61-171006 discloses an insulated wire in which an insulator composed of an SBS block copolymer, a polyolefin polymer, a softening agent and a fatty acid metal salt is provided on the outer circumference of the conductor. ing. In this case, it is possible to provide an insulated electric wire that is excellent in heat aging resistance and is also excellent in flexibility, extrusion processability, heat deformation resistance, and dispersibility without crosslinking the insulator. However, in order to obtain a non-halogen flame-retardant insulated wire, mechanical properties and flame retardancy cannot be achieved at the same time simply by adding a flame retardant such as a metal hydrate to this insulator composition. JP-A-58
No. 132032 discloses a crosslinkable composition obtained by 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 during the kneading of the resin composition, so that the crosslinking eventually proceeds. In this case, it is difficult to keep the degree of cross-linking at a relatively low stage, re-extrusion is not possible after forming the molded body, and in addition, a large amount of a filler such as a metal hydrate which tends to contain water is added. It was found that when added, the water-crosslinking reaction further proceeded, and that a phenomenon such as hard spots, rough appearance, and difficult extrusion occurred during molding of the molded body. JP-A-5
JP-A-9-131613 discloses that a composition comprising a hydrogenated derivative of a block copolymer, a softening agent for a non-aromatic rubber, and a peroxide-decomposable olefin resin is kneaded in advance, and then an organic peroxide and a crosslinking assistant are used. Disclosed is a method for producing a molded body in which the compound is partially crosslinked and melt-molded.
In this case, partial crosslinking proceeds well, but this alone maintains the mechanical strength and the scratch resistance of the molded body,
It has been found difficult to improve wear resistance.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above problems, has heat resistance, is excellent in flexibility, does not whiten when a wire or insulating member is bent, and is a recyclable 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 or insulating member using the same. Further, the present invention, while having a high degree of flame retardancy and excellent mechanical properties, excellent flexibility, does not whiten when the cable or forming member is bent, 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 insulating member which are free from the elution of heavy metal compounds, generate a large amount of smoke and corrosive gas, and can be recycled.

[0006]

[Means for Solving the Problems] We use, for example, styrene.
・ Block copolymers such as isoprene block copolymers
And polypropylene as the base resin, non-softening agent
Vinyl Aromatic Thermoplastic with Aromatic Rubber Softener
Elastomer composition with silane surface treated metal hydration
Partial cross-linking using organic peroxide
It has high strength, excellent wear resistance, and
A resin composition having flame retardancy is obtained.
Found that fat composition can be re-extruded after molding
did. The present invention has been completed based on this finding
Is. In order to achieve the above object, in the present invention
Is (1) (a) Main constituent of vinyl aromatic compound
And at least two polymer blocks A and a conjugated diene
At least one compound whose main constituent is
A block copolymer comprising a polymer block B, and
/ Or hydrogenated block co-gravity obtained by hydrogenating this
100 parts by weight of coalescence, (b) 50 softening agent for non-aromatic rubber
To 150 parts by weight, (c) polypropylene resin 40 to 60
0 parts by weight, and (d) organic peroxide 0.1 to 3
Vinyl aromatic thermoplastic elastomer blended with parts by weight
Composition (A) is the main resin component, and
Aromatic thermoplastic elastomer composition (A) 100 parts by weight
On the other hand, it contains 50 to 300 parts by weight of metal hydrate.
As the metal hydrate of (i) the metal hydrate is 50 parts by weight or more.
Above 100 parts by weight, vinyl aromatic thermoplastic
Part 5 per 100 parts by weight of the elastomer composition (A)
0 parts by weight or more, and (ii) metal hydrate 100 parts by weight
If more than 300 parts by weight, at least half
Pretreated metal hydrates pretreated with orchid coupling agents
RuThe insulating resin composition is prepared by kneading the mixture under heating.
A partially crosslinked structure is formed in the presence of organic peroxide.
Let me downAn insulating resin composition, (2) The vinyl aromatic thermoplastic elastomer according to the item (1)
The mar composition (A) is the main resin component, and
100 aromatic aromatic thermoplastic composition (A)
2.5 to 16 parts by weight of red phosphorus and metallic water based on parts by weight
Includes 50 to 180 parts by weight of a hydrate and its metal hydrate
And (i) the metal hydrate is 50 parts by weight or more and 100 parts by weight or less.
When full, vinyl aromatic thermoplastic elastomer composition
50 parts by weight or more based on 100 parts by weight of the article (A),
(Ii) 100 parts by weight or more and 180 parts by weight of metal hydrate
Silane coupling of at least half of the following
Pretreated metal hydrate pretreated with chemicalsInsulating resin composition
However, the organic peroxide can be obtained by kneading the mixture under heating.
A partially crosslinked structure is formed in the presence ofCharacterized by
An insulating resin composition,(3) Further, it is characterized in that a crosslinking aid is added.
The insulating resin composition according to item (1) or (2), (4) That the kneading is performed at 180 to 240 ° C.
Insulation according to any one of (1) to (3), which is characterized by
Resin composition, (5) The metal hydrate pretreated with the silane coupling agent
Characterized by being reactive with resin components
(1), (2), (3)Or (Four) Insulation resin set
Adult, (6) The silane coupling agent is a vinyl group and / or
Is characterized by having an epoxy group
(1), (2), (3), (4)Or (5) Item
Edge resin composition, (7) (1) ~ (6) Insulation tree according to any one of
An insulated wire characterized by coating a conductor with a fat composition,
as well as (8) (1) ~ (6) Insulation tree according to any one of
An insulating member made of a fat composition is provided. Starting
In the light, metallic water pretreated with silane coupling agent
The Japanese product has reactivity with the resin component. Reactive here
Is the anti-reflective property that improves strength, wear resistance, and scratch resistance.
It means to generate a response.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. 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) means (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound. And a block copolymer containing at least one polymer block B containing a conjugated diene compound as a main component, and /
Alternatively, (b) 50 to 150 parts by weight of a non-aromatic softening agent for rubber, and (c) a 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) organic peroxide 0.
It is a composition containing 1 to 3 parts by weight. The vinyl aromatic thermoplastic elastomer composition (A) in the present invention is
When kneaded and heat-treated, the component (a) is cross-linked due to the presence of the component (d), while the component (c) is thermally decomposed to have an appropriately low molecular weight, so that the composition as a whole has excellent extrudability. It becomes a partially crosslinked product.

