JPS62215644A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:The tilted composition, obtained by blending a base polymer containing straight-chain polyethylene with hydrate of a metal oxide, having improved flame retardance, etc., without smoking, emission of corrosion gases, etc., in combustion because of the halogen-free composition and suitable for insulating covering of electric wires and cables. CONSTITUTION:A composition, obtained by blending 100pts.wt. base polymer which is a mixture of straight-chain polyethylene having 0.91-0.94 density and 0.1-10 melt index with one or more of the group consisting of poly-alpha-olefins and polypropylene, etc., with 50-300pts.wt., preferably 70-200pts.wt. hydrate of a metal oxide, e.g. hydrated alumina, hydrated magnesia, etc., and further, as necessary, flame retardant assistant, antioxidant, processing aid, carbon black and coupling agent.

Description

[Detailed description of the invention] Hiisen Yodan■Rikata! The present invention relates to a flame retardant resin composition.

No. 41, Conventionally known flame-retardant resin compositions include halogen-containing polymers or non-halogen-based polymers to which organic halogen-based flame retardants are added. However, although all products obtained using such flame-retardant resin compositions self-extinguish when kept away from flames, when they are exposed to high-temperature flames such as in the event of a fire, they are resistant to up to 100% of acid. There are drawbacks such as continued combustion, generation of a large amount of smoke, and thermal decomposition that generates corrosive and highly toxic acidic gases, leading to secondary disasters.

On the other hand, attempts have also been made to overcome the above drawbacks by blending halogen-free flame retardants with low-density ethylene homopolymers, medium-density ethylene homopolymers, or high-density ethylene homopolymers. However, in order to increase the flame retardance of a resin composition containing a halogen-free flame retardant to a practically sufficient degree, it is necessary to incorporate a large amount of the halogen-free flame retardant, which results in the following drawbacks: It is inevitable that this will occur. That is, when a large amount of halogen-free flame retardant is blended into a low-density ethylene homopolymer or a medium-density ethylene homopolymer, the resulting molded resin composition has poor mechanical properties, especially mechanical strength and elongation. This decreases significantly, causing practical inconvenience. Furthermore, even when a large amount of halogen-free flame retardant is blended into a high-density ethylene homopolymer, the resulting resin composition molded product has impaired mechanical properties, especially mechanical strength and elongation. With the passage of time, the above-mentioned mechanical properties deteriorate significantly, making it impossible to maintain practically sufficient mechanical properties. As described above, in the case of halogen-free resin compositions, flame-retardant resin compositions that have excellent flame retardancy and can impart practically sufficient mechanical properties to molded products over a long period of time have not yet been fully developed. Currently, it has not been developed.

An object of the present invention to reduce IO deficiency is to provide a halogen-free resin composition with excellent flame retardancy.

Another object of the present invention is to provide a flame-retardant resin composition that can be used for a long period of time and impart practically sufficient mechanical properties to molded articles.

Other features of the invention will become apparent from the description below.

The flame-retardant resin composition of the present invention comprises (A) about 100 parts by weight of a pace polymer containing linear polyethylene, and (B) about 50 to 300 parts by weight of a metal oxide hydrate.

In the present invention, the linear polyethylene used as component (A) is a copolymer of olefin having 4 to 16 carbon atoms and ethylene, and has a density of greater than 0.90 and less than or equal to 0.96. , melt index (MFR)
refers to essentially linear polyethylene having a polyethylene of from 0.1 to 20. Such linear polyethylene is produced, for example, by the method shown below.

That is, it is produced by polymerizing a mixture of ethylene and an olefin having 4 to 16 carbon atoms under low pressure in the presence of a catalyst. The mixing ratio of ethylene and olefin is as follows:
Usually about 3 to about 20 parts by weight of the latter per 100 parts by weight of the former,
Preferably, it is about 5 to about 10 parts. Catalysts used include, for example, silica, alumina, zirconia, so-called Phillips catalysts represented by chromium oxide using silica/alumina as carriers, and catalysts from Groups 1V to 15 of the Periodic Table of Elements.
Examples include Ziegler catalysts produced by a combination of a Group Ⅰ transition metal compound and an organic gold ash compound of Groups 1 to 1V. A specific example of Ziegler catalyst is T'1CQ.
t and alkyl aluminum (e.g. AQ2 (Ej3)CQ
3, AQ (Ej)20Q, Al2E'j3, etc.). Furthermore, nBu2Mg・1/6 AQ
A mixture of an organomagnesium compound such as E i3, the aforementioned Ti compound, and an organometallic halide may be used as a catalyst. The amount of such catalyst used is usually 0.01 to about 50 parts by weight, preferably about 0.01 to about 50 parts by weight, per 100 parts by weight of the mixture of ethylene and olefin having 4 to 16 carbon atoms.
The amount is preferably from 0.05 to about 20 parts by weight. The pressure during this polymerization is usually about normal pressure to about 20 atm, preferably about normal pressure to about 10 atm. Preferred specific manufacturing methods for these linear polyethylenes include JP-A-51-1
12891, JP 55-45722, JP 55-113542, U.S. Patent No. 39574
For example, the method described in the specification of No. 48 and the like can be exemplified.

