JP2001210151A - Heat degradation resistant flame-retardant insulated wire and cable - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide heat degradation resistant flame-retardant insulated wire and cable prevented the generation of toxic halogenous gases if they burn. SOLUTION: A wire and a cable are coated with a resin composition composed of 100 pts.wt. of halogen-free synthetic resin and 10 to 500 pts.wt. of magnesium hydroxide particles having <=2 μm mean secondary particle diameter (i), <=20 m2/g specific surface area measured by BET method (ii), and <=0.02 wt.% total content of iron compounds and manganese compounds in terms of metals (iii) to obtain heat degradation resistant flame-retardant insulated wire and cable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant insulated wire and cable which do not generate or emit little harmful gas such as halogen-based gas at the time of combustion and have excellent heat deterioration resistance.

[0002]

2. Description of the Related Art The demand for flame retardancy for synthetic resins is increasing year by year and is becoming more severe. In order to respond to such a demand for flame retardancy, heretofore, a flame retardant using an organic halide and antimony trioxide in combination has been proposed and widely practiced. However, this flame retardant is partially decomposed during molding to generate halogen gas, which corrodes the processing and molding machines, is toxic to workers, and has a bad influence on the heat resistance or weather resistance of resins and rubber. Various problems, such as generating a large amount of smoke containing a harmful gas at the time of fire or burning of a used article after use, and generating dioxin.

[0003] With regard to coating materials such as electric wires, cables, wire harnesses for automobiles, and tubes for electronic devices such as personal computers, a high level of flame retardancy is required due to the high performance, high functionality and high density of urban functions. It has become.

Conventionally, insulators and sheath materials, such as electric wires, cables, and electric wires for electronic devices such as wire harnesses and personal computers, are all flammable. In many cases, the demand for the development of flame-retardant electric wires and cables has increased, and various studies have been made.

[0005] In the case of flame retardation of polyolefin and halogen-containing resins which have been used for electrical insulation, a method of blending a flame retardant such as an organic halide flame retardant and antimony trioxide has been generally employed. Such a flame-retardant electrical insulating composition generates a large amount of non-flammable halogen-based gas in the event of a fire, and as a result, 'OH,' O necessary for the continuation of combustion around the burning wires and cables. It is a substance that supplements such radicals, carbonizes electric wires and cables, blocks oxygen, and prevents combustion, and has an excellent flame retardant effect. However, the halogen-based gas generated at that time is harmful to the human body, and furthermore, the halogen-based gas reacts with moisture in the air to form hydrohalic acid, corrode equipment and the like, and cause environmental pollution. Under these circumstances, the need for flame retardants that are safe for the human body and generate less corrosive gas has increased due to the addition of metal hydroxides to polyolefins. For wires and cables that use a flame-retardant electrical insulating composition as an insulator. (See JP-A-1-108235 and JP-A-5-247281) has been proposed.

[0006] Among metal hydroxides, aluminum hydroxide has a dehydration reaction starting at about 200 ° C. Therefore, many polymers are thermally decomposed at a processing temperature to foam a molded article. In the case of calcium hydroxide, the dehydration temperature starts at about 450 ° C. and dehydration is completed at about 550 ° C. Therefore, the dehydration temperature is higher than the combustion temperature of the polymer, and the combustion effect is considerably higher than that of magnesium hydroxide. Inferior.

The combination of these hydroxides is disclosed in
Japanese Patent Publication No. 181305 proposes a combination of aluminum hydroxide and magnesium hydroxide. However, since thermal decomposition of aluminum hydroxide starts at about 200 ° C., it can be applied only to those having a resin processing temperature lower than 200 ° C. There are drawbacks.

[0008] As a polymer flame retardant, dehydration does not occur at the processing temperature of the polymer, and in order to impart higher flame retardancy to the polymer, it is necessary to dehydrate at a temperature that overlaps as much as possible with the combustion temperature of the polymer. Is important, and magnesium hydroxide is an excellent material satisfying such conditions.

Magnesium hydroxide has a dehydration start temperature of about 3
Since it is 40 ° C., it is applied to most resins.