Component (a) Block Copolymer The component (a) of the present invention comprises at least two polymer blocks A containing a vinyl aromatic compound as a main constituent.
And a block copolymer comprising at least one polymer block B containing a conjugated diene compound as a main component, or a block copolymer obtained by hydrogenating the same, or a mixture thereof, for example, A- B-A, B-A-B
Examples thereof include vinyl aromatic compound-conjugated diene compound block copolymers having a structure such as —A and ABABABA, and hydrogenated products thereof. The (hydrogenated) block copolymer (hereinafter, the (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer) is a vinyl aromatic compound in an amount of 5 to 60. %, Preferably 20 to 50% by weight. The polymer block A, whose main constituent is a vinyl aromatic compound, preferably consists only of the vinyl aromatic compound or is more than 50% by weight, preferably 7%.
0% by weight or more of a vinyl aromatic compound and a (hydrogenated) conjugated diene compound (hereinafter, a (hydrogenated) conjugated diene compound means a conjugated diene compound and / or a hydrogenated conjugated diene compound. ) Is a copolymer block with. The polymer block B, whose main constituent is a (hydrogenated) conjugated diene compound, preferably consists only of a (hydrogenated) conjugated diene compound or is greater than 50% by weight, preferably 70% by weight. %
It is a copolymer block of the above (hydrogenated) conjugated diene compound and vinyl aromatic. In each of the polymer block A containing these vinyl aromatic compounds as its main constituents and the polymer block B containing its (hydrogenated) conjugated diene compound as its main constituents,
Distribution of repeating units derived from vinyl aromatic compounds or (hydrogenated) conjugated diene compounds in the molecular chain is random, tapered (one in which the monomer component increases or decreases along the molecular chain), partially block-shaped or these May be any combination. In the case where there are two or more polymer blocks A containing a vinyl aromatic compound as a main constituent, or polymer blocks B containing a (hydrogenated) conjugated diene compound as a main constituent,
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. Of these, styrene is preferred. As the conjugated diene compound, for example, one kind or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, butadiene,
Isoprene and combinations thereof are preferred. Polymer block B mainly composed of conjugated diene compound
The microstructure in can be arbitrarily selected. For example, in the polybutadiene block, those having a 1,2-microstructure of 20 to 50%, particularly 25 to 45% are preferable, and those in which at least 90% of butadiene-based aliphatic double bonds are hydrogenated are preferable. In the polyisoprene block, 70 to 1 of the isoprene compound is used.
00% by weight has a 1,4-microstructure and at least 90% of the 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 further preferably 100,000. ˜550,000, particularly preferably 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 radial or any combination thereof.

Many methods have been proposed as a method for producing these (hydrogenated) block copolymers, and a typical method is, for example, the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert solvent using a lithium catalyst or a Ziegler type catalyst. Further, for example, the hydrogenated block copolymer is obtained by hydrogenating the block copolymer obtained by the above method in the presence of a hydrogenation catalyst in an inert solvent. 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. You can In the present invention, a particularly preferred (hydrogenated) block copolymer is a polymer block A whose main component is styrene, and isoprene whose main component is 7
0-100% by weight has a 1,4-microstructure and at least 90% of the isoprene-based aliphatic double bonds
Is a hydrogenated block copolymer having a weight average molecular weight of 50,000 to 550,000 and a polymer block B which has been hydrogenated. More preferably, 90 to 100% by weight of isoprene is the hydrogenated block copolymer having a 1,4-microstructure.

Component (b) Non-aromatic Softening Agent for Rubber As the component (b) of the present invention, a non-aromatic mineral oil or a liquid or low molecular weight synthetic softening agent can be used. The mineral oil softening agent used for rubber is a mixture of three aromatic ring, naphthene ring and paraffin chain, and paraffin chain carbon number occupies 50% or more of total carbon number. Those having a naphthene ring carbon number of 30 to 40% are called naphthene type, and those having an aromatic carbon number of 30% or more are called aromatic type. The mineral oil type rubber softening agents used as the component (b) of the present invention are paraffin type and naphthene type softeners in the above categories. The aromatic softening agent is not preferable because the component (a) becomes soluble due to its use, the crosslinking reaction is inhibited, and the physical properties of the obtained composition cannot be improved. As the component (b), a paraffinic one is preferable, and a paraffinic one having a small amount of aromatic ring components is particularly preferable. The properties of these non-aromatic softeners for rubber 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
Those exhibiting 70 to 300 ° C. are preferable. The blending amount of the component (b) is 50 to 150 relative to 100 parts by weight of the component (a).
Parts by weight, preferably 80 to 120 parts by weight. 150
A blending amount of more than parts by weight is liable to cause bleeding out of the softening agent, may give tackiness to the final product, and deteriorates mechanical properties. Further, if the blending amount is less than 50 parts by weight, the flexibility of the obtained composition will be lost.
A part of the component (b) may be added after the heat treatment in the presence of peroxide, but this may cause bleeding out. The component (b) preferably has a weight average molecular weight of 100 to 2,000.