In the present invention, among the above linear polyethylenes,
It is preferable that the olefin as a comonomer copolymerized with the ethylene chain constituting the polyethylene has about 4 to 10 carbon atoms, and more specifically, the comonomer is butene-1, octene-1, and 4-methylpentene-1. 1 is most preferred.

Also, among the above-mentioned linear polyethylenes, ASTMDl
505 is preferably about 0.91 to about 0.96, more preferably about 0.91 to about 0.94, and most preferably about 0.911 to about 0.925. Furthermore, among the above linear polyethylenes, ASTM
Those having a VFR of about 0.1 to about 10 as measured by D1238 are preferred. Specific examples of such linear polyethylene include Mitsubishi Polyethylene-LL H20E, F30F.
, F30H (all manufactured by Mitsubishi Yuka Co., Ltd.), Urtozex 202OL, 3010F, 3021F (all manufactured by Mikata Petrochemical Co., Ltd.), DFDA-7540 (manufactured by Union Carbide), NUCG-5651, G5-650. GR3
N-7047, GR3N-7042 (all manufactured by Nippon Unicar), Idemitsu polyethylene-10134H, 023
4H (all manufactured by Idemitsu Petrochemical Co., Ltd.), etc. can be exemplified.

Further, in the present invention, poly-α-
A mixture of olefins can be used. Here, poly-α-olefin is a copolymer of ethylene and α-olefin having 4 to 8 carbon atoms polymerized using a Ziegler catalyst, and has a density of 0.85 to 0.90 and an MFR of 1
〜10 things. Among these poly-α-olefins, those having a density of about 0.86 to about 0.89 are preferable, and those having an MFR of about 1 to about 5 are preferable. Such a poly
As a specific example of α-olefin, for example, Tafmer A-
4090, A-4085, P-0180, P-0480
(both manufactured by Mikata Petrochemical Co., Ltd.).

When poly-α-olefin is mixed with the above-mentioned linear polyethylene, the mixing ratio is usually:
The weight ratio of invaders is about 1 to 99: about 99 to 1, preferably about 95 to 40: about 5 to 60.

Further, in the present invention, polypropylene may be mixed with the linear polyethylene. Here, the polypropylene has an MFR of about 0.1 to about 5, for example,
Examples of polypropylene having a density of about 0.88 to about 0.91 include BO2-D, EC9 (both manufactured by Mitsubishi Yuka Co., Ltd.), and 5B210. F2O3 (all manufactured by Mikata Petrochemical Co., Ltd.), E250G (manufactured by Idemitsu Oil Co., Ltd.),
Examples include MK112 (manufactured by Showa Denko).

When polypropylene is mixed with the above-mentioned linear polyethylene, the mixing ratio is usually about 50 to 99: about 50 to 1, preferably about 70:
-99: It is preferable to set it to about 30-1.

Furthermore, when using a blend of the linear polyethylene, poly-α-olefin and polypropylene, the weight ratio of the linear polyethylene and poly-α-olefin is 30 to 70: 70 to 30. It is preferable to mix about 66 to 150 parts of polypropylene per 100 parts by weight of the blended mixture.

Further, an ethylene-vinyl acetate copolymer (EVA) may be mixed with the above-mentioned linear polyethylene. The EVA used here has an MFR of about 0.2, for example.
~30 and vinyl acetate (VA) content is about 5~
Examples include those having a VA content of about 75% by weight, and preferably those having an MFR of about 0.5 to about 20 and a VA content of about 5 to 50% by weight. As a specific example, for example, Evaflex EV660. V527
-4, EV-270, Vl 70. EV45L
X (all manufactured by DuPont Sani Polychemicals), N
tJC-8450, DQDJ-3269, NUC-30
50, NLLC-3270 (all manufactured by Nippon Unicar), Yucalon-Eva V213, V403E, V6O1
3, V2O3 ((, 'fl'L is also manufactured by Mitsubishi Yuka Co., Ltd.), etc.).