[0010] Magnesium hydroxide has properties suitable for flame-retardant insulated wires and cables when mixed with resin, but it has been found that with the recent increase in required characteristics, there are still problems to be solved. .

That is, to mix magnesium hydroxide particles with a halogen-free synthetic resin and to meet the VO standard with a thickness of 1/8 inch to 1/16 inch in UL-94 flame retardant standard. It is necessary to blend about 150 to 250 parts by weight of magnesium hydroxide particles with respect to 100 parts by weight of the resin. The addition of such a relatively large amount of magnesium hydroxide particles promotes deterioration of the molded article due to heating during molding and heating during use, and reduces the original physical properties of the molded article, particularly, elongation and tensile strength. This will cause problems.

[0012]

SUMMARY OF THE INVENTION The present invention relates to a novel and excellent halogen-free, heat-resistant, flame-retardant, insulated wire and cable (such as a wire harness for automobiles and equipment wires, etc.) comprising magnesium hydroxide particles which have solved the above-mentioned problems. , Etc.). Examples of the electric cable include insulated electric wires such as outdoor and indoor power cables, fire-resistant cables, and communication cables.

The present inventors have studied the purity and physical properties of magnesium hydroxide particles in order to achieve the above object industrially. As a result, it was found that the amount of the specific metal compound as an impurity in the magnesium hydroxide particles, the value of the average secondary particle diameter, and the value of the specific surface area mutually affected the thermal deterioration of the resin, It has been found that setting these to certain specific values can result in a flame retardant having excellent heat deterioration resistance, and has already been proposed. [Japanese Patent Application Hei 8-31
6023 (JP-A-9-227784).

In the manufacturing process, magnesium hydroxide particles mainly contain various impurities in the raw material, and there are impurities caused by mixing from equipment materials due to corrosion and friction of the equipment. It is mixed as a solid solution or contaminant in the magnesium hydroxide particles. According to the study of the present inventors, in various impurities, when an iron compound and a manganese compound are present in trace amounts, not only as impurities but also as solid solutions, they affect the thermal degradation of the resin. It was found to give.

Thus, according to the study of the present inventors, high-purity magnesium hydroxide particles containing iron compounds and manganese compounds as impurities in a certain amount or less and having an average secondary particle diameter of 3 μm or less. (That is, this means that most of the particles are primary particles that are not secondary aggregated.) Further, the value of the specific surface area is 20 m 2 / g.
It has been found that the following makes it possible to obtain a resin composition and a molded article having excellent mechanical strength and little decrease in physical properties due to thermal deterioration.

[0016]

According to the study of the present invention,
An object of the present invention is to provide a halogen-free synthetic resin 10.
0 parts by weight, magnesium hydroxide particles 10 to 50
0 parts by weight, wherein the magnesium hydroxide particles have the following requirements (i) to (iii): (i) an average secondary particle diameter of 3 μm or less; (ii) a BET specific surface area of 20 m 2 / g or less (iii) Halogen-free, heat-resistant, flame-retardant, flame-retardant insulated wire coated with a resin composition satisfying a total content of Fe compound and Mn compound of 0.02% by weight or less in terms of metal. And achieved by cable.

Thus, according to the present invention, there are provided insulated wires and cables containing almost no halogen as a coating composition. Thus, the insulated wires and cables of the present invention do not generate toxic halogen gas even if they are burned as a matter of course during the manufacturing and processing thereof.

In the present invention, the insulated wires and cables are obtained by coating and insulating a conductive wire (single wire and a bundled wire) such as a copper wire or an aluminum wire and an optical fiber with a resin, and bundling the wires and cables. Also included. For example, ordinary electric cords, automobile wire harnesses, wiring wires for various devices, power cables, fire-resistant cables, communication cables, and the like are included in the category of insulated wires and cables.