Component (c) Polypropylene resin As the polypropylene resin, homotype polypropylene or a copolymer of propylene and a small amount of other α-olefins such as 1-butene, 1-hexene and 4-methyl-1-pentene. Can be used. When the elastomer composition (A) is subjected to heat treatment in the present invention to produce a partially crosslinked product, the polypropylene resin as the component (c) may be partly blended after heat treatment (crosslinking). The polypropylene resin compounded in (A) before the heat (crosslinking) treatment is
Due to the presence of the component (d), it is thermally decomposed to have an appropriately low molecular weight. As polypropylene resin to be blended before heat treatment,
MFR (ASTM-D-1238, L condition, 230 ° C)
Is preferably 0.1 to 10 g / 10 minutes, more preferably 0.1 to 5 g / 10 minutes, still more preferably 0.1 to 3 g.
/ 10 minutes is used. 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 resulting elastomer is poor. On the other hand, when MFR exceeds 10 g / 10 minutes, the molecular weight becomes too low and The rubber elasticity of the resulting elastomer composition is deteriorated, which is not preferable. The polypropylene resin to be blended after the heat treatment may be one that meets the conditions at the time of extrusion for forming the coating layer or at the time of molding the insulating member by injection molding or the like, and the MFR is preferably 5 to 200 g / 10 min. , And more preferably 8 to 1
50 g / 10 minutes, more preferably 10-100 g / 10
Use the minute one. When compounded 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.
If the amount exceeds the limit, the rubber elasticity of the obtained elastomer composition deteriorates, which is not preferable. The compounding amount of the polypropylene resin (c) is 4 with respect to 100 parts by weight of the component (a).
The amount is 0 to 600 parts by weight, preferably 50 to 500 parts by weight, and more preferably 100 to 200 parts by weight. If the compounding amount of this polypropylene is less than 40 parts by weight, the strength will be significantly reduced and the extrusion fluctuation will be large. On the other hand, if the blending amount exceeds 600 parts by weight, the flexibility is significantly 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 and 2,5-dimethyl-2,5-di-from the viewpoint of odor, coloring and scorch stability. Most preferred is (tert-butylperoxy) hexyne-3. The amount of peroxide (d) added is in the range of 0.1 to 3 parts by weight, preferably 0.1, based on 100 parts by weight of component (a).
~ 1.5 parts by weight. If it is less than 0.1 part by weight, the required crosslinking cannot be obtained. If it exceeds 3 parts by weight, crosslinking will proceed too much, resulting in poor dispersion of the partially crosslinked product and extremely poor fluidity of the composition.

In the production of the thermoplastic elastomer composition (A) of the present invention, a polyfunctional vinyl monomer such as divinylbenzene or triallyl cyanurate, or ethylene glycol dimethacrylate during the partial crosslinking treatment with an organic peroxide, A polyfunctional methacrylate monomer such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate or allyl methacrylate can be added 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 action, and acts as a dispersion aid of peroxide, so that the crosslinking effect by heat treatment is uniform and effective, and the hardness and It is most preferable because a partially crosslinked thermoplastic elastomer having a balanced rubber elasticity can be obtained. The addition 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 parts by weight, based on 100 parts by weight of the component (a). Yes, and more preferably 0.3 to 0.75 parts by weight. The amount of the crosslinking aid added is about 2 to 2.5 times the amount of the peroxide added by weight.
It is preferable to double the amount. If the amount is less than 0.02 parts by weight relative to 100 parts by weight of the component (a), the required crosslinking cannot be obtained. On the other hand, if the amount exceeds 1.5 parts by weight, the polymerization of the excessive crosslinking aid proceeds too much to easily form a crosslinked gel, and the fluidity of the composition is extremely deteriorated.

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

As the aluminum hydroxide pretreated with a silane coupling agent that can be used in the present invention, surface-untreated aluminum hydroxide (such as Hydilite H42M (trade name, manufactured by Showa Denko KK)) is used as the vinyl group or Examples thereof include those surface-treated with a silane coupling agent having an epoxy group at the end. The surface-untreated magnesium hydroxide pretreated with a silane coupling agent that can be used in the present invention (such as Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd. as a commercially available product)), stearic acid, olein A silane cup having the above vinyl group or epoxy group at the end thereof, such as those surface-treated with a fatty acid such as acid (Kisuma 5A, Kisuma 5B (trade name, manufactured by Kyowa Chemical Co., Ltd.), etc. A commercially available product of magnesium hydroxide (Kisuma 5) 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 the end.
LH, Kisuma 5PH (both are 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 the terminal is additionally performed on magnesium hydroxide or aluminum hydroxide partially surface-treated with a fatty acid or a phosphoric acid ester in advance. The hydrated metal hydrate and the like can also be used.

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

In addition to a metal hydrate surface-treated with a silane coupling agent having a vinyl group or an epoxy group at the terminal, a metal hydrate surface-treated with a material other than the silane coupling agent having a vinyl group or an epoxy group at the terminal. Although a metal hydrate or untreated metal hydrate can be used, 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 end. To be the hydrated metal hydrate.

