JP3515439B2 - Flame retardant resin composition and molded parts 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 a flame-retardant resin composition having excellent mechanical properties and flexibility as well as heat resistance, a wiring material using the composition as a coating material, an optical fiber cord and other molded parts. It is a thing. More specifically, the present invention provides
Insulated electric wires, electric cables, electric cords and optical fiber core wires used for internal or external wiring of electrical and electronic equipment,
A flame-retardant resin composition suitable as a coating material for optical fiber cords, etc., and wiring materials and other molded parts using the same, in particular, at the time of disposal such as landfill and combustion, elution of heavy metal compounds and a large amount of smoke, The present invention relates to a flame-retardant resin composition that does not generate a corrosive gas and is suitable for recycling after use, and that is environmentally friendly, and a wiring material and other molded parts using the same.

[0002]

2. Description of the Related Art Insulated wires, cables, cords, optical fiber cores, and optical fiber cords used for internal and external wiring of electrical and electronic equipment have flame retardancy, heat resistance, mechanical properties (for example, tensile properties). , Abrasion resistance) and various other characteristics are required. Therefore, as a coating material used for these wiring materials, a polyvinyl chloride (PVC) compound or a polyolefin compound containing a halogen-based flame retardant containing a bromine atom or a chlorine atom in the molecule is mainly used. It was However, if these materials are disposed of without proper treatment and landfilled, the plasticizer and heavy metal stabilizer contained in the coating material will elute, and if burned, they will be included in the coating material. A corrosive gas may be generated from the halogen compound to be generated, and in recent years, this problem has been discussed. For this reason, wiring materials coated with non-halogen flame-retardant materials that are not likely to cause harmful plasticizers or heavy metals to elute or generate halogen-based gas, which are feared to affect the environment, are being studied. . Non-halogen flame retardant materials exhibit flame retardancy by blending a flame retardant that does not contain halogen with resin.
1-butene copolymer, ethylene / propylene copolymer,
Ethylene-based copolymers such as ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene-diene terpolymer, and metal water such as aluminum hydroxide and magnesium hydroxide as flame retardants. A material containing a large amount of Japanese products is used for the wiring material.

Standards such as flame retardancy, heat resistance, mechanical properties (for example, tensile properties, wear resistance) required for wiring materials for electric and electronic devices are defined by UL, JIS and the like. In particular, regarding flame retardancy, the test method changes depending on the required level (use thereof) and the like. So in fact,
It should have flame retardancy at least according to the required level. For example, UL1581 (related standards for wires, cables and flexible cords (Reference St
and for for Electrical Wire
s, Cables and Flexible Cor
ds)) vertical combustion test (Vertical)
Frame Test) (VW-1) and JIS C
3005 (rubber / plastic insulated wire test method) specifies the flame resistance and the like that pass the horizontal test and the tilt test. Among these, in the case of imparting a high degree of flame retardancy to a non-halogen flame-retardant material so far as to pass VW-1 or a gradient test, 100 parts by weight of a resin component such as an ethylene-based copolymer, It is necessary to mix 120 parts by weight or more of a metal hydrate which is a flame retardant, and as a result, there is a problem that mechanical properties such as tensile properties and abrasion resistance of the coating material are significantly reduced. In order to solve this problem, the compounding amount of the metal hydrate is decreased (for example, 1 part of the metal hydrate as a flame retardant is added to 100 parts by weight of the resin).
About 20 parts by weight) and red phosphorus are used. By the way, wiring materials that are currently used in electrical and electronic equipment, such as polyvinyl chloride compounds and polyolefin compounds mixed with halogen-based flame retardants, are used as coating materials for the purpose of distinguishing the type of wiring material and the connection part. It is used by printing on the surface of electric wires, electric cables and electric cords, or by coloring it in several different colors. However, the non-halogen coating material containing metal hydrate and red phosphorus in order to achieve both high flame retardancy and mechanical properties is
There is a problem that a wiring material, which cannot be printed on or colored in an arbitrary color because of the color development of red phosphorus, cannot easily provide a wiring material whose type and connection portion can be distinguished. Further, regarding phosphorus released from a flame-retardant material containing phosphorus after disposal, environmental impact, for example, pollution of water resources due to eutrophication has become a problem.

Further, wiring materials used in electric and electronic equipment may be required to have heat resistance of 80 ° C. to 105 ° C., and further 125 ° C. in a continuous use state. In such a case, a method of cross-linking the coating material by an electron beam cross-linking method, a chemical cross-linking method, or the like is used for the purpose of imparting high heat resistance to the wiring material. However, while the cross-linked wiring material has improved heat resistance of the coating material, it cannot be re-melted, which makes reuse difficult,
It has been pointed out that recyclability is poor. For example, when recovering the metal used for the conductor, it is often necessary to burn the coating material, etc., and avoid the above-mentioned environmental problems associated with conventional coating materials containing halogen or phosphorus. I can't. On the other hand, as a method of achieving heat resistance of about 105 ° C. in a wiring material that does not crosslink, there is a method of using a resin having a high melting point such as polypropylene resin. However, although such a resin has good heat resistance, it is poor in flexibility, and when the wiring material covering it is bent, the phenomenon of whitening of the surface is observed. This whitening phenomenon is not observed in the wiring material coated with polyvinyl chloride compound that is currently used in electric and electronic devices. On the other hand, in a wiring material coated with a non-halogen flame-retardant material containing a large amount of metal hydrate, this whitening phenomenon is severe regardless of the presence or absence of crosslinking. Therefore, there is still a demand for improvement in using a non-halogen flame-retardant material that is whitened by the current bending as a wiring material. Since the maximum operating temperature of the wiring material coated with polyvinyl chloride compound is about UL 105 ° C., the non-halogen flame-retardant material that substitutes for this wiring material also needs to have this heat resistance. Specifically, UL105 ℃
Since a heat deformation test in a 136 ° C. atmosphere, a heat aging test, etc. are required for the heat resistance of No. 1, it is necessary that the non-halogen flame-retardant material to be substituted does not melt at least at 136 ° C. In addition, molded parts such as power plugs have the same problems as above, heat resistance, flexibility,
Development of recyclable and remoldable molded parts that are flame retardant is required.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above problems and is excellent in flame retardancy, heat resistance and mechanical properties, and elutes heavy metal compounds at the time of disposal such as landfill and combustion, It is an object of the present invention to provide a flame-retardant resin composition and a molded article that do not generate a large amount of smoke and corrosive gas and that meet recent environmental problems. Further, the present invention is a flame-retardant resin composition which is reusable because the coating material can be remelted while satisfying these characteristics, does not whiten even when bent, and is hard to be scratched, and wiring using the same. The object is to provide a material, an optical fiber core wire, an optical fiber cord, and other molded parts.