Hereinafter, the present invention will be described in more detail. The magnesium hydroxide particles in the present invention have an average secondary particle diameter of 3 μm or less, preferably 0.4 to 2 μm, as measured by a laser diffraction scattering method, and have little or no secondary aggregation. The specific surface area of the magnesium hydroxide particles measured by the BET method is 20 m2 / g or less, preferably 1 to 10 m2 / g. Further, in the magnesium hydroxide particles of the present invention, the total amount of iron compound and manganese compound as impurities is calculated as metal (Fe
+ Mn) is 0.02% by weight or less, preferably 0.01% by weight or less.

As described above, the magnesium hydroxide particles of the present invention have a total amount of metal (Fe + Mn) in the above range as an impurity. More preferably, they are a cobalt compound, a chromium compound, a copper compound, a vanadium compound and It is desirable that the content of the heavy metal compound as a metal, including the content of the nickel compound, be within the above range.
That is, the magnesium hydroxide particles are used as the metal (F
(e + Mn + Co + Cr + Cu + V + Ni) The total content is more preferably 0.02% by weight or less, preferably 0.01% by weight or less. The greater the content of heavy metal compounds such as iron compounds and manganese compounds in the magnesium hydroxide particles, the more significantly the thermal stability of the resin composition is reduced. However, the thermal stability of the resin is excellent only when the total amount of the iron compound and the manganese compound satisfies the above range, and it does not mean that the physical properties and the water-resistant insulating property and the acid resistance of the resin are not impaired. It is necessary that the average secondary particle diameter and the specific surface area each satisfy the above ranges. As the average secondary particle diameter of the particles increases, the contact surface with the resin decreases and the thermal stability improves, but problems such as a decrease in mechanical strength and poor appearance arise.

As described above, the magnesium hydroxide particles have (i) an average secondary particle diameter, (ii) a specific surface area, and (iii)
When the total content of the iron compound and the manganese compound (or the total amount of the other metal compounds) is within the above range, the compatibility with the resin, the dispersibility, the thermal stability, the molding and processability,
A resin composition that satisfies various properties such as appearance, mechanical strength, and flame retardancy of a molded article can be obtained.

The method for preparing the magnesium hydroxide particles of the present invention is not particularly limited as long as the requirements (i), (ii) and (iii) are satisfied. Magnesium hydroxide particles satisfying the average secondary particle diameter of (i) and the specific surface area of (ii) are described in, for example, JP-A-52-1.
It can be manufactured by basically employing the method and conditions described in US Pat. However, industrially, raw materials are magnesium raw materials such as natural brine, ion bitter, and seawater, and alkali substances such as alkali metal hydroxide, ammonia, magnesium oxide, and calcium hydroxide, and these are placed in an aqueous medium under pressurized conditions ( It can be produced by heating (preferably 2 to 30 kg / cm2). At this time, by selecting impurities that do not contain impurities, especially iron compounds and manganese compounds (and, if necessary, other metal compounds), or have extremely low contents, the requirements of (iii) above can be satisfied. Can be obtained.

It is preferable that the magnesium raw material and the alkaline substance are subjected to a purification treatment in order to reduce the content of iron compounds and manganese compounds therein.

In order to industrially produce the magnesium hydroxide of the present invention, it is necessary to pay attention to the material of the chemical equipment used. That is, it is necessary to use a FRP resin or a PVC resin which does not have a problem in corrosiveness, or a corrosion-resistant Hastelloy steel or stainless steel as a material of a chemical device to be used. Chemical devices made of highly corrosive materials such as carbon steel, when in direct contact with raw materials, Fe, Mn, etc. are eluted from the chemical devices, and the eluted Fe, Mn, etc. Or as a solid solution.

Therefore, in the production of the magnesium hydroxide particles of the present invention, a highly corrosive chemical device such as carbon steel is not used when it comes into direct contact with the raw material.

The magnesium hydroxide particles of the present invention can be directly blended with a resin as a flame retardant having heat deterioration resistance, but can be used after being treated with a surface treating agent.
Such surface treatment agents are selected from the group consisting of higher fatty acids, anionic surfactants, phosphate esters, coupling agents (silane-based, titanate-based, aluminum-based) and esters of fatty acids with polyhydric alcohols. At least one kind is mentioned.