In the insulating resin composition of the present invention, one of the molecular (cross-linked) structures formed by the cross-linking reaction in the presence of the component (d) organic peroxide is the (a) component block copolymer. A cross-linking structure (I) between resin and resin formed by bonding a cross-linking aid between molecular chains,
The other is a resin-metal hydrate (resin-filler) formed between the molecular chain in the component (a) block copolymer and a pretreated metal hydrate pretreated with a silane coupling agent. It is considered to be a crosslinked structure (II) between the two. In particular, regarding the latter (II), the pretreated metal hydrate pretreated with the silane coupling agent has a reactive site (a) of the silane coupling agent due to the organic peroxide of the component (d) during kneading and forming the resin composition. It is believed that it will function as a reinforcing agent for the resin molded product by combining with the block copolymer of the component). As a result, the mechanical strength, particularly the microdeformation strength, is improved, so that the molded body is kept from scratching and wear resistance is maintained. Therefore, by adding a sufficient amount of the pretreated metal hydrate pretreated with the silane coupling agent to the resin, a resin composition and a resin molded product having strength, abrasion resistance and scratch resistance can be obtained. If the addition amount of the pretreated metal hydrate pretreated by this silane coupling is small, desired characteristics cannot be obtained. Further, even if the amount of organic peroxide added is small, desired characteristics cannot be obtained. Further, since any crosslinked structure is a partial crosslink for the resin,
That is, since it contains a flowable —CH ₂ — chain, it can be extruded after kneading as in the case of a normal thermoplastic elastomer, and it is also possible to collect and re-extrude a molded body. Further, the reaction with the organic peroxide can further improve the heat distortion temperature of the resin composition or the extrusion molded body. As a conventionally known composition, for example, there is a composition described in JP-A-58-132032, which does not require crosslinking with electron beams, ultraviolet rays, water and the like. Rather, it has a molecular structure different from that of the insulating resin composition of the present invention, which is intended to simultaneously perform resin-resin crosslinking and resin-filler crosslinking. That is, in the case of the composition described in JP-A-58-132032, the role of the unsaturated silane compound is mainly to cross-link the resins with each other. It is a resin mixture obtained by water-crosslinking in which the resin reacts with each other and the resin molecules crosslink with each other due to the catalytic action when the molded body is produced. In this case, it is impossible to re-extrude after forming the molded body, and it is hard to get scratches,
The effect of maintaining strength is small. Further, in this case, the crosslinking reaction proceeds due to the water content of the filler, and the water crosslinking reaction proceeds when a large amount of a filler such as a metal hydrate that easily contains water is added, and the molding and molding may have a nuisance or appearance. A phenomenon occurs in which extrusion becomes difficult.

Further, it is preferable to use a metal hydrate together with red phosphorus when it is desired to further improve the flame retardancy. When added, the content of the metal hydrate is 50 parts by weight when used in combination with red phosphorus, relative 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 are preferable, and when not used together, it is 50 parts by weight to 300 parts by weight. Particularly when used in combination with red phosphorus, it is particularly preferable to use 90 parts by weight to 150 parts by weight of a metal hydrate together with 8 parts by weight to 16 parts by weight of red phosphorus, which makes it possible to meet vertical flame retardancy. Becomes In addition, when the metal hydrate is used without the combined use of red phosphorus, the metal hydrate is 50 parts by weight or more, and in the system in which the red phosphorus is also used, the metal hydrate is added in an amount of 50 parts by weight or more to obtain JIS C It is compatible with the horizontal flame retardancy specified in 3005. However, if the compounding amount exceeds 300 parts by weight in the system containing no red phosphorus and exceeds 180 parts by weight in the system containing red phosphorus, the strength is greatly reduced. The compounding amount is preferably 280 parts by weight or less in a system containing no red phosphorus, and 150 parts by weight or less in a system containing red phosphorus. For insulating members such as power plugs, the content of the metal hydrate is 100% by weight of the vinyl aromatic thermoplastic elastomer composition (A) in the resin composition of the present invention in combination with red phosphorus. When it is used, it is preferably 50 to 180 parts by weight, and when it is not used in combination, it is preferably 50 to 300 parts by weight. In the present invention, a predetermined amount of the metal hydrate used is a pretreated metal hydrate pretreated with a silane coupling agent. That is, when the amount of the metal hydrate (i) is 50 parts by weight or more and less than 100 parts by weight, 50 parts by weight or more of the vinyl aromatic thermoplastic elastomer composition (A) and (ii) ) When the amount of the metal hydrate is 100 parts by weight or more, at least half of the amount is a pretreated metal hydrate pretreated with a silane coupling agent. It is considered that the silane coupling agent causes a grafting reaction on the metal hydrate by this pretreatment. When the amount of the pretreated metal hydrate pretreated with the silane coupling agent is not more than the predetermined amount, the strength is remarkably reduced, and further the abrasion resistance and scratch resistance of the molded body are remarkably reduced. Further, in the pre-treated metal hydrate pretreated with the silane coupling agent, the reactive site is bonded and retained with the component (a) block copolymer during kneading and forming the resin composition,
Even if a large amount of metal hydrate is added, the strength does not decrease, and a large amount of filler can be added to the resin. Therefore, if the combined amount of the metal hydrates, pretreated and untreated, is 180 parts by weight or less when used in combination with red phosphorus, and 300 parts or less when not used in combination, no significant decrease in strength occurs. Does not happen.

(C) Red phosphorus In the present invention, red phosphorus may be added to the resin composition of the present invention for the purpose of improving the flame retardancy of the insulated wire or insulating member. Red phosphorus is particularly preferably used in combination with the metal hydrate to remarkably improve flame retardancy. When added, the content of red phosphorus is preferably 2.5 to 16 parts by weight, more preferably 8 to 13 parts by weight, based on 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A). is there. Red phosphorus content is 2.5
If it is less than 16 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 16 parts by weight, mechanical properties such as tensile strength and tensile elongation are deteriorated, which is not preferable. Further, more preferably, by setting the compounding amount of red phosphorus to 8 parts by weight or more, not only the graded flame retardancy defined by JIS C 3005 but also the vertical flame retardancy defined by UL1581 is maintained. You can For red phosphorus, heat,
From the viewpoint of stability against moisture and dispersibility in the resin composition, those subjected to surface treatment are preferable, and further, from the viewpoint of suppressing deterioration of physical properties of the resin composition and improving flame retardancy, the average particle diameter is 10 μm. The following is more preferable, and that of 5 μm or less is more preferable. "Novaret", "Nova Excel", "Novaquel" (brand name,
Commercial products such as Rin Kagaku Kogyo Co., Ltd. can be used.