[0006]

In order to achieve the above object, in the present invention, (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 ) A thermoplastic resin component comprising 10 to 100 parts by weight of a non-aromatic rubber softening agent, (c) 30 to 400 parts by weight of an ethylene / α-olefin copolymer, and (d) 0 to 200 parts by weight of a polypropylene resin ( A) For 100 parts by weight, (e)
0.01 to 0.6 part by weight of organic peroxide, (f)
(Meth) acrylate-based and / or allyl-based cross-linking aid 0.03 to 1.8 parts by weight, and the metal hydrate (B) at a ratio of 50 to 300 parts by weight, the metal hydrate (B (I) When the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher; (2) (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 ) A thermoplastic resin component comprising 10 to 100 parts by weight of a non-aromatic softening agent for rubber, (c) 50 to 250 parts by weight of an ethylene / α-olefin copolymer, and (d) 0 to 100 parts by weight of a polypropylene resin. A) relative to 100 parts by weight,
(E) 0.01 to 0.6 parts by weight of organic peroxide,
(F) 0.03 to 1.8 parts by weight of a (meth) acrylate-based and / or allyl-based crosslinking aid, and 50 to 300 parts by weight of the metal hydrate (B), When the amount of the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) 100 is
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of not more than 1 part by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition obtained by heating and kneading at a melting temperature or higher, (3) the crosslinking aid (f)
But the general formula

[0007]

[Chemical 2]

(Wherein R is H or CH ₃ and n is an integer of 1 to 9) is a (meth) acrylate-based cross-linking aid (1) or The flame-retardant resin composition according to the item (2). (4) The flame-retardant resin composition according to any one of (1) to (3), wherein the metal hydrate (B) is magnesium hydroxide, and (5) a silane coupling agent. Is a silane compound having a vinyl group and / or an epoxy group at the terminal, and the flame-retardant resin composition according to any one of (1) to (4), (6) (1), (3) to (5) The flame-retardant resin composition according to any one of (1) to (3), which has a conductor, or an optical fiber element wire or / and an optical fiber core wire as a coating layer on the outside, (7) (2)
To (5), a molded part obtained by molding the flame-retardant resin composition according to any one of (5), (8), (1) to
The flame-retardant resin composition according to any one of (5), wherein (a) at least two polymer blocks A containing a vinyl aromatic compound as a main constituent and a conjugated diene compound as a constituent A block copolymer consisting of at least one polymer block B mainly composed of
Alternatively, a hydrogenated block copolymer obtained by hydrogenating the same, (b) a non-aromatic rubber softening agent, (c) ethylene
α-olefin copolymer, (d) polypropylene resin,
(E) Organic peroxide, (f) (meth) acrylate-based and / or allyl-based crosslinking aid, and metal hydrate (B) are simultaneously heated at a melting temperature of the thermoplastic resin component (A) or higher. A method for producing a flame-retardant resin composition, which comprises kneading and crosslinking, and (9) (1) to
In the flame-retardant resin composition according to any one of (5), in the first step, (a) 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, and / or a hydrogenated block copolymer obtained by hydrogenating the same, (b) Non-aromatic rubber softener,
(C) Ethylene / α-olefin copolymer and (d) polypropylene resin are heated and kneaded to obtain a thermoplastic resin component (A). In the second step, the resin component (A) and (e) organic par Oxide, (f) (meth) acrylate-based and / or allyl-based crosslinking aid, and metal hydrate (B) are heated and kneaded at a temperature not lower than the melting temperature of the thermoplastic resin component (A) to carry out a crosslinking treatment. The present invention provides a method for producing a flame-retardant resin composition.

In the present invention, the amount of the organic peroxide and the amount and kind of the crosslinking aid contained together with the resin component can be appropriately set within the above range to form a loose crosslinked structure having a low crosslinking density. By selecting a specific metal hydrate, a large amount of metal hydrate can be blended.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, each component of the flame-retardant resin composition of the present invention will be described. (A) Thermoplastic resin component The thermoplastic resin component (A) includes (a) at least two polymer blocks A containing a vinyl aromatic compound as a main component, and a conjugated diene compound as a component. A block copolymer mainly composed of at least one polymer block B, and / or a hydrogenated block copolymer obtained by hydrogenating the same, (b) a non-aromatic rubber softener, c) an ethylene / α-olefin copolymer,
(D) Made of polypropylene resin.

Component (a) Block Copolymer The component (a) of the present invention comprises at least two polymer blocks A mainly composed of vinyl aromatic compounds.
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 greater 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 a vinyl aromatic compound. In each of the polymer block A containing the vinyl aromatic compound as the main constituent and the polymer block B containing the (hydrogenated) conjugated diene compound as the main constituent, the vinyl aromatic in the molecular chain is Distribution of repeating units from group compounds or (hydrogenated) conjugated diene compounds is random, tapered (increasing or decreasing monomer content along the molecular chain), partially blocky or any combination of these May be. 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. That is, those having a carbon number of naphthene ring 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-based softening agent for rubber used as the component (b) of the present invention is a paraffin-based or naphthene-based softener 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 resulting composition cannot be improved.
The component (b) is preferably paraffinic,
Further, among paraffins, those having a small amount of aromatic ring components are 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 10 to 100 with respect to 100 parts by weight of the component (a).
Parts by weight, preferably 30 to 70 parts by weight. If the blending amount is less than 10 parts by weight, the flexibility of the obtained wiring material will be lost. Further, if the amount exceeds 100 parts by weight, bleeding out of the softening agent is likely to occur, the wiring material may have tackiness, and the mechanical properties thereof are deteriorated.
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) Both ethylene and α-olefin
Polymer The component (c) of the present invention includes ethylene / α-olefin
A copolymer is used. Ethylene / α-olefin copolymerization
The body (c) is preferably ethylene and has 3 to 12 carbon atoms.
It is a copolymer with α-olefin,
Specific examples include propylene, 1-butene, 1-hexene.
, 4-methyl-1-pentene, 1-octene, 1-de
Examples include sen and 1-dodecene. For (c) ingredient
And when the α-olefin is propylene, propylene
The content of the component is less than 50%. Ethylene / α-ole
As the fin copolymer, LLDPE (linear low density polymer
Polyethylene), LDPE (low density polyethylene), VL
DPE (Ultra Low Density Polyethylene) and Single Site
Ethylene / α-olefin copolymerization synthesized in the presence of catalyst
There is coalescence etc. Among them, the filler acceptance to be filled
And the flexibility of the resin composition targeted by the present invention are considered.
Then, the ethylene synthesized in the presence of a single-site catalyst
And .alpha.-olefin copolymers are preferable, and the density is 0.
93 g / cm ³The following is preferable, and more preferably 0.
925g / cm³The following, particularly preferably 0.92 g / c
m³It is the following. There is no particular lower limit to this density
But usually 0.850 g / cm³Is the lower limit. In addition,
As the ethylene / α-olefin copolymer (c),
Tough Flow Index (ASTM D-1238)
It is preferably 0.5 to 30 g / 10 minutes.

The ethylene / α-olefin copolymer synthesized in the present invention in the presence of a single site catalyst is
As the manufacturing method, a known method described in JP-A-6-306121 or JP-A-7-500622 can be used. Single-site catalyst
It has a single polymerization active point and has a high polymerization activity, and is also called a metallocene catalyst or a Kaminsky catalyst.The ethylene / α-olefin copolymer synthesized using this catalyst has a molecular weight distribution and It is characterized by a narrow composition distribution. Since the ethylene / α-olefin copolymer synthesized in the presence of such a single-site catalyst has high tensile strength, tear strength, impact strength, etc., it is necessary to highly fill with a metal hydrate. When used as a flammable material (wiring material coating material), there is an advantage that deterioration of mechanical properties due to highly filled metal hydrate can be reduced. On the other hand, when an ethylene / α-olefin copolymer synthesized using a single-site catalyst is used, the melt viscosity increases and the melt tension decreases compared to the case of using a normal ethylene / α-olefin copolymer. However, there is a problem in moldability. In this regard,
Introducing long-chain branching using an asymmetric catalyst as a single-site catalyst (Constrained Geometo
ry Catalytic Technology),
Alternatively, two peaks are created in the molecular weight distribution by connecting two polymerization tanks during the synthesis (Advanced Pe).
There is also one having improved molding processability by using the rformanceTerpolymer).