Examples of the surface treatment agent preferably used are as follows. Higher fatty acids having 10 or more carbon atoms such as stearic acid, erucic acid, palmitic acid, lauric acid, and behenic acid; higher fatty acid salts; sulfate salts of higher alcohols such as stearyl alcohol and oleyl alcohol; sulfate salts of polyethylene glycol ether Amide bond sulfate, ester bond sulfate, ester bond sulfonate, amide bond sulfonate, ether bond sulfonate, ether bond alkylaryl sulfonate, ester bond alkylaryl sulfonate, amide bond alkylaryl sulfone Anionic surfactants such as acid salts; orthophosphoric acid and mono- or diesters such as oleyl alcohol and stearyl alcohol or a mixture of both, and their acid type or alkali metal salts or amine salts, etc. Phosphates; γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N-vinyl (Benzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ -Chloropropyltrimethoxysilane, hexamethyldisilazane,
γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ
-Chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane,
β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropylmethylethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldi Ethoxysilane, γ-methacryloxypropyltriethoxysilane,
N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-βaminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxy Silane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane,
Silane coupling agents such as isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, isopropyl tridecylbenzenesulfonyl titanate, tetraoctyl bis (ditridecyl phos) Phyto) titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, isopropyltridodecylbenzenesulfonyl titanate, tetraisopropylbis (dioctylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis-
(Ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate , Dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, and other titanate-based coupling agents;
Aluminum-based coupling agents such as acetoalkoxy aluminum diisopropylate, triphenyl phosphite, diphenyl tridecyl phosphite, phenyl ditridecyl phosphite, phenyl isodecyl phosphite, tri nonyl phenyl phosphite,
Polyhydric alcohols such as 4,4'-butylidene-bis (3-methyl-6-t-butylphenyl) -ditridecylphosphite, trilaurylthiophosphite, glycerin monostearate, glycerin monooleate and fatty acids Esters.

The surface coating treatment of the magnesium hydroxide particles using the above-mentioned surface treating agent can be carried out by a known wet or dry method. For example, as a wet method, the surface treatment agent is added to a slurry of magnesium hydroxide particles in a liquid or emulsion state,
Mixing may be sufficient mechanically at temperatures up to about 100 ° C.
As a dry method, a magnesium hydroxide particle powder is added in a mist, liquid, emulsion, or solid state with sufficient stirring with a mixer such as a Henschel mixer, and the mixture is thoroughly mixed with or without heating. I just need. The amount of the surface treatment agent can be appropriately selected, but is preferably about 10% by weight or less based on the weight of the magnesium hydroxide particles.

The surface treating agent may be added as an integral blend when kneading the magnesium hydroxide particles and the synthetic resin.

The magnesium hydroxide particles having been subjected to the surface treatment can be subjected to a method such as washing with water, dehydration, granulation, drying, pulverization, classification, or the like, as necessary, to obtain a final product form. Magnesium hydroxide particles in the resin composition of the present invention, based on 100 parts by weight of the synthetic resin,
10 to 500 parts by weight, preferably 30 to 400 parts by weight,
More preferably, it is blended in a proportion of 50 to 300 parts by weight. If the amount is less than 10 parts by weight, the flame retardancy is insufficient, and
When the amount is more than 00 parts by weight, the mechanical strength decreases.

The synthetic resin in which the magnesium hydroxide particles of the present invention are blended may be any resin which is usually used as a molded article, and examples thereof include polyethylene, polypropylene, ethylene / propylene copolymer, polybutene, and polybutene. Polymers or copolymers of C2-C12 olefins (α-olefins), such as 4-methylpentene-1;
Copolymers of these olefins and dienes, ethylene-
Thermoplastic resins containing no halogen in their molecular structure, such as acrylate copolymers, MBS resins, ethylene vinyl acetate copolymer resins, vinyl acetate resins, urethane resins, polyamides, and ionomer resins can be exemplified.