(D) Ammonium polyphosphate In the present invention, an ammonium polyphosphate flame retardant may be added to the resin composition of the present invention in order to impart flame retardancy to the insulated wire or insulating member. Ammonium polyphosphate is preferable because it is a colorless phosphorus flame retardant and can be easily colored. Ammonium polyphosphate flame retardants include ammonium polyphosphate alone or those containing isocyanuric acid or its derivative, melamine /
Examples include those coated with formaldehyde resin. When ammonium polyphosphate containing isocyanuric acid or its derivative is used, the flame retardancy of the insulated wire or the insulating member can be further improved, and among them, tris (2-hydroxyethyl) isocyanurate and polypropylene resin It is preferable in terms of affinity and flame retardancy. Further, 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. As such, "Hostaflam AP422", "Hostaflam AP423", "Hostaflam AP462"
"Hostaflam AP745" (trade name, Hoechst
Manufactured by Sumitomo Chemical Co., Ltd.), “Sumisafe P” and “Sumisafe PM” (trade name, manufactured by Sumitomo Chemical Co., Ltd.). When added, the amount of ammonium polyphosphate is preferably 25 parts by weight to 100 parts by weight, more preferably 40 to 70 parts by weight, based on 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A). is there. If the content is less than 25 parts by weight, flame retardancy will be a problem, and if it is more than 100 parts by weight, the elongation will be significantly low.

The partially crosslinked molded article of the vinyl aromatic thermoplastic elastomer composition (A) in the present invention is not only flexible and hardly causes whitening when bent, but also red phosphorus and metallic water. It has the property that whitening does not easily occur when bent even when a large amount of filler such as Japanese powder is added. Also, when polyolefin resin such as ordinary polyethylene resin or polypropylene resin is used as a base resin and a large amount of red phosphorus or metal hydrate is added, the strength is greatly reduced. By using the thermoplastic elastomer composition (A), even if these fillers are added, the decrease in strength is suppressed to a minimum, and satisfactory properties as a wire coating material and insulating member forming material can be obtained. Furthermore, by using magnesium hydroxide whose surface has been treated with a silane coupling agent as magnesium hydroxide, it is possible to greatly reduce the decrease in strength, and to prevent scratches and bend insulating members such as electric wires and power plugs. It is possible to minimize the bleaching caused by blemishes. In particular, when a silane coupling agent having a vinyl group and / or an epoxy group as the terminal group is used, it is preferable because the strength retention and the scratch resistance are large.

In the present invention, silicone rubber, silicone oil, or silicone gum is used as a resin in order to further improve the flame retardancy and to control the adhesion between the conductor and the insulating layer (the coating layer containing the resin composition). It may be added to the composition, and examples thereof include linear, ladder-type silicone-containing compounds such as silicone rubber, silicone gum, and silicone oil. Although not particularly limited, examples of the silicone oil include polymethyl silicone oil, and examples of the silicone gum and silicone oil include polymethyl silicone gum and those having a three-dimensional structure. As a material, "SFR-100" (trade name, GE
Manufactured by Toray Silicone Co., Ltd.) and “CF-9150” (trade name, manufactured by Toray Silicone Co.). When added, the silicone rubber, silicone oil, and silicone gum are preferably
Vinyl aromatic thermoplastic elastomer composition (A) 10
0.5 to 6 parts by weight is blended with 0 parts by weight. 0.5
If it is less than 6 parts by weight, the effect is substantially lost, and if it exceeds 6 parts by weight, the appearance is deteriorated and the extrusion linear velocity is remarkably decreased, resulting in poor mass productivity. Silicone powder may be added to the resin composition, and examples of the silicone powder include silicone-containing compounds having a three-dimensional structure. The silicone powder is not particularly limited,
Product names include "Trefill" (manufactured by Toray Silicone) and "Tospearl" (manufactured by Toshiba Silicone). When added, this silicone resin powder is preferably
Vinyl aromatic thermoplastic elastomer composition (A) 10
2 to 20 parts by weight is blended with 0 parts by weight. If it is not added in an amount of 2 parts by weight or more, the substantial effect cannot be obtained, and if it exceeds 20 parts by weight, the mechanical strength and the elongation are remarkably lowered, and the extrusion property is remarkably lowered.

Other resins can be introduced into the electric wire coating resin composition of the present invention to the extent that the object of the present invention is not impaired, but at least the vinyl aromatic thermoplastic elastomer composition (A) is mainly used. Use as a resin component. Here, the term “main resin component” means usually 70% by weight or more, preferably 85% by weight or more, in the resin component of the insulating resin composition of the present invention.
More preferably, it means that the vinyl aromatic thermoplastic elastomer composition (A) occupies the whole amount of the resin component. Insulating resin composition for wire coating or insulating member formation in the present invention, various additives commonly used in wires, cables and power plugs,
For example, an antioxidant, a metal deactivator, a flame retardant (auxiliary) agent, a filler, a lubricant and the like can be appropriately added within a range that does not impair the object of the present invention. In particular, a resin composition containing a metal hydrate and / or an ammonium polyphosphate-based flame retardant without red phosphorus is white, so that a color batch containing a colorant and a polyolefin-based resin as a base resin is used. By blending, it can be easily colored in any color. Examples of the antioxidant include amine-based antioxidants such as 4,4'-dioctyl diphenylamine, N, N'-diphenyl-p-phenylenediamine, and a polymer of 2,2,4-trimethyl-1,2-dihydroquinoline. 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 other phenolic antioxidants, 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).