The ethylene / α-olefin copolymer (c) synthesized in the presence of the single-site catalyst used in the present invention is preferably the one having the above-mentioned molding processability improved. Dow Che
"AFFINITY" and "ENGAG" from Mical
"E" (trade name) is marketed by Exxon Chemical Company as "EXACT" (trade name). When the flame-retardant resin composition of the present invention is used as a covering material for insulated electric wires, electric cables, electric cords, optical fiber cores, optical fiber cords, etc. The amount of component c) is 30 to 400 parts by weight, preferably 50 to 300 parts by weight, more preferably 50 to 300 parts by weight.
It is 250 parts by weight. If the blending amount is less than 30 parts by weight, it is difficult to highly fill the metal hydrate, and the mechanical properties of the obtained composition deteriorate. On the other hand, if it exceeds 400 parts by weight, the softness is lost and the non-aromatic softening agent for rubber bleeds. When used as a molded part, the compounding amount of the component (c) is 50 to 250 parts by weight with respect to 100 parts by weight of the component (a).
When the content is within this range, the moldability is particularly easy and the mechanical properties of the molded part are sufficient.

Component (d) Polypropylene Resin Polypropylene resins that can be used in the present invention include homopolypropylene, ethylene / propylene random copolymers, ethylene / propylene block copolymers, propylene and other small amounts of α-olefins. (Eg 1
-Butene, 1-hexene, 4-methyl-1-pentene and the like). Here, the ethylene / propylene random copolymer means an ethylene component content of about 1 to 4% by weight, and the ethylene / propylene block copolymer means an ethylene component content of about 5 to 20% by weight. When the polypropylene resin as the component (d) is kneaded with the resin component (A) by heating in the present invention to produce a partially crosslinked product, a part of the polypropylene resin may be blended after the heat kneading. The polypropylene resin blended in (A) before heat kneading is thermally decomposed by the presence of the component (e) in the subsequent heat kneading and is appropriately reduced in molecular weight. As the polypropylene resin to be blended before heating and kneading, MFR (A
STM-D-1238, L condition, 230 ° C.) is preferably 0.1 to 10 g / 10 minutes, more preferably 0.1 to 5
g / 10 min, more preferably 0.1 to 3 g / 10 min. MFR of polypropylene resin is 0.1g
If it is less than / 10 minutes, the molecular weight of the polypropylene resin does not decrease even after heat treatment, and the moldability of the obtained resin composition (elastomer) may deteriorate, while the MFR is 1 or less.
If it exceeds 0 g / 10 minutes, the molecular weight becomes too low and the rubber elasticity of the obtained resin composition may deteriorate. As the polypropylene resin when blended after heating and kneading,
It may be any as long as it meets the conditions for extrusion for forming the coating layer, and the MFR is preferably 5 to 200 g / 10 minutes, more preferably 8 to 150 g / 10 minutes, and further preferably 1
The thing of 0-100g / 10min is used. When compounded after heating and kneading, polypropylene resin has MFR of 5 g / 10
If it is less than minutes, the moldability of the obtained resin composition may deteriorate, and if the MFR exceeds 200 g / 10 minutes, the rubber elasticity of the obtained resin composition may deteriorate. When the flame-retardant resin composition of the present invention is used as a covering material for an insulated electric wire, an electric cable, an electric cord, an optical fiber core wire, an optical fiber cord, or the like, (100 parts by weight of the component (a): The compounding amount of component d) is 0 to 200 parts by weight, preferably 0 to 60 parts by weight, and more preferably 10 to 60 parts by weight. If the blending amount of the polypropylene resin (d) exceeds 200 parts by weight, there is a problem that the resin composition becomes hard and flexibility deteriorates. The component (d) has the function of improving the extrudability of the resin composition while ensuring heat resistance, but the component (d) can be omitted when high heat resistance is not required. When the component (d) is not used, the amount of the component (b) used is usually adjusted so that the resin composition has good extrusion properties as a whole. When used as a molded part, the compounding amount of the component (d) is 0 to 100 parts by weight with respect to 100 parts by weight of the component (a). When the compounding amount is within this range, the moldability is particularly easy, and the mechanical properties as a molded part are sufficient.

Component (e) Organic peroxide Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (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 blending amount of the organic peroxide (e) is the thermoplastic resin component (A).
The amount is 0.01 to 0.6 part by weight, preferably 0.1 to 0.6 part by weight, based on 100 parts by weight. By selecting the organic peroxide within this range, the crosslinking does not proceed too much, so that a partially crosslinked composition excellent in extrudability can be obtained without causing lumps.

(F) Component (meth) acrylate-based and / or allyl-based cross-linking aid In the production of the flame-retardant resin composition of the present invention or the thermoplastic resin component (A) used therefor, the presence of an organic peroxide is used. In the above, a partially crosslinked structure is formed between the vinyl aromatic thermoplastic elastomer and the ethylene / α-olefin copolymer via the crosslinking aid. The crosslinking aid used at that time is represented by the general formula

[0021]

[Chemical 3]

(Here, R is H or CH ₃ , and n is an integer of 1 to 9.) A (meth) acrylate-based cross-linking aid represented by Here, the (meth) acrylate-based crosslinking aid refers to acrylate-based and methacrylate-based crosslinking aids. Specific examples include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate. In addition, those having an allyl group at the terminal such as diallyl fumarate, diallyl phthalate, tetraallyloxyethane and triallyl cyanurate can be used. Among these, (meth) acrylate crosslinking aids in which n is 1 to 6 are particularly preferable, and examples thereof include ethylene glycol diacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate. In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle, has good compatibility with other components, and has a peroxide solubilizing action, and acts as a dispersion aid of peroxide, so that it is heated. It is most preferable because the crosslinking effect at the time of kneading is uniform and effective, and a partially crosslinked thermoplastic resin having a well-balanced hardness and rubber elasticity can be obtained. By using such a compound, neither insufficient crosslinking nor excessive crosslinking can be expected, and a uniform and efficient partial crosslinking reaction can be expected during heat kneading. The addition amount of the crosslinking aid used in the present invention is 100 parts by weight of the thermoplastic resin component (A).
The range of 0.03 to 1.8 parts by weight is preferable, and the range of 0.03 to 1.2 parts by weight is more preferable. By selecting the cross-linking aid within this range, it is possible to obtain a composition having excellent extrudability without causing excessive vulcanization without causing excessive cross-linking. The blending amount of the cross-linking aid is about 1.5 to the addition amount of the organic peroxide in a weight ratio.
It is preferably 4.0 times.