Preferable examples of these thermoplastic resins are polyolefins or copolymers thereof excellent in the flame retardant effect, heat deterioration preventing effect and mechanical strength retention characteristics of magnesium hydroxide particles. , Atactic polypropylene, such as polypropylene resin, low density polyethylene, linear low density polyethylene,
Ultra low density polyethylene, EVA (ethylene vinyl acetate resin), EEA (ethylene ethyl acrylate resin), EMA (ethylene methyl acrylate copolymer resin), EAA (ethylene acrylic acid copolymer resin), polyvinyl butyral resin (PVB), polyvinyl Polyethylene resins such as alcohol resins (PVA), and polymers or copolymers of C2-C12 olefins (α-ethylene) such as polybutene, poly-4-methylpentene-1, polyhexene-1, and polyheptene-1 And TPO.

Further, synthetic rubbers such as EPDM, butyl rubber, isoprene rubber, SBR, NBR, NIR, urethane rubber, butadiene rubber, acrylic rubber, silicone rubber and fluoro rubber can be exemplified.

In the present invention, the synthetic resin used is not limited by the production method. For example, in the case of polyolefin, any polymerization catalyst such as metallocene, Ziegler, Ziegler-Natta, Friedel Kraft, etc. may be used. It may be one manufactured by:

The resin composition of the present invention is substantially formed of (a) a halogen-free synthetic resin and (b) magnesium hydroxide particles, and further comprises a flame retardant auxiliary (c).
In a small amount. By blending the flame retardant aid (c), the blending ratio of (b) magnesium hydroxide particles can be reduced, and the flame retardant effect can be increased.

The flame retardant aid (c) is preferably red phosphorus, carbon powder, silicone or a mixture thereof. As the red phosphorus, for example, red phosphorus whose surface is coated with a thermosetting resin, a polyolefin, a carboxylic acid polymer, titanium oxide, or a titanium aluminum condensate can be used in addition to ordinary red phosphorus for a flame retardant. Examples of the carbon powder include carbon black, activated carbon and graphite, and carbon black is preferable because it is inexpensive and fine particles. The carbon black may be prepared by any of an oil furnace method, a gas furnace method, a channel method, a thermal method and an acetylene method.

As the silicone, silicone resin, silicone oil, silicone grease and silicone rubber can be used. When the flame retardant aid (c) is blended, the proportion thereof is 0.5 to 20% by weight, preferably 1 to 15% by weight based on the total weight of (a) the synthetic resin and (b) the magnesium hydroxide particles. Is appropriate. The resin composition of the present invention comprises (a) a halogen-free synthetic resin and (b) magnesium hydroxide particles, and if necessary, (c) a flame-retardant auxiliary in the above-mentioned ratios according to a means known per se. What is necessary is just to mix.

In order to improve the mechanical strength of the heat-degradable flame-retardant insulated wire and cable of the present invention before molding, the polymer alloy compatibilizer may be added. good. Specific examples of the polymer alloy compatibilizer include maleic anhydride-modified styrene-ethylene butylene resin, maleic anhydride-modified styrene-ethylene butadiene resin, maleic anhydride-modified polyethylene, maleic anhydride-modified EPR, and maleic anhydride-modified polypropylene. , Carboxyl-modified polyethylene, epoxy-modified polystyrene / PMMA, polystyrene-polyimide block copolymer, polystyrene-polymethyl methacrylate block copolymer, polystyrene-polyethylene block copolymer, polystyrene-ethyl acrylate graft copolymer, polystyrene-polybutadiene graft copolymer, polypropylene-ethylene-propylene Diene graft copolymer, polypropylene-polyamide graft copolymer, polyacryl Ethyl chromatography polyamide graft copolymer and the like.

The resin composition having heat resistance deterioration and flame retardancy in the present invention may contain other conventional additives in addition to the above components. Such additives include, for example, antioxidants, antistatic agents, pigments, foaming agents, plasticizers,
Examples include fillers, reinforcing agents, crosslinking agents, light stabilizers, ultraviolet absorbers, lubricants, and the like.