As the metal deactivator, N, N'-bis (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyl) hydrazine, 3- (N-salicyloyl) amino-1, 2,4-triazole, 2,2'-
Oxamido bis- (ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) and the like can be mentioned. Further, as flame retardant (auxiliary) agents and fillers, carbon, clay, zinc oxide, tin oxide, titanium oxide, magnesium oxide, molybdenum oxide, antimony trioxide, silicone compounds, quartz, talc, calcium carbonate, magnesium carbonate, boric acid. Examples include zinc and white carbon. Examples of lubricants include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based (eg magnesium stearate),
Among them, "Wax E""WaxOP" (trade name,
Ester-based lubricants having internal lubricity and external lubricity at the same time, such as those manufactured by Hoechst) 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 component (a) and the component (b) and at least a part of the component (c) (preferably 5 to 100% by weight in the amount of the component (c) used, more preferably 30 to). 100% by weight), metal hydrate, ammonium polyphosphate, flame retardant such as metal hydrate and red phosphorus, and if necessary, various additives such as filler, antioxidant, light stabilizer and colorant, Melt and knead in advance. The kneading temperature is preferably 160 to 240 ° C. As a kneading method, any method commonly used for rubber, plastic and the like can be satisfactorily used. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders can be used. By this step, a composition in which each component is uniformly dispersed can be obtained. In the second step, to the composition obtained in the first step, an organic peroxide as a component (d) and optionally a cross-linking aid are added, and further kneaded under heating to cause partial cross-linking. The temperature at this time is preferably 180 to 240 ° C. In this way, the components (a) to (c) are melt-kneaded in advance to generate a micro dispersion, and then the organic peroxide (d) is added and kneading is performed under heat treatment to form a partially crosslinked product. Provides particularly preferable physical properties. This process is
Generally, the 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 components may be mixed and melt-kneaded. In the third step, the partially crosslinked composition obtained in the second step is mixed with the remaining amount of each component. The kneading temperature is preferably 180 to 240 ° C. The kneading can be generally performed using a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders. In this step, the reaction is completed at the same time as the dispersion of each component further progresses. It is also possible to combine the first, second, and third steps into a single step, and melt-knead each component at once. In addition, the total amount of the component (c) is added in the first step, and then the second step is performed.
You may obtain the insulating resin composition of this invention through a process.

When a metal hydrate not surface-treated with a silane coupling agent, ammonium polyphosphate, red phosphorus or the like is added to the insulating resin composition of the present invention, the vinyl aromatic thermoplastic elastomer composition is partially cross-linked. After getting as a thing,
Alternatively, it may be added before partial crosslinking. However, when using pretreated magnesium hydroxide pretreated with a silane coupling agent, it must be added before or at the time of partial crosslinking. When added in the state before partial crosslinking, the silane coupling agent on the surface of the metal hydrate and the resin are bonded to each other, whereby a molded product that retains a large amount of strength and is hardly scratched can be obtained. In particular, the effect is remarkable when a silane coupling agent having a vinyl group and / or an epoxy group at the terminal is used. Further, in order to add a large amount of a filler such as magnesium hydroxide, it is preferable to add it at a stage before partial crosslinking even in the case of a metal hydrate that has not been surface-treated with a silane coupling agent, in terms of kneading ease. . The insulated wire of the present invention is not particularly limited, except that it has at least one coating layer formed by extrusion coating on the outer periphery of the conductor, the coating layer comprising the resin composition of the present invention. For example, as the conductor, any known wire such as a single wire or a twisted wire around the entire circumference can be used. 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 usual molding method such as injection molding. In the insulated wire of the present invention, the thickness of the insulating layer (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 wire of the present invention, it is preferable that the resin composition of the present invention, which is a partially cross-linked product, is extrusion coated to form the coating layer as it is, but for the purpose of further improving heat resistance. It is also possible to crosslink the coating layer after extrusion. However, if this cross-linking treatment is applied,
The coating layer cannot be reused as an extruded material. As a method for crosslinking, conventionally known electron beam irradiation crosslinking method and chemical crosslinking method can be adopted. In the case of the electron beam cross-linking method, the resin composition is extrusion-molded to form a coating layer, which is then cross-linked by irradiating it with an electron beam by a conventional method. The dose of the electron beam is appropriately 1 to 30 Mrad, and in order to carry out the crosslinking efficiently, the resin composition constituting the coating layer contains a methacrylic compound such as trimethylolpropane triacrylate or an allyl compound such as triallyl cyanurate. You may mix | blend a polyfunctional compound, such as a compound, a maleimide type compound, and a divinyl type compound, as a crosslinking aid. In the case of the chemical crosslinking method, the resin composition is blended with an organic peroxide as a crosslinking agent, extrusion-molded to form a coating layer, and then crosslinked by heat treatment by a conventional method.

[0030]

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

Unless otherwise noted, the numbers indicate parts by weight. Hydrogenated styrene-isoprene block copolymer (SEPS) as the component (a), paraffin oil as the component (b), homopolypropylene (MFR 8 g / 10 min) as the component (c), and dioctane as the component (d). A vinyl aromatic thermoplastic elastomer composition was produced in three steps using a twin screw extruder with L / D = 44, using mill peroxide and blending the components as shown in Table 1. First, the total amount of each of the components (a) and (b) other than the component (c) and the component (d) shown in Table 1 and the component (c).
15% by weight of the mixture was melt-kneaded (first step), and then component (d) and 2 parts by weight of triethylene glycol dimethacrylate as a crosslinking aid were added from the middle of the extruder and melt-kneaded (second step). ), And the rest of the component (c) was added from the middle of the extruder and melt-kneaded (third step). Melt-kneading was performed using a twin-screw extruder (L / D = 47) 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, 2nd step: 200-220 ° C, 3rd step: 2
00-220 ° C.

[0032]

[Table 1]

On the other hand, magnesium hydroxide surface-treated with a silane coupling agent having a vinyl group at the terminal (trade name, Kisuma 5LH, manufactured by Kyowa Chemical Industry Co., Ltd.) or magnesium hydroxide not surface-treated is used. An insulating resin composition having a composition as shown in Tables 2 to 4 was prepared using a surface-treated (pre-treated) silane coupling agent having a vinyl group at the terminal. Here, each composition was dry-blended at room temperature, put into a kneader, and melt-kneaded. A kneader having a capacity of 20 liters was used, and the number of rotations of the rotor was 40 rpm, and kneading was performed until the temperature of the melt-kneaded product reached 180 to 220 ° C.
Pelletized with a granulator.