(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. It is necessary that at least part of the metal hydrate is treated with a silane coupling agent, but untreated metal hydrate without surface treatment or metal water treated with other surface treatment agents such as fatty acids. Japanese products can be used in combination as appropriate.

The silane coupling agent used for the surface treatment of the metal hydrate is vinyltrimethoxysilane, vinyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyltriethoxysilane, glycid. Xypropylmethyldimethoxysilane, methacryloxypropyltrimethoxysilane,
A silane coupling agent having a vinyl group or an epoxy group at the terminal such as methacryloxypropyltriethoxysilane and methacryloxypropylmethyldimethoxysilane.
A silane coupling agent having a mercapto group at the terminal such as mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-
(Β-aminoethyl) -γ-aminopropyltripropyltrimethoxysilane, N- (β-aminoethyl) -γ
Crosslinkable silane coupling agents such as amino group-containing silane coupling agents such as aminopropyltripropylmethyldimethoxysilane 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.
You may use it in combination of 1 or more types.

The surface-treated magnesium hydroxide having a silane coupling agent which can be used in the present invention is not surface-treated (as a commercial product, Kisuma 5 (trade name, manufactured by Kyowa Chemical Co., Ltd.), stearic acid, A silane coupling agent having a vinyl group or an epoxy group at the end, such as those surface-treated with a fatty acid such as oleic acid (Kisuma 5A (trade name, manufactured by Kyowa Chemical Co., Ltd.), etc.) Commercially available products of magnesium hydroxide (Kisuma 5LH, Kisuma 5PH (both are trade names, manufactured by Kyowa Chemical Co., Ltd.), etc. that have been surface-treated with, or have been surface-treated with a silane coupling agent having a vinyl group or an epoxy group at the end. ). In addition to the above, silane coupling having a functional group such as a vinyl group or an epoxy group at a terminal is further added to magnesium hydroxide or aluminum hydroxide whose surface is partially pretreated with a fatty acid or a phosphoric ester. It is also possible to use a metal hydrate or the like which has been surface-treated with an agent.

When the metal hydrate is treated with the silane coupling agent, it is necessary to blend the silane coupling agent with the metal hydrate in advance. At this time, the silane coupling agent is appropriately added in an amount sufficient for the surface treatment.
2% by weight is preferred. The silane coupling agent may be an undiluted solution or may be diluted with a solvent.

The metal hydrate content in the resin composition of the present invention is 100 parts by weight of the thermoplastic resin component (A).
50 to 300 parts by weight, particularly preferably 100 to 2
It is 50 parts by weight. In the present invention, when (i) the metal hydrate is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A) is used in an amount of 50 parts by weight or more based on 100 parts by weight, and (ii) the metal hydrate. When the amount of the metal hydrate is 100 parts by weight or more, at least half of the amount is a metal hydrate pretreated with a silane coupling agent. It becomes possible to mix a filler with. It is particularly preferable that at least 100 parts by weight of the metal hydrate is magnesium hydroxide treated with a silane coupling agent.

When a polyolefin resin such as a normal polyethylene resin or polypropylene resin is used as a base resin and a large amount of metal hydrate is added to satisfy the required flame retardancy, the mechanical strength is lowered. Very big.
On the other hand, the thermoplastic resin component (A) in the present invention
Has a low cross-linking density and the resin components are in a partially cross-linked state through the component (f), and thus have excellent filler acceptability,
When such a thermoplastic resin component (A) is used as a base resin, a large amount of metal hydrate can be blended. Among them, only when a specific amount of a metal hydrate treated with a silane coupling agent is blended, a decrease in mechanical strength is suppressed to a minimum, whitening hardly occurs when bent, and a coating material for a wiring material. It is possible to obtain satisfactory characteristics as a molded part or the like.

Although the details of the reaction mechanism at the time of heating and kneading the resin composition of the present invention are not clear yet, it is considered as follows. That is, when the thermoplastic resin component (A) in the present invention is heated and kneaded, the component (e) is
The components (a) and (c) are crosslinked via the component (f). On the other hand, when the component (d) is present, the melt viscosity of the resin composition can be appropriately adjusted by appropriately lowering the molecular weight by the action of the component (e), and the resin can also be adjusted by the component (b). The melt viscosity of the composition can be adjusted, and the composition as a whole becomes a crosslinked product having excellent extrudability.
Crosslinking of the composition of the present invention may be carried out in the presence of a small amount of component (e), and it can be referred to as partial crosslinking because it has fewer crosslinking points than ordinary crosslinking. The degree of crosslinking of this flame-retardant resin composition can be represented by the gel fraction and dynamic elastic modulus of the thermoplastic resin component (A) as a guide. For the gel fraction, 1 g of the sample was wrapped in 100 mesh wire mesh, and it was 1 in boiling xylene using a Soxhlet extractor.
It can be expressed as a ratio of the weight of the residual solid content to 1 g of the sample after extraction for 0 hour. The dynamic elastic modulus can be expressed by the storage elastic modulus of melt viscoelasticity using a parallel plate. In the present invention, the degree of crosslinking is preferably 30 to 45% by weight, more preferably 40 to 45% by weight in terms of gel fraction, and preferably 10 ⁵ to 10 ⁷ Pa in terms of storage elastic modulus. When the thermoplastic resin component (A) is filled with a metal hydrate, when a specific amount of the metal hydrate treated with the silane coupling agent is blended with the components (e) and (f) at the same time. As long as it is possible to mix a large amount of metal hydrate without impairing the extrusion processability at the time of molding, it has heat resistance and mechanical properties while maintaining excellent flame retardancy, and after use A flame-retardant resin composition that can be re-extruded and can be recycled can be obtained. The mechanism of the action of the metal hydrate treated with the silane coupling agent is not clear yet, but it is considered as follows. That is, the silane coupling agent bonded to the surface of the metal hydrate by treating with the silane coupling agent has one alkoxy group bonded to the metal hydrate and a vinyl group or an epoxy group present at the other end. The various reactive sites such as the first bond with the vinyl aromatic thermoplastic elastomer as the component (a) and the uncrosslinked portion of the ethylene / α-olefin copolymer as the component (c). This allows
A large amount of metal hydrate can be blended without impairing extrusion moldability, the adhesion between resin and metal hydrate becomes strong, and mechanical strength and abrasion resistance are good, and it is difficult to scratch A flammable resin composition is obtained.

The flame-retardant resin composition of the present invention contains various additives which are generally used in electric wires, electric cables and electric cords, such as antioxidants, metal deactivators and flame retardants ( Auxiliary agents, fillers, lubricants, acid anhydrides and modified products thereof, etc. can be appropriately added within a range not impairing the object of the present invention. As the antioxidant, 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, sulfur-based antioxidants such as pentaerythritol-tetrakis (3-lauryl-thiopropionate), and the like. As a 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′-oxamidobis- (ethyl 3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate) and the like.