Furthermore, in the present invention, an ethylene-ethyl acrylate copolymer (EEA) can be mixed with the linear polyethylene. Examples of the EEA used here include those having a VFR of about 0.2 to about 25 and an ethyl acrylate (EA) content of about 3 to about 35%, preferably VFR is about 0.4 to about 2
0 and the EA content is about 5 to about 25% by weight. Specific examples include Nu, I
C-6220, DQDJ-6182, Nu, IC-65
70 (all manufactured by Nippon Unicar), A170, A27
0. T4340-16 (both manufactured by Nippon Petrochemicals)
, XC-300E, C-400K [all manufactured by Mitsubishi Yuka Co., Ltd.], A-701, A-702, A-706, A-71
0 (all manufactured by Mikata, DuPont Polychemical Co.), and the like.

When the linear polyethylene is mixed with the EVA or EEA, the mixing ratio is usually the former:
The weight ratio of the latter is preferably about 20 to 99: about 80 to 1, preferably about 50 to 99: about 50 to 1.

In the present invention, hydrates of metal oxides used as component (B) include, for example, those in Group A, Group [A, Group MB, Group 1 Va, and Group 1 Vb of the Periodic Table of Elements]. Hydrates of oxides of metal elements belonging to this group, and double salts or compounds of these with carbonates of metal elements belonging to Group 1a or Group 1Ia are mentioned, and specific examples thereof include AQ203·nH2O (n is 0. 5-6, especially 2.5-
3.5) (hereinafter referred to as "hydrated alumina"), Mg
0-nH2O (nl, to, 5-5, especially 1.5-2.
5) (hereinafter referred to as "hydrated magnesia"), Ba0
・9H20, BaO・H2C, zro・2H20, Sn
O*nH20 (n is a number from 1 to 10), 3M (jcOa
・MQ(OH)2 ・3H2O16MgO・Al2O3
・H20, NaCO3・AQ203・nH2O (n is 1
~10), Na2O.BaO3.5H20, etc. In the present invention, one type or a mixture of two or more types of these can be used. The particle size of these metal oxide hydrates is usually about 10 μm or less, especially about 5 μm or less.
Suitably less than μm, practically about 0.1 to about 5 μm
is suitable. Also, among the hydrates of these metal oxides, hydrated alumina and hydrated magnesia are particularly suitable. A specific example of hydrated alumina is Hysilite H-42M
Examples include [manufactured by Showa Light Metal Company], 81403, and B1403S [all manufactured by Nippon Light Metal Company].

Further, particularly suitable hydrated magnesia is one having a specific surface area of 3 to 15 m<2>/Q by the BET method and a particle size distribution of 5 microns or more being 0% by the Luzex method. Specific examples include Kisuma 75B, Kisuma 5A, Kisuma 5E (all manufactured by Kyowa Chemical Industry Co., Ltd.), and K.
Examples include X-43 (manufactured by Asahi Glass Co., Ltd.).

In the present invention, the above (B) component is usually (6) (A) component 10
0 parts by weight, about 50 to about 300 parts by weight, preferably about 70 to about 200 parts by weight, more preferably about 90 to about 1
It is preferable to mix 50 parts by weight.

(If the blending amount of component (B) exceeds 300 parts by weight, there will be a disadvantage that the mechanical properties of the resulting resin composition will deteriorate.On the other hand, if the blending amount of component (B) is less than 50 parts by weight, A drawback arises that the flame retardancy of the resulting resin composition is reduced.

In the present invention, red phosphorus, zinc borate,
It is preferable to incorporate titanium dioxide or the like into the composition of the present invention. Here, as the red phosphorus, a wide variety of commercially available ones can be used, for example, the red phosphorus content is about 80% or more, the loss on drying is about 0.8% or less, and the 74 mesh sieve residue is about 7%. The following are preferred. Moreover, it is preferable that the surface of the red phosphorus is coated with a thermosetting resin such as phenol-formalin resin. A specific example is No Bullet #120. Novellet #120LIF (both manufactured by Rin Kagaku Kogyo Co., Ltd.) and the like can be mentioned.