[0034]

[Table 2]

[0035]

[Table 3]

[0036]

[Table 4]

[0037] (Example 1-19 and Comparative Example 1-16, Reference
Examples 1 to 3 ) First, dry-blend each component shown in Table 5 at room temperature,
A resin composition was prepared by melt-kneading with a Banbury mixer. From the obtained resin composition, by pressing,
1 mm sheets corresponding to Reference Examples 1 to 3 were prepared. next,
A conductor (conductor diameter:
0.95mmφ tinned annealed copper stranded wire Composition: 21/0.
18 mmφ) was coated with an insulating resin composition melt-kneaded in advance by an extrusion method so as to have an outer diameter of 2.63 mm to form an insulating coating layer, to produce insulated wires corresponding to Reference Examples 1 to 3. Separately from this, using each insulating resin composition obtained by melting and kneading the components shown in Tables 2 to 4 and pelletizing the components,
Extrusion coating on the conductor in the same manner as described above, Examples 1 to 19 ,
Insulated electric wires corresponding to Comparative Examples 1 to 16 were manufactured.

The tensile properties (elongation (%) and strength (tensile strength, MPa)) and heat deformation properties of each of the obtained sheets were evaluated, and the results are also shown in Tables 5-8. Each property was performed based on JIS K 6723, and the heat deformation test was performed at 120 ° C. Regarding each characteristic of the sheet, an elongation of 100% or more and a strength of 10 MPa or more were passed, and a heat deformation was 30% or less of a deformation rate. on the other hand,
For each of the obtained insulated wires, tensile properties, flame retardancy 1, flame retardancy 2, appearance, flexibility, whitening properties when the cable is bent,
The heat deformation characteristics were evaluated, and the results are also shown in Tables 5-8. Tensile properties are the strength (tensile strength) (MPa) and elongation (%) of the coating layer of each insulated wire, the distance between marked lines is 25 mm, the pulling speed is 500 mm / min. It was measured under the conditions. Growth is 1
The composition must have a strength of 50% or higher and a strength of 10 MPa or higher. Flame retardancy 1 is UL1581 for each insulated wire.
Vertical combustion test (VW-1) was conducted and the result is shown by the number of passed / the number of tests. Regarding the flame retardance 2, the horizontal flame retardancy test shown in JIS C 3005 was performed on each insulated wire, and the number of passed products / the number of tests was shown. For the appearance, visually check the appearance of the insulated wire, and if it is good, ○,
The ones that are slightly rough are indicated by △, and those that are severely rough are indicated by ×. Those marked with x and Δ cannot be put to practical use.
The flexibility was evaluated by the test method whose schematic diagram is shown in FIG. A sample (1) was prepared by cutting each insulated wire to a length of 20 cm, 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
When it is less than m, it is ×, when it is 1 cm or more and less than 3 cm, Δ,
In case of 3 cm or more, it is indicated by ◯. Those with × are poor in flexibility and cannot be put to practical use as insulated wires. The whitening property when the cable was bent was evaluated based on whether the whitening occurred when the cable was wound around a mandrel having a self-diameter. It was wound 10 times, and when there was no whitening at all, it was shown as O when whitening occurs 3 times or less, and when whitening occurs 4 times or more. Those marked with X cannot be put to practical use. UL1 heat distortion characteristics
581, according to a heat deformation test, was carried out at 136 ° C. The results are shown by the 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 Micro structure: 1,4-micro structure number average molecular weight: 260 Weight average molecular weight: 320,000 Molecular weight distribution: 1.23 Hydrogenation rate: 90% or more Component (b): Non-aromatic softening agent for rubber Idemitsu Kosan Co., Ltd. Product name: Diana Process Oil PW-
90 types: paraffin oil weight average molecular weight: 540 Aromatic component content: 0.1% or less Component (c): polypropylene resin Tokuyama product name: ME140 Type: homopolymer melt index (measurement temperature 190 ° C , Measured load
2.16 kg): 8.5 g / 10 min.-Component (d): Organic peroxide chemical agent manufactured by Akzo Co., Ltd. Product name: Kayakumil D Type: Dicumyl peroxide / Crosslinking aid: Shin Nakamura Chemical Co., Ltd. Product name: NK Ester 3G Type: Triethylene glycol dimethacrylate

Magnesium hydroxide Kyowa Chemical Co., Ltd. product name: Kisuma 5B (magnesium hydroxide surface-treated with oleic acid) Kyowa Chemical Co., Ltd. product name: Kisuma 5LH (silane coupling agent having a vinyl group at the end Surface-treated magnesium hydroxide) Kyowa Scientific Co., Ltd. product name: Kisuma 5 (non-surface treatment) -Silane coupling agent Toshiba Silicone product name: TSL8370 (silane coupling agent having a vinyl group at the end) -Polyphosphoric acid Ammonium flame retardant Hoechst Co. product name: Hostaflam AP462 ・ Antioxidant pentaerythrityl-tetrakis (3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionate) Ciba-Geigy product name: Irganox 1
010-Lubricant montanic acid partially saponified ester wax Hoechst Co. product name: Wax OP-Akarin Rin Kagaku Co. product name: Nova Excel F5-Random polypropylene grand polymer 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 of Tables 5 to 8, (a) at least two polymer blocks A containing a vinyl aromatic compound as a main component and at least one polymer block B containing a conjugated diene compound as a main component. (B) 50 to 150 parts by weight of a softening agent for non-aromatic rubber, and (c) polypropylene based on 100 parts by weight of a block copolymer and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer. Resin 40
To 600 parts by weight, (d) organic peroxide 0.1 to 3
It can be seen that the system using the vinyl aromatic thermoplastic elastomer composition blended with parts by weight is excellent in heat resistance, flexibility and strength. In addition, red phosphorus and metal hydrate, metal hydrate,
A predetermined amount of ammonium polyphosphate is blended, and when a metal hydrate is used, a predetermined amount of the pretreated metal hydrate is pretreated with a silane coupling agent to obtain flame retardancy and strength, and further heat resistance, It can be seen that a flame-retardant insulated wire that is excellent in flexibility and does not whiten even when bent is obtained.