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, carbonic acid. Examples include magnesium, zinc borate, and white carbon. In particular, a silicone compound such as silicone rubber or silicone oil not only imparts and improves flame retardancy, but also in an electric wire / cord, an insulator (a coating layer containing the flame retardant resin composition) and a conductor. By controlling the adhesion force of the cable and imparting lubricity to the cable, it is possible to reduce external damage. Specific examples of the silicone compound used in the present invention include:
"SFR-100" (trade name, manufactured by GE), "CF-9"
150 ”(trade name, manufactured by Toray Dow Silicone Co., Ltd.) and the like. When added, the silicone compound is preferably added in an amount of 0.
5 to 5 parts by weight are blended. If it is less than 0.5 parts by weight, it has practically no effect on flame retardancy and lubricity, and if it exceeds 5 parts by weight, the appearance of electric wires, cords and cables may be deteriorated, and extrusion molding speed may be reduced, resulting in mass productivity. May get worse. Examples of the lubricant include hydrocarbon-based, fatty acid-based, fatty acid amide-based, ester-based, alcohol-based, metal soap-based and the like. Examples of the acid anhydride and its modified product include maleic anhydride and polyethylene modified with maleic anhydride. By using an acid anhydride or a modified product thereof, the interaction between the polyolefin (components (c) and (d)) and the metal hydrate is improved. Therefore, the mechanical properties can be improved. When added, the acid anhydride is preferably used in an amount of 3.0 to 8.0 parts by weight, and the modified product of the acid anhydride is preferably used in an amount of 10 to 40 parts by weight, based on 100 parts by weight of the component (a).

The above-mentioned additives and other resins can be introduced into the flame-retardant resin composition of the present invention within a range that does not impair the object of the present invention, but at least the thermoplastic resin component (A) is mainly used. Use as a resin component. Here, the term “main resin component” means that it is usually 7 in the resin component of the flame-retardant resin composition of the present invention.
It means that the thermoplastic resin component (A) occupies 0% by weight or more, preferably 85% by weight or more, and more preferably the total amount of the resin component. Here, in the thermoplastic resin component (A), each of the components (a), (b), (c) and (d) has an amount used within the specified range, and the thermoplastic resin component (A) is the component. 100% by weight in total of (a) to (d)
Becomes The following is shown as a preferred embodiment of the resin composition of the present invention. (A) Block copolymerization consisting of at least two polymer blocks A whose main constituent is a vinyl aromatic compound and at least one polymer block B whose main constituent is a conjugated diene compound. 100 parts by weight of a hydrogenated block copolymer obtained by coalescing and / or hydrogenating the same, (b) 30 to 70 parts by weight of a softening agent for non-aromatic rubber, and (c) 10 to 60 parts by weight of polypropylene resin. Parts, (d) 50 to 200 parts by weight of an ethylene / α-olefin copolymer having a density of 0.91 g / cm ³ or less synthesized in the presence of a single-site catalyst, and (e) an organic peroxide 0.1 to 1. A flame-retardant resin composition comprising 100 to 250 parts by weight of a metal hydrate (B) with respect to 100 parts by weight of a thermoplastic resin composition (A) contained at a ratio of 5 parts by weight. .

The method for producing the flame-retardant resin composition of the present invention will be described below. The components (a) to (d), the metal hydrate (B), and the components (e) and (f) are added and kneaded by heating. The kneading temperature is preferably 160 to 240 ° C. The kneading conditions such as the kneading temperature and the kneading time are such that the resin components (a) to (d) are melted and the organic peroxide acts to realize the required partial cross-linking. It can be appropriately set to a sufficient degree. The kneading method can be satisfactorily used as long as it is a method commonly used for rubber, plastics and the like, and as the apparatus, for example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders can be used. Through this step, it is possible to obtain a flame-retardant resin composition in which each component is uniformly dispersed. Metal hydrate (B)
Is 50 parts by weight or more and less than 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin component (A), the metal hydrate treated with the silane coupling agent is 50 parts by weight or more,
When the metal hydrate (B) is 100 parts by weight or more and 300 parts by weight or less, at least half of the metal hydrate (B) needs to be a metal hydrate pretreated with a silane coupling agent. . In this case, it is important that the metal hydrate treated with the silane coupling agent is previously treated with the silane coupling agent. By using a metal hydrate that has been surface-treated in advance, it is possible to add a sufficient amount of metal hydrate to ensure flame retardancy, and especially good mechanical strength and wear resistance. A flame-retardant resin composition that is hard to scratch is obtained. As another method, first, the components (a) to (d) are heated and kneaded in the first step to obtain the thermoplastic resin component (A). In the second step, the components (e), (f), and the metal hydrate (B) are added to the thermoplastic resin component (A) obtained in the first step, and the mixture is heated and kneaded. The temperature at this time is preferably 160 to 240 ° C. In this case as well, the kneading conditions such as kneading temperature and kneading time are such that the organic peroxide melted and contained in the thermoplastic resin component (A) is sufficient for partial crosslinking. Can be appropriately set to be used for. In this way, the components (a) to (d) may be heated and kneaded in advance to disperse them microscopically, and then the components (e) and (f) may be added and kneaded by heating. Also in this case, when the surface-treated metal hydrate is used, it is necessary to finish the surface treatment before blending.

The flame-retardant resin composition of the present invention is suitable for coating and manufacturing of wiring materials used for internal and external wiring of electric / electronic devices, optical fiber cores, and molded parts such as optical fiber cords. When the resin composition of the present invention is used as a coating material for a wiring material, at least one coating layer made of the flame-retardant resin composition of the present invention formed on the outer periphery of a conductor is preferably formed by extrusion coating. There is no particular limitation other than having it. As the flame-retardant resin composition, it is particularly preferable that at least 100 parts by weight of the metal hydrate is magnesium hydroxide treated with a silane coupling agent. For example, as the conductor, a known arbitrary wire such as a single wire or a twisted wire of annealed copper can be used. As the conductor, in addition to the bare wire, a tin-plated conductor or a conductor having an enamel coating insulating layer may be used. The wiring material of the present invention can be produced by extrusion-coating the flame-retardant resin composition of the present invention around conductors or insulated wires using a general-purpose extrusion coating device. At this time, the temperature of the extrusion coating apparatus is preferably about 180 ° C. in the cylinder part and about 200 ° C. in the crosshead part. In the wiring material of the present invention,
The thickness of the insulating layer (coating layer made of the flame-retardant resin composition of the present invention) formed around the conductor is not particularly limited, but is usually about 0.15 mm to 5 mm.

In the wiring material of the present invention, it is preferable that the resin composition of the present invention is extrusion-coated to form a coating layer as it is, but for the purpose of further improving heat resistance, coating after extrusion is performed. It is also possible to crosslink the layers. However, this cross-linking treatment makes it difficult to reuse the coating layer as an extruded material. As a method for crosslinking, a conventional electron beam irradiation crosslinking method or a 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. Electron beam dose is 1 to 30 Mrad
Is suitable, in order to efficiently perform crosslinking, in the resin composition constituting the coating layer, a methacrylate compound such as trimethylolpropane triacrylate, an allyl compound such as triallyl cyanurate, a maleimide compound, a divinyl system. You may mix | blend polyfunctional compounds, such as a 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.