As zinc borate, conventionally commercially available ones can be widely used, for example, those with the chemical formula 2Zn0.3B203.3.5H
20 with a particle size of about 2 to about 10μ and a crystal density of about 2.6 to about 2.8 (J/Cm3).Specific examples include zinc borate 2335 (UK 3
orax Co., Ltd.].

As titanium dioxide, a wide range of commercially available titanium dioxides can be used, such as titanium dioxide containing at least about 90% of titanium dioxide and having a particle size that can pass through a 100-mesh sieve;
At least about 90% T! Preferred examples include those containing 0.02 and having a 149μ sieve residue of 0% and a moisture content of 0.7% or less. More specifically, Taitone A-15
0, Titone R-650 (all manufactured by Sakai Chemical Industry Co., Ltd.)
etc.

In the present invention, these flame retardant aids are usually blended in an amount of about 0.5 to about 50 parts by weight, preferably about 2 to about 25 parts by weight, per 100 parts by weight of component (A). The amount of flame retardant aid is 50
If it exceeds the heavy assembly part, the mechanical properties of the resulting resin composition tend to deteriorate, which is not preferable. On the other hand, if the amount of the flame retardant aid is less than 0.5 parts by weight, the effect of adding the flame retardant aid tends to be lost, which is not preferable.

In the present invention, it is preferable to incorporate an anti-aging agent into the composition of the present invention. Examples of the anti-aging agent include hindered phenol-based anti-aging agents, amine-based anti-aging agents, and the like. As the hindered phenol anti-aging agent, a wide variety of conventionally known anti-aging agents can be used, such as tetrakis[methylene-5-(3,5-di-tert-butyl-4-hydroxyphenol)propionate]methane[Irganox 1010. manufactured by Ciba Geigy),
2,2-thio(diethyl-bis-3-(3,5-dit)
ert-butyl-4-hydroxyphenol) propionate] [Irganox 1035, manufactured by Ciba Geigy), 4,4'-thiobis(3-methyl-5-ter
t-butylphenol) (Santonox, Monsanto Company 1), 4,4'-methylene-bis(3,5-di-t
ert-butylphenol) [Ionox 220,
Examples include Ei I (manufactured by I Company). Furthermore, as the amine-based anti-aging agent, a wide variety of conventionally known anti-aging agents can be used, and specific examples include the antioxidant DDA.
(DDA1 manufactured by Bayer), N,N'-di-β-naphthyl-p-phenylenediamine (Tsukrak White, manufactured by Iriuchi Shinko Co., Ltd.), N,N'-diphenyl-p-phenylenediamine (Tsukrac DP, Ouchi Shinko Co., Ltd.) (manufactured by Shinkosha), N, N'
-diisopropyl-p-phenylenediamine [Antioxidant No. 23, manufactured by DuPont] and the like. In the present invention, these anti-aging agents may be used alone or in combination of two or more.

The amount of the anti-aging agent added is usually about 0.1 to about 5 parts by weight, preferably about 0.2 to about 3 parts by weight, more preferably about 0.3 to about 5 parts by weight, per 100 parts by weight of component (A). The amount is preferably about 2 parts by weight. Even if the amount of the anti-aging agent exceeds 5 parts by weight, the anti-aging effect will not improve significantly and this is not economically preferable.

On the other hand, if the amount of anti-aging agent is less than 0.1 part by weight, the anti-aging effect will be difficult to exhibit, which is undesirable.

The composition of the present invention preferably contains higher fatty acids or metal salts thereof as processing aids. Examples of higher fatty acids include stearic acid and oleic acid, and examples of metal salts include zinc salts and calcium salts.

The blending amount of the higher fatty acid or its metal salt is usually 0.1 to about 10 parts by weight, preferably about 0.5 to about 5 parts by weight, per 100 parts of component (6) (A). It is better to do so. If the amount of the higher fatty acid or its metal salt exceeds 10 parts by weight, there will be a tendency for the resulting resin composition to deteriorate in properties such as mechanical properties. If the amount is less than 0.1 part by weight, the effect of addition as a processing aid will not be recognized.

Further, it is preferable to incorporate carbon black into the composition of the present invention. As carbon black, for example, DBP
Oil absorption is 100-160cm3/1009 and AS
Furnace black whose TM code is recognized as N330-N351, DBP oil absorption 30-50cm3/
An example is thermal black of 10oQ. Specific examples of such carbon black include FEF carbon black, HAF carbon black, 15AF carbon black, SRF carbon black, and more specifically, for example, Dia Black H1 Dia Black H3.
(all manufactured by Mitsubishi Chemical Corporation), VUIkan-3, Vu
l kan-3H (both manufactured by Cabot), GEST H1 GEST 3 (both manufactured by Tokai Electrode), Ketsuen Black HAFC (manufactured by Ketsuen), etc. Among these, Diamond Black H and ■ulkan-3 are listed. preferable.