These additives are preferably non-halogen compounds according to the gist of the present invention. If a halogen compound is used, the content of the halogen compound in the resin composition is 1% by weight or less, preferably 0.1% by weight or less, more preferably 0.01% by weight, including the amount derived from other components.
%.

The structure and manufacturing method of the halogen-free heat-degradable flame-retardant insulated wire and cable of the present invention are not particularly limited. Any structure and manufacturing method can be adopted as long as the object of the present invention is achieved.

That is, a conductor (copper, copper alloy, aluminum, aluminum alloy, optical fiber, or the like) is coated with the above-described flame-retardant resin composition having excellent heat resistance and mechanical strength as an insulating portion and / or a sheath portion. Thus, the heat-deteriorating flame-retardant electric wires and cables of the present invention can be obtained.

At the time of coating, cross-linking such as chemical cross-linking, radiation cross-linking, and silane cross-linking may be performed, but not necessarily.

The structure may be a single core,
It may be a multi-core type, a round type, or a flat type.

Hereinafter, the present invention will be described in more detail with reference to examples. However, all% means weight%.

The measurement of the particle properties of the magnesium hydroxide particles and the measurement of the physical properties of the resin composition molded article were carried out by the following methods.

(1) Average secondary particles of magnesium hydroxide
Diameter MICROTRAC particle size analyzer SPA type [LEED
S &amp; NORTHRUPINSTRUMENT
TS Co., Ltd.]. Sample powder 700m
g was added to 70 ml of water, and subjected to a dispersion treatment for 3 minutes by an ultrasonic wave (manufactured by NISSEI, MODELUS-300, current: 300 μA), and 2-4 ml of the dispersion was taken.
After adding 250 ml of degassed water to the sample chamber of the above particle size analyzer, activating the analyzer and circulating the suspension for 8 minutes, the particle size distribution is measured. Take a total of two measurements,
(2) BET specific surface area of magnesium hydroxide particles Measured by liquid nitrogen adsorption method.

(3) Fe and M of magnesium hydroxide particles
n, Fe, Mn, Cu, V, Co, N
i, Cr total content of heavy metals ICP-MS method (Inductively Coupled)
ed Plasma-Mass Spectrometer
ry) or the atomic absorption method.

(4) Tensile strength and elongation of molded article Measured according to JIS K7113. (5) Flame retardancy of molded article Measured according to the UL 94 VE method. The oxygen index is
It measured according to JISK7201.

(6) Thermal stability of molded product The following test was conducted at 150 ° C. using a gear oven. The test piece used had a thickness of 2.1 mm. 1. The number of days until the molded article thermally degrades and powders (mainly white powder) 2. Tensile strength and elongation after 10 days at 150 ° C thermal stability test

Examples 1 and 2 and Comparative Examples 1 and 2 The following resin compositions were prepared. 100 parts by weight Ethylene vinyl acetate copolymer (vinyl acetate content 30% by weight) 150 parts by weight Magnesium hydroxide particles (Table 1 was used.) Surface with 1.0% by weight of sodium oleate based on magnesium hydroxide particles Treated products AI, A-II, BI, B-II) 1 part by weight DCP (di-cumyl peroxide) 1 part by weight Antioxidant (Irganox 1076 manufactured by Ciba Special Chemicals Co., Ltd.) This composition The mixture was kneaded at 120 ° C with a single kneading extruder, and pre-formed at 120 ° C for 5 minutes with a compression molding machine.
Crosslinking was performed for 5 minutes to obtain 2.1 mm and 3 mm plates. A test piece was prepared from this plate and the physical properties were measured. Table 2 shows the results. Test piece AI ... Magnesium hydroxide particle compound of sample AI Test piece A-II ... Magnesium hydroxide particle compound of sample A-II Test piece BI ... Sample BI Test piece B-II ... magnesium hydroxide particle compound of sample B-II

[0052]

[Table 1]

[0053]

[Table 2]

In the examples, heat stability, tensile strength, elongation and flame retardancy are excellent. On the other hand, in the comparative examples, there is a serious drawback in the measurement items, particularly in thermal stability.