The optical fiber core wire or optical cord of the present invention uses a general-purpose extrusion coating device, and the flame-retardant resin composition of the present invention as a coating layer, around the optical fiber element wire, or a tensile strength fiber. Is produced by extrusion coating around the optical fiber core wire which is vertically attached or twisted.
At this time, the temperature of the extrusion coating device is 18
It is preferable that the temperature is 0 ° C. and the crosshead portion is about 200 ° C. The optical fiber core wire of the present invention may be used as it is without further providing a coating layer around it depending on the application. The optical fiber core wire or cord of the present invention includes, as a coating layer of the flame-retardant resin composition of the present invention, all those coated on the outer circumference of the optical fiber element wire or core wire, and particularly its structure is restricted. Not something to do. The thickness of the coating layer, the type of tensile strength fiber that is vertically attached or twisted to the optical fiber core wire,
The amount and the like vary depending on the type and application of the optical fiber cord, and can be set appropriately.

1 to 3 show structural examples of the optical fiber core wire and the cord of the present invention. FIG. 1 is a cross-sectional view of an example of an optical fiber core wire of the present invention in which a coating layer 2 made of a flame-retardant resin composition is provided directly on the outer circumference of an optical fiber element wire 1.
FIG. 2 is a cross-sectional view of one embodiment of the optical fiber cord of the present invention in which a coating layer 5 is formed on the outer circumference of one optical fiber core wire 3 in which a plurality of tensile strength fibers 4 are vertically attached. FIG. 3 shows an optical fiber cord of the present invention in which a plurality of tensile strength fibers 4 are vertically attached to the outer peripheries of two optical fiber core wires 3 and 3 and a coating layer 6 is further formed on the outer perimeter thereof (optical fiber two-core cord). 2) is a cross-sectional view of one embodiment of FIG.

The shape of the molded part of the present invention is not limited, and examples thereof include a power plug, a connector, a sleeve, a box, a tape base material, a tube and a sheet. The molded part of the present invention is molded from the flame-retardant resin composition of the present invention by a usual molding method such as injection molding.

[0039]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited thereto. The numbers indicate parts by weight unless otherwise specified.

Examples 1 to 19 and Comparative Examples 1 to 12 Hydrogenated styrene / ethylene / propylene / styrene copolymer (SEPS) as component (a), paraffin oil as component (b), and Table 1 as component (c). ~ 6 ethylene ethylene 1-octene copolymer (c-1) having a density of 0.87 g / cm ³ , ethylene having a density of 0.915 g / cm ³
1-octene copolymer (c-2), density 0.925 g /
cm ³ linear low-density polyethylene (c-3), (d)
As a component, the polypropylene described in Tables 1 to 6 (MFR8g
/ 10 minutes) (d-1) or (d-2), 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane as the component (e), and triethylene glycol as the component (f). Dimethacrylate, magnesium hydroxide (B-1) surface-treated with vinylsilane as the component (B), magnesium hydroxide (B-2) surface-treated with a fatty acid, or untreated magnesium hydroxide (B-3) And a silane coupling agent were used to prepare the composition with the respective components being blended as shown in Tables 1 to 6.

In Examples 3 and 7, (a) to (d) were dry blended at room temperature and heated and kneaded at 200 ° C. using a Banbury mixer to prepare a thermoplastic resin component (A). Subsequently, (e), (f) and (B) metal hydrate were added, kneading was performed with a Banbury mixer, and the mixture was discharged.
A flame-retardant resin composition was obtained. The discharge temperature was 200 ° C. In Examples 11 and 13, (B) metal hydrate was placed in a blender, and the silane coupling agent was added dropwise with stirring to perform silane treatment of the metal hydrate in advance. The metal hydrate surface-treated with the silane coupling agent thus obtained and all other components were dry blended at room temperature, heated and kneaded with a Banbury mixer at 200 ° C., and discharged. A flammable resin composition was obtained. The discharge temperature was 200 ° C. In the other Examples and Comparative Examples (excluding Comparative Examples 8 and 9), all components were dry blended at room temperature, heated and kneaded using a Banbury mixer at 200 ° C., and discharged. Got The discharge temperature was 200 ° C. In Comparative Example 8, each component except the organic peroxide and the silane coupling agent was heated and kneaded with a Banbury mixer, and then the organic peroxide and the silane coupling agent were added and kneaded. Further, in Comparative Example 9, after all components except (B) metal hydrate were kneaded with a Banbury mixer, (B) metal hydrate was blended and kneaded and discharged to obtain a flame-retardant resin composition. Obtained.

From the obtained resin composition, by pressing,
A 1 mm sheet corresponding to each example and comparative example was prepared.
Next, a conductor (conductor diameter: 1.14 mmφ tin-plated annealed copper twisted wire structure: 30 pieces /
0.18 mmφ) was extrusion-coated with a resin composition for insulation coating, which had been melted in advance, to produce insulated wires having an outer diameter of 2.74 mm corresponding to Examples 1 to 17 and Comparative Examples 1 to 12. Further, using a general-purpose extrusion coating device, the obtained composition was applied to the outer periphery of an optical fiber nylon core wire (3) having an outer diameter (φ) of 0.90 mm, to which tensile strength fibers (aramid fibers) (4) were attached. The optical fiber cord of the structure of FIG. 2 extruded and coated with 0.35 mm, and the light of the structure of FIG. 1 in which the composition was directly coated on the optical fiber element wire (1) of φ0.25 mm to have an outer diameter of 0.9 mm. A fiber core wire was produced (Examples 1, 2,
9). Further, on the power plug terminal to which two electric wires produced in Example 2 were connected, injection molding was performed by using an injection molding machine using Examples 18 and 19, to form a power plug. These power plugs were molded at an injection temperature of 230 ° C. Tensile properties (elongation (%)) of each of the obtained sheets
And tensile strength (MPa) and heat distortion characteristics were evaluated, and the results are also shown in Tables 1 to 6. Each characteristic is JISK 6
723, and the heat deformation test was performed at 121 ° C. For each characteristic of the sheet, the elongation is 100% or more,
A tensile strength of 10 MPa or more was passed, and a deformation rate of 30% or less was passed for heat deformation.

Further, with respect to the coating layer of each of the obtained insulated wires, tensile properties, wear resistance, horizontal combustion test, 60 ° inclined combustion test, heat deformation rate test, whitening test (whether there is whitening phenomenon), extrudability Tests and flexibility tests were conducted to evaluate each property, and the results are shown in Tables 1 to 6 together. Tensile properties are
The tensile strength (MPa) and breaking elongation (%) of the insulator (covering layer) of each insulated wire are indicated by a marked line interval of 25 mm and a pulling speed of 500 m.
It was measured under the condition of m / min. The elongation must be 100% or more and the strength must be 10 MPa or more. Abrasion resistance was evaluated using a test apparatus whose front view is shown in FIG. Cut it to a length of 75 cm, remove the insulating coating layers (7a) on both ends, and remove the conductor (7
Insulated wire (7) with exposed b) is placed on a horizontal base (8)
Secure with a clamp (9) on the top of the
The blade (11) while applying 700 gf of load (10) at a speed of 50 to 60 times per minute over a length of 0 mm or more.
Was reciprocated (in the direction of the arrow in the figure) to measure the number of blade reciprocations required until the insulating coating layer was removed by abrasion and the blade contacted the conductor of the electric wire. FIG. 5 shows a front view of the blade. The blade (11) is formed by forming a blade portion with a width of 3 mm by two surfaces (11a, 11b) so that the angle formed is 90 °, and the tip of the blade portion is formed. The radius of curvature (R) of the part is 0.125 mm. The number of reciprocations of the blade is 100 before the blade contacts the conductor of the electric wire.
Those that were 0 times or more were evaluated as ◯, those that were 500 times or more and less than 1000 times were evaluated as Δ, and those that were less than 500 times were regarded as unacceptable and were shown as x. A level of Δ or higher is a level at which there is practically no problem, and the grade is acceptable.