On the other hand, particularly Comparative Examples 11, 12, and 1
In No. 3, since no pretreated metal hydrate was used, any of the properties was extremely inferior to the examples of the present invention. Comparative Example 11: Since the metal hydrate was added after the partial crosslinking reaction of the elastomer composition (A) was completed, the effects (strength, appearance) of the present invention were not recognized. Comparative Example 12: After completion of the silane grafting and the partial crosslinking reaction of the elastomer composition (A), a metal hydrate (pretreated or untreated, treated with a substance other than the silane coupling agent) was used. It was the same when used.)
However, as in Comparative Example 11, the effect of the present invention was not recognized. Comparative Example 13: A compound having the composition of Example 20 was prepared by the following method in which magnesium hydroxide and the silane coupling agent were not mixed in advance. Hydrogenated styrene
Isoprene block copolymer (SEPS), paraffin oil, homopolypropylene (MFR 8g / 10min),
The surface-untreated metal hydrate was first mixed with a Banbury mixer, then dicumyl peroxide and silane coupling were added, and the mixture was kneaded with the Banbury mixer and discharged. The obtained compound was difficult to re-mold, and many lumps were present on the sheet surface, and extrusion was impossible.

With respect to the compositions I, J and K, in addition to the evaluation with electric wires, the characteristics after molding into plug terminals were evaluated. The composition I, J or K was used to perform injection molding on each of the terminals for the power plug to which the two electric wires prepared in Example 4 were connected by an injection molding machine to mold the power plug. These power plugs were molded at an injection temperature of 230 ° C. The obtained molded plugs all had a good appearance and did not shrink due to the material. Furthermore, the flame of the burner used in the flame retardant test specified by JIS C3005 was applied to the power plug for 15 seconds, but when the flame was separated, extinguishing was confirmed instantly.

[0048]

INDUSTRIAL APPLICABILITY 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 and combustion. . Further, the insulated wire and the insulating member of the present invention are excellent in flame retardancy, strength, heat resistance and flexibility, and do not whiten even when bent. As described above, the insulated wire of the present invention has excellent characteristics as a non-halogen 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 high heat resistance can be achieved without crosslinking the entire resin composition. The insulated wire of No. 2 has high heat resistance, and the coating layer can be remelted and is highly recyclable. From the above, the insulated wire of the present invention is very useful as a wire or a cord for electric / electronic equipment in consideration of environmental problems. Further, the resin composition of the present invention, as a coating material for such wiring or cord,
It is also suitable as a material for the insulating member, and also as a tube or tape material.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a flexibility testing method.

[Explanation of symbols]

1 Electric wire sample 2 walls L Height difference (cm)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI H01B 15/00 H01B 15/00 // H01B 7/29 17/56 A 17/56 17/58 F 17/58 7/34 A (72) Inventor Gakuyuki Kajiyama 3-20-3 Ryoke, Urawa City, Saitama Prefecture (72) Inventor Shinzo Saito 1-9-9, Higashi Kojiya, Ota-ku, Tokyo (56) Reference JP-A-60-180009 (JP, A) ) JP-A-4-23842 (JP, A) JP-A-9-31267 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) H01B 3/00 H01B 3/44 H01B 7 / 29 H01B 15/00 H01B 17/56 H01B 17/58 C08K 9/00 C08L 23/10 C08L 53/02

Claims (8)

(57) [Claims] 1. (a) at least two polymer blocks A whose main constituent is a vinyl aromatic compound,
A block copolymer composed of at least one polymer block B containing a conjugated diene compound as a main component, and / or 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the same, (b ) 50 to 150 parts by weight of a non-aromatic softening agent for rubber, (c) 40 to 600 parts by weight of polypropylene resin, and (d) a vinyl aromatic thermoplastic elastomer containing 0.1 to 3 parts by weight of organic peroxide. The composition (A) is a main resin component, and further, a vinyl aromatic thermoplastic elastomer composition (A)
If the metal hydrate is contained in an amount of 50 to 300 parts by weight with respect to 100 parts by weight and (i) the metal hydrate is 50 parts by weight or more and less than 100 parts by weight, the vinyl aromatic The silane coupling agent is 50 parts by weight or more based on 100 parts by weight of the thermoplastic elastomer composition (A), and (ii) at least half of the metal hydrate is 100 parts by weight or more and 300 parts by weight or less. An insulating resin composition that is a pretreated metal hydrate that has been pretreated with
Partial crosslinking in the presence of organic peroxide by kneading below
Insulating resin composition characterized by comprising to form a structure. 2. The vinyl aromatic thermoplastic elastomer composition (A) according to claim 1 is a main resin component, and further, the 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 are included with respect to 100 parts by weight, and (i) the metal hydrate is 50 parts by weight or more and 100 parts by weight as the metal hydrate. When the amount is less than 50 parts by weight, 50 parts by weight or more of 100 parts by weight of the vinyl aromatic thermoplastic elastomer composition (A) and (ii) 100 parts by weight or more of 180 parts by weight of the metal hydrate are contained.
Insulating resin containing at least half of its weight as pretreated metal hydrate pretreated with silane coupling agent
The composition is a mixture of organic components by kneading the mixture under heating.
An insulating resin composition comprising a partially crosslinked structure formed in the presence of oxide . 3. A cross-linking aid is further included in the composition.
The insulating resin composition according to claim 1, which is a characteristic of the insulating resin composition. 4. The kneading is performed at 180 to 240 ° C.
Characterized by The method according to any one of claims 1 to 3.
Insulating resin composition. 5. The insulating resin composition according to claim 1, 2 , 3 or 4 , wherein the metal hydrate pretreated with the silane coupling agent is reactive with the resin component. 6. silane coupling agent, claims 1, 2, 3, characterized in that those having a vinyl group and / or an epoxy group, 4 or 5 the insulating resin composition. 7. An insulated electric wire comprising a conductor coated with the insulating resin composition according to any one of claims 1 to 6 . 8. An insulating member comprising the insulating resin composition according to any one of claims 1 to 6 .