In the present invention, the above carbon black is usually (6) (A)
From about 0.5 to about 40 parts by weight, preferably from about 1 to about 20 parts by weight, per 100 parts by weight of component.

If the amount of carbon black exceeds 40 parts by weight, the mechanical properties of the resulting resin composition tend to be impaired, which is not preferable. Also, the amount of carbon black added is 0.
If the amount is less than 5 parts by weight, the ashing properties will be difficult to develop, which is not preferable.

In the present invention, it is desirable to incorporate a coupling agent into the composition of the present invention. As the coupling agent, a wide variety of conventionally known coupling agents can be used, and examples include monoalkoxy type, neoalkoxy type, coordination type, chelate type titanate coupling agents and silane coupling agents. Among the titanate coupling agents mentioned above, those containing phosphorus are preferred. A specific example is tetraisoprovir di(dioctyl phosphite) titanate [KR-4
18, manufactured by Kenrich Co., Ltd.], isoprogol tris(dioctyl pyrophosphate) titanate (KR38S, manufactured by the same company), and bis(dioctyl pyrophosphate) oxyacetate titanate (KR138S, manufactured by the same company).

Specifically, the chelate-type titanate coupling agent is diisostearoyloxyacetate titanate (
KR-101, manufactured by Kenrich Corporation], dicumylferrate oxyacetate titanate (KR-1343, manufactured by the same company), di(dioctyl phosphate) ethylene titanate (KR-212, manufactured by the same company), 4-aminebenzenesulfonyldodecylbenzene Sulfonyl ethylene titanate (KR-2268, manufactured by the same company), di(butyl).

methyl pyrophosphate) ethylene titanate (KR-
262ES, manufactured by the same company].

As the silane coupling agent, trialkoxysilane having a carbon-carbon double bond or an epoxy group is preferable, and specifically, vinyl-tris(β-methoxyethoxysilane) (A172, manufactured by Nippon Unicar Co., Ltd.), γ-methacrylate Roxypropyltrimethoxysilane (A174, manufactured by the same company), β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (A186, manufactured by the same company), γ-
Glycidyloxypropyltrimethoxysilane (SH6
040, manufactured by Toray Silicone Co., Ltd.).

The amount of the above-mentioned coupling agent is usually as specified in (6) above.
About 0.1 to about 5 parts by weight, preferably about 0.3 to about 3 parts by weight, more preferably about 0.1 to about 5 parts by weight, per 100 parts by weight of component (A).
5 to about 2 parts by weight is preferred.

If the amount of the coupling agent exceeds 5 parts by weight, the flame retardance, heat resistance, etc. of the resulting resin composition will tend to decrease, which is not preferable. Also, the amount of coupling agent blended is o,
When the amount is less than 1 iti part, workability tends to be poor.

In the present invention, when the above-mentioned polypropylene is mixed with linear polyethylene and used as the component (6) (A), it is particularly suitable to incorporate a copper damage inhibitor into the composition of the present invention. As the copper damage inhibitor used, a wide variety of conventionally known ones can be used, such as N,N'-bis(3-(
3',5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hydrazine, (3-(N
-salicyloyl)amino-1,2,4-tetrazole)
, N, N'-dibenderoxalyl dihydrazide, N,
Examples include N'-disalicylidene oxalyl hydrazide. The amount of the copper damage inhibitor to be added is usually about 0.02 to about 5 parts by weight, preferably about 0.1 to about 2 parts by weight, per 100 parts by weight of the polypropylene. Even if the amount of the copper damage inhibitor exceeds 5 parts by weight, the effect of adding the copper damage inhibitor will not improve much, and this is not economically preferable.

Furthermore, if the amount of the copper damage inhibitor is less than 0.02 parts by weight, the effect of preventing documentation will be difficult to exhibit.

In addition to the above-mentioned various components, the composition of the present invention may contain various fillers, small amounts of organic flame retardants, plasticizers, pigments, and the like.