The horizontal combustion test is conducted according to J
A horizontal burning test specified by IS C 3005 was performed, and the self-extinguishing within 30 seconds was counted as a pass, and the pass number in 10 was shown. In the 60-degree combustion test, each insulated wire was subjected to a 60 ° inclined combustion test specified in JIS C 3005, and the self-extinguishing test within 30 seconds was counted as a pass, and the result was shown as the number of passes out of 10. Regarding flame retardancy, it is not necessary to pass both of the above two types of combustion tests, and those in which all the specimens pass the horizontal combustion test are considered to pass the combustion test.
The heat deformation rate is based on the UL1581 heat deformation test (Deformat
ion test) was performed at a temperature of 121 ° C. and a load of 500 gf. 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 presence or absence of the whitening phenomenon was evaluated by whether or not whitening occurred when each insulated wire was wound around a mandrel having a self-diameter. Wrap 6 times, if there is no whitening once, ○,
If whitening occurs 1 to 5 times, it is indicated by Δ, and whitening occurs 6 times or more, it is indicated by x. Poor ones are not preferable for practical use. In the extrudability test, extruding was carried out with an extruder of 30 mmφ, and extruding was performed within the normal range of the motor load and good appearance was ○, extruding load was slightly large or appearance was slightly bad △, The case where the extrusion load was extremely large and the extrusion was difficult or impossible was evaluated as x. A level of Δ or higher is a level at which there is practically no problem, and the grade is acceptable. The flexibility was evaluated by the test method whose schematic diagram is shown in FIG. A sample (12) was prepared by cutting each insulated wire to a length of 20 cm, one end of which was fixed to a vertically standing wall (13), and the difference between the fixed position and the height of the other end lowered by its own weight. L (cm) was measured. When the height difference (L) is less than 1 cm, it is indicated by x, when it is 1 cm or more and less than 3 cm, it is indicated by Δ, and when it is 3 cm or more, it is indicated by o. Those with × are poor in flexibility and cannot be put to practical use as insulated wires.

The following compounds were used as the compounds shown in Tables 1-6. (A) Thermoplastic resin component (a): Hydrogenated block copolymer manufacturer: Kuraray Co., Ltd. Product name: Septon 4077 Type: Styrene / ethylene / propylene / styrene copolymer Styrene component content: 30% by weight Content of isoprene component: 70% by weight Weight average molecular weight: 320,000 Molecular weight distribution 1.23 Hydrogenation rate: 90% or more Component (b): Non-aromatic rubber softener manufacturer: Idemitsu Kosan product name: Diana Process Oil PW-90 Type: Paraffin oil Weight average molecular weight: 540 Aromatic component content: 0.1% or less

Component (c): Single-site catalyst system ethyl
-Α-olefin copolymer (C-1) Manufacturer: Dow Chemical Japan Product Name: Engage EG8100 Type: Ethylene / 1-octene copolymer Density: 0.870g / cm³ (C-2) Manufacturer: Dow Chemical Company Product name: Affinity FM1570 Type: Ethylene / 1-octene copolymer Density: 0.915g / cm³ (C-3) Manufacturer: Mitsui Chemicals Product Name: Evolution SP2510 Type: Linear low density polyethylene Density: 0.925g / cm³

Component (d): polypropylene resin (D-1) Manufacturer: Made by Grand Polymer Product name: CJ-700 Type: Homo polypropylene Density: 0.9g / cm³ (D-2) Manufacturer: Made by Grand Polymer Product name: F229D Type: Random polypropylene Density: 0.9g / cm³

Component (e): Organic peroxide manufacturing company: NOF Corporation brand name: Perhexa 25B Type: 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane Component (f): Crosslinking agent Manufacturer: Shin-Nakamura Chemical Co., Ltd. Product name: NK ester 3G Type: Triethylene glycol dimethacrylate

(B) Metal hydrate (B-1) Manufacturer: Kyowa Chemical Co., Ltd. Product name: Kisuma 5LH Type: Magnesium hydroxide surface-treated with a silane coupling agent having a vinyl group at the end (B-2) ) Manufacturer: Kyowa Chemical Co., Ltd. Product Name: Kisuma 5B Type: Fatty Acid Treated Magnesium Hydroxide (B-3) Manufacturer: Kyowa Chemical Co., Ltd. Product Name: Kisuma 5 Type: Untreated Magnesium Hydroxide

(Silane coupling agent) TSL8370 (trade name) Manufacturer: Toshiba Silicone Type: Silane coupling agent with vinyl group at the end TSL8350 (trade name) Manufacturer: Toshiba Silicone Type: Silane coupling agent with epoxy group at the end

Other components Maleic acid modified polyethylene (LLDPE) Manufacturer: Mitsui Chemicals, Inc. Product name: Admer XE070 Type: Maleic acid modified polyethylene phenolic antioxidant Manufacturer: Ciba-Geigy Product name: Irganox 1010 Type: Penta Erythrityl-tetrakis (3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate) Lubricant manufacturer: Hoechst, trade name: Wax OP Type: montanic acid saponified ester wax

[0052]

[Table 1]

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

[0057]

[Table 6]

As is clear from the results of Tables 1 to 6, the flame-retardant resin compositions obtained in Examples 1 to 17 and the sheet, electric wire, optical fiber core wire and optical fiber cord using the same were
It has the required elongation and tensile strength, is good in all of the combustion test, abrasion resistance test, whitening test, and heat distortion rate, and is also excellent in extrudability and flexibility. Example 18,
No. 19 shows almost no material shrinkage after molding, and a molded plug having a good appearance is obtained. In addition to the power plug J
The flame of the burner used in the flame retardant test specified by IS C 3005 was applied for 15 seconds, but when the flame was separated, extinguishing was confirmed instantly. On the other hand, in Comparative Examples 1 to 12,
If uniform kneading or extrusion is not possible, or if tensile strength,
There is a problem with either whitening, extrusion, or flexibility,
Electric wires with all good properties have not been obtained. The compound of Comparative Example 8 obtained by adding magnesium hydroxide without pretreatment with a silane coupling agent and then adding a silane coupling agent and an organic peroxide was difficult to re-mold, and the sheet surface also had a hard spot. There were many, and extrusion was impossible. The electric wire of Comparative Example 3 was extruded but bleeded. In Comparative Example 9 in which vinylsilane-treated magnesium hydroxide was added after the partial crosslinking reaction was completed, the effect of improving the mechanical properties of the electric wire was not sufficiently obtained. It can be seen that the metal hydrate is not effective unless it is added before or at the same time as the partial crosslinking reaction.