Example 3 and Comparative Examples 3 and 4 The EVA resin used in Example 1 was changed to an EEA resin (ethylene ethyl acrylate resin; ethyl acrylate content: 20 wt%), and the magnesium hydroxide particles used were: In Example 3, A-III and Comparative Example 3
An experiment was performed in the same manner as in Example 1 except that B-III was used and B-IV was used in Comparative Example 4. A-III particles are those having the specific properties defined in the present invention, B-III and B
-IV particles whose content of heavy metals such as Fe and Mn are within the range specified by the present invention, but whose average secondary particle diameter and / or BET specific surface area are out of the range specified by the present invention are used. . However, the flame retardancy was measured using a test piece having a thickness of 4 mm.
The surface treatment is performed so that 4.5% of stearic acid is adsorbed on the magnesium hydroxide particles. Table 3 shows the results.

In Examples, the thermal stability, tensile strength, elongation, and flame retardancy were all excellent, but in Comparative Examples, one or more of the measured items had serious drawbacks. The kneading workability of the resin composition was also evaluated. In Example 3 and Comparative Example 4 using magnesium hydroxide having a relatively small BET specific surface area, there was no problem in kneading workability, but in Comparative Example 3 having a large BET specific surface area, kneading workability was extremely difficult. there were.

[0057]

[Table 3]

Examples 4, 5, and 6 The magnesium hydroxide particles in Example 1 were changed to the following A-IV particles in Example 4, to the following AV particles in Example 5, and to the following A-VI particles in Example 6. The same test as in Example 1 was performed except that the test was performed. A-IV particles are stearyl phosphate diethanolamine salt

[0059]

Embedded image

With 50% of diester of

[0061]

Embedded image

The surface treatment was carried out at 3 wt% with respect to the AI particles before surface treatment using a mixture of 50% of monoester. The amount of adsorption was 2.6 wt%, and the content of Mg (OH) 2 was 97.0%.

The AV particles are obtained by subjecting the AI particles before surface treatment to a surface treatment with 3 wt% of isopropyl triisostearoyl titanate in a mixed solvent of water and triethanolamine. The amount of adsorption is 2.6w
t%, and the content of Mg (OH) 2 was 97.0%.

The A-VI particles are obtained by subjecting the A-I particles before the surface treatment to a surface treatment with 1 wt% of a silane coupling agent (NUC A-172, manufactured by Nippon Yunika Co., Ltd.). The amount of adsorption was 1 wt%, and the content of Mg (OH) 2 was 98.6%. A-IV particles, A-V particles, and A-VI particles have a different adsorbed substance and amount of adsorption, and a different content of Mg (OH) 2, compared with the A-I particles. , A-I particles were substantially equivalent to the particle properties.

As in Example 1, the flame retardancy (oxygen index) of the resin composition in which the EVA resin was filled with A-IV particles, AV particles, and A-VI particles was about 38. The thermal stability (the number of days until white powdering) was all 35 days or more.

Example 7 In Example 1, the compounding amount of the AI particles was reduced from 150 parts by weight to 60 parts by weight, and 10 parts by weight of red phosphorus (Nova Excel F-5 manufactured by Rin Kagaku Kogyo Co., Ltd.) and carbon black were used. UL94 (Shift SO FEF manufactured by Tokai Carbon) was added in the same manner as in Example 1 except that 5 parts by weight was newly added.
A test piece for VE was prepared. Flame retardant is UL94VE
It was V-0 by the method (1/8 inch).

Example 8 The following composition was prepared, masticated at 70 ° C. with an open roll, and vulcanized one day later at 160 ° C. for 30 minutes to obtain a １ ／ inch thick plate. . A test piece having a thickness of 1/8 inch for a UL94-VE test was prepared from the obtained plate. About this test piece, UL94V
E was tested. As a result of the test, the flame retardancy was V-1.