[0059]

EFFECTS OF THE INVENTION According to the present invention, it is excellent in flame retardancy, heat resistance and mechanical properties, and when it is discarded such as landfill and combustion,
It is possible to provide a flame-retardant resin composition and a wiring material that are free from the elution of heavy metal compounds, generate a large amount of smoke, and a corrosive gas and that meet the recent environmental problems. Further, according to the present invention, while satisfying these characteristics, the coating material can be reused because it can be remelted, does not whiten even when bent, and is hardly scratched, and a flame-retardant resin composition and the same are used. Wiring material,
Optical fiber cores, optical fiber cords, and other molded parts may be provided. The flame-retardant resin composition of the present invention is a halogen-free flame-retardant material and is composed of a material that does not contain phosphorus, not only excellent mechanical properties, flame retardancy, heat resistance, flexibility, but also landfill and At the time of disposal such as combustion, there is no elution of harmful heavy metal compounds and generation of large amounts of smoke and corrosive gas. Further, the wiring material of the present invention is excellent in mechanical properties, flame retardancy and heat resistance, and also excellent in flexibility, and in particular, does not whiten even when bent. As described above, the wiring material of the present invention has excellent characteristics as a non-halogen flame-retardant wiring material containing no phosphorus, which can achieve both flexibility and mechanical strength. Furthermore, the coating layer of the wiring material of the present invention can be formed by using a remeltable material as the coating material while having a high heat resistance of UL105 ° C. Therefore, it is a cross-linked product which is a current coating material. This makes it possible to provide a wiring material that is more recyclable than a covered wiring material. From the above, the wiring material of the present invention is very useful as a wiring material for electric / electronic devices in consideration of environmental problems, such as a power cable. The flame-retardant resin composition of the present invention is also suitable as a coating material for such wiring materials, optical fiber core wires, optical fiber cords, etc., as a material for molded parts, and as a tube or tape material. It is something.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an embodiment of an optical fiber core wire of the present invention in which a coating layer is directly provided on the outer circumference of an optical fiber element wire.

FIG. 2 is a cross-sectional view of an example of an optical fiber cord of the present invention in which a coating layer is formed on the outer circumference of one optical fiber core wire in which a plurality of tensile strength fibers are vertically attached.

FIG. 3 is a cross-sectional view of another embodiment of the optical fiber cord of the present invention in which a plurality of tensile strength fibers are vertically attached to the outer circumferences of two optical fiber core wires, and a coating layer is further formed on the outer circumferences thereof.

FIG. 4 is a front view of a wear resistance test apparatus.

5 is a front view of the blade in the wear resistance test apparatus shown in FIG. 4. FIG.

FIG. 6 is a schematic diagram showing a flexibility testing method.

[Explanation of symbols]

1 Optical fiber strand 2 coating layer 3 Optical fiber core 4 tensile strength fiber 5 coating layer 6 coating layer 7 insulated wire 7a Insulation coating layer 7b conductor 8 units 9 clamps 10 load 11 blade 11a, 11b Blade surface of blade 12 Electric wire sample 13 walls L Height difference (cm)

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI C08L 23/08 C08L 23/08 H01B 7/295 H01B 3/00 A // H01B 3/00 3/44 F 3/44 P C08L 23:10 (C08L 53/02 H01B 7/34 B 23:10) (72) Inventor Dai Hashimoto 3-25 Tatsumidai Higashi, Ichihara-shi, Chiba (56) Reference JP-A-59-6236 (JP, A) Kai 60-170651 (JP, A) JP 63-57662 (JP, A) JP 5-32830 (JP, A) JP 8-291239 (JP, A) JP 9-302156 ( JP, A) JP 9-324100 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 53/02 C08L 23/08

Claims (9)

(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 ) A thermoplastic resin component comprising 10 to 100 parts by weight of a non-aromatic rubber softening agent, (c) 30 to 400 parts by weight of an ethylene / α-olefin copolymer, and (d) 0 to 200 parts by weight of a polypropylene resin ( A) 0.01 to 0.6 parts by weight of organic peroxide, and (f) (meth) acrylate-based and / or allyl-based crosslinking aid 0.03 to 100 parts by weight of A).
1.8 parts by weight and 50 to 300 of metal hydrate (B)
The metal hydrate (B) is contained at a ratio of (parts by weight), and (i) when the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A). 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. 2. (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 ) A thermoplastic resin component comprising 10 to 100 parts by weight of a non-aromatic softening agent for rubber, (c) 50 to 250 parts by weight of an ethylene / α-olefin copolymer, and (d) 0 to 100 parts by weight of a polypropylene resin ( A) 0.01 to 0.6 parts by weight of organic peroxide, and (f) (meth) acrylate-based and / or allyl-based crosslinking aid 0.03 to 100 parts by weight of A).
1.8 parts by weight and 50 to 300 of metal hydrate (B)
The metal hydrate (B) is contained at a ratio of (parts by weight), and (i) when the metal hydrate (B) is 50 parts by weight or more and less than 100 parts by weight, the thermoplastic resin component (A). 100
50 parts by weight or more of the metal hydrate pretreated with the silane coupling agent based on parts by weight; (ii) 100 parts by weight or more of the metal hydrate (B) 300
In the case of less than or equal to parts by weight, at least half of the metal hydrate (B) is a mixture having a composition in which the metal hydrate is pretreated with a silane coupling agent, and the thermoplastic resin component (A) A flame-retardant resin composition characterized by being heated and kneaded at a melting temperature or higher. 3. The cross-linking aid (f) has the general formula: (Wherein R is H or CH ₃ and n is an integer of 1 to 9), which is a (meth) acrylate-based crosslinking aid. Flame-retardant resin composition. 4. The metal hydrate (B) is magnesium hydroxide, according to any one of claims 1 to 3.
The flame-retardant resin composition according to the item. 5. The flame-retardant resin composition according to any one of claims 1 to 4, wherein the silane coupling agent is a silane compound having a vinyl group and / or an epoxy group at a terminal. 6. The flame-retardant resin composition according to any one of claims 1 and 3 to 5 is provided as a coating layer on the outside of a conductor or an optical fiber element wire or / and an optical fiber core wire. And molded articles. 7. A molded part formed by molding the flame-retardant resin composition according to any one of claims 2 to 5. 8. The flame-retardant resin composition according to claim 1, wherein (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 a hydrogenated block copolymer obtained by hydrogenating the same, (b) non-aromatic Group rubber softening agent, (c) ethylene / α-olefin copolymer, (d)
Polypropylene resin, (e) organic peroxide,
(F) A (meth) acrylate-based and / or allyl-based crosslinking aid and a metal hydrate (B) are simultaneously heated and kneaded at a melting temperature of the thermoplastic resin component (A) or higher to perform a crosslinking treatment. A method for producing a flame-retardant resin composition, comprising: 9. The flame-retardant resin composition according to any one of claims 1 to 5, wherein in the first step, (a) at least two polymers whose main constituent is a vinyl aromatic compound. A block copolymer composed of the block A and at least one polymer block B containing a conjugated diene compound as a main component, and / or a hydrogenated block copolymer obtained by hydrogenating the same, ( b) A non-aromatic softening agent for rubber, (c) ethylene / α-olefin copolymer, and (d) polypropylene resin are heated and kneaded to obtain a thermoplastic resin component (A). Resin components (A) and (e) organic peroxide, (f) (meth)
Flame-retardant property characterized by heating and kneading an acrylate-based and / or allyl-based crosslinking aid and a metal hydrate (B) at a temperature not lower than the melting temperature of the thermoplastic resin component (A) to carry out a crosslinking treatment. A method for producing a resin composition.