Composition 100 parts by weight EPDM rubber (ethylene / propylene ratio = 50/50 mol) 170 parts by weight Magnesium hydroxide particles (AI) 3 parts by weight Dicumyl peroxide 0.5 parts by weight Poly (2,2, 4-trimethyl-1,2-dihydroquinoline) 1 part by weight Silane coupling agent (A-172 manufactured by Nippon Yunika) 1 part by weight Stearic acid 1 part by weight Sulfur Example 9 Coating each of the admixtures of Examples 1 to 7. Used as material,
A test piece for a JIS C3005 flame retardancy test was prepared, and a JIS C3005 flame retardancy test was performed.
However, the thickness of the coating material was 3 mm, and the conductor was a test piece using a copper wire and an optical fiber, respectively. The results of the flame retardant tests were all self-extinguishing.

Example 10 The composition of Example 8 was used as a coating material and JIS C30
Test piece for flame retardant test of JIS 04
A 3004 flame retardancy test was performed. However, the thickness of the coating material is 3
mm, the conductor was a test piece using a copper wire and an aluminum wire, respectively. The results of the flame retardant tests were all self-extinguishing.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) H01B 3/00 H01B 7/34 BF term (reference) 4J002 AC031 AC061 AC071 AC081 BB031 BB061 BB071 BB121 BB151 BB171 BB191 BB231 BD121 BE021 BE061 BF021 BG041 BN161 CK021 CL001 CP031 DE076 FB086 FB096 FB106 FB116 FB136 FB146 FB166 FB216 FB236 FD130 FD136 GQ01 5G303 AA06 AB20 BA12 CA09 CA11 CC08 CD03 5G315 CA03 CD02 CD08 CD08

Claims (10)

[Claims] 1. A resin composition comprising 100 parts by weight of a halogen-free synthetic resin and 10 to 500 parts by weight of magnesium hydroxide particles, wherein the magnesium hydroxide particles have the following (i) to (iii): (I) The average secondary particle diameter is 3 μm or less. (Ii) The BET specific surface area is 20 m 2 / g or less. (Iii) The total content of the Fe compound and the Mn compound is 0.02% by weight in terms of metal. A heat-resistant, flame-retardant, insulated wire and cable coated with a resin composition satisfying the following. 2. The resin composition is characterized in that magnesium hydroxide particles 3 are added to 100 parts by weight of a halogen-free synthetic resin.
The heat-deteriorating flame-retardant insulated wire and cable according to claim 1, which is a composition containing 0 to 400 parts by weight. 3. The resin composition according to claim 1, wherein said magnesium hydroxide particles are added to 100 parts by weight of a halogen-free synthetic resin.
The heat-deteriorating flame-retardant insulated wire and cable according to claim 1, which is a composition containing 0 to 300 parts by weight. 4. The magnesium hydroxide particles include an iron compound, a manganese compound, a cobalt compound, a chromium compound,
The total content of the copper compound, the vanadium compound, and the nickel compound is 0.02% by weight in terms of metal.
The flame-retardant insulated wire and cable according to claim 1, wherein 5. The flame-resistant insulated wire according to claim 1, wherein the magnesium hydroxide particles have a total content of iron compound and manganese compound of 0.01% by weight or less in terms of metal. cable. 6. The magnesium hydroxide particles have an average secondary particle diameter of 0.4 to 2 μm measured by a laser diffraction scattering method.
2. The heat-degradable flame-retardant insulated wire and cable according to claim 1, wherein m is m. 7. The flame-retardant insulated wire and cable according to claim 1, wherein the magnesium hydroxide particles have a specific surface area measured by a BET method of 1 to 10 m 2 / g. 8. The insulated wire and cable according to claim 1, wherein the synthetic resin is a polyolefin resin composition. 9. The magnesium hydroxide particles may contain higher fatty acids, anionic surfactants, phosphate esters, silane coupling agents, titanate coupling agents, aluminate coupling agents, and fatty acid esters of polyhydric alcohols. The flame-retardant insulated wire and cable according to claim 1, which has been surface-treated with at least one kind of surface treatment agent selected from the group consisting of: 10. The flame-retardant insulated wire and cable according to claim 1, wherein the resin composition contains the surface treating agent according to claim 9.