Examples of fillers include zinc oxide, magnesium oxide,
Metal oxides such as beryllium oxide, boron oxide, and aluminum oxide, carbonates such as magnesium carbonate and calcium carbonate, silicates such as clay, talc, and feldspar powder, graphite, graphite, barium sulfate, lithopone, silicas, and diatomaceous earth. , mica powder, silica sand, slate powder, asbestos, aluminum sulfate, calcium sulfate, molybdenum disulfide, and titanic acid strength. The amount of such filler blended is usually about 5 to about 200 weight U per 100 parts by weight of component (A).
parts, preferably about 10 to about 150 parts by weight, more preferably about 5 to about 50 parts by weight. If the amount of filler added exceeds 200 double bases, the mechanical properties of the resulting resin composition tend to deteriorate, which is undesirable. Furthermore, if the amount of the filler added is less than 5 parts by weight, the effect of adding the filler will not be observed, which is also undesirable.

Examples of organic flame retardants include tris(2,3-dibromopropyl)in cyanurate, 2,3-dibromopropyl methacrylate, pentabromotoluene, decabromodiphenyl ether, tetrabromogosphenol S,
2. Organobromine compounds such as 2'-bis(4-hydroxy-3,5-dibromophenyl)propane, bis(2,3-
Organic bromophosphorus compounds such as dibromopropyl dichloropropyl phosphate, chlorinated paraffin, dimethyl chlorendate, organic chlorine compounds such as Dechlorane Plus 25 (manufactured by Hooker, USA), phenylphosphonic acid, di(polyoxyethylene) Examples include organic phosphorus compounds such as hydroxymethylphosphonate. The amount of the flame retardant to be blended is usually about 0.5 to about 10 parts by weight, preferably about 1 to about 5 parts by weight, per 100 parts by weight of component (6) (A). If the amount of the organic flame retardant exceeds 10 parts by weight, the resulting resin composition tends to emit a large amount of smoke upon combustion and generate a large amount of toxic hydrogen halide.

Also, if the amount of organic flame retardant is less than 0.5 parts by weight,
This is not preferable because the effect of adding the organic flame retardant will not be recognized.

Examples of plasticizers include naphthenic plasticizers, aromatic plasticizers, process oils, phthalic acid esters, trimellitic acid esters, epoxy resins, etc., and the blending amount thereof is usually 100% of component (6) (A) above. Approximately 0.2 per part by weight
~50 parts by weight, preferably from about 1 to about 10 parts by weight.

Examples of pigments include phthalocyanine blue, chrome yellow, and red iron oxide, and the amount thereof is usually about 0.1 to about 2 parts per 100 parts by weight of component (A).
0 parts by weight, preferably about 0.5 to about 10 parts by weight.

Note that the resin composition of the present invention can be used after being crosslinked. The crosslinking method in such a case may be, for example, a method using an organic peroxide, a crosslinking method using an electron beam, a crosslinking method using radiation, or a method using water crosslinking. As the crosslinking method for the resin composition of the present invention, the first two methods are preferred.

The composition of the present invention can be obtained by suitably blending predetermined amounts of the above-mentioned various components and uniformly mixing them using a Banbury mixer, Henschel mixer, etc. according to a conventionally known method. Although all of the above components can be mixed at the same time, it is better to add the coupling agent at the same time as the filler is added. Moreover, when using two or more types of polymers as component (6) (A), it is preferable to mix the polymers uniformly first and then mix the other components.

When using the composition of the present invention, various conventionally known molding methods can be widely adopted. For example, the composition of the present invention is kneaded using a mixing machine such as a roll or a kneader, and then this is used for the intended purpose. It may be formed into various shapes depending on the requirements.

Since the composition of the present invention is essentially halogen-free, it does not generate a large amount of smoke even when left in a high-temperature flame such as during a fire, and does not undergo thermal decomposition. There is little chance of corrosive gas or acid gas being generated.
Moreover, it has excellent flame retardancy, mechanical strength, electrical properties, aging resistance, etc.

Therefore, the composition of the present invention is suitable as a coating material for building materials, pipes, hoses, sheets, seat covers, wall materials, electric wires and cables (internal insulators, external sheaths, etc.), and the like.

In particular, the composition of the present invention can be suitably used as a flame-retardant resin composition for insulation coating or sheath coating of electric wire cables. In such cases, the composition of the present invention can be used for various communication cables,
It is used as an electrical insulating layer on the conductors of power cables, control cables, etc., on the internal semiconducting layer, etc., and it is also used as a protective layer ( In either case, the electric wire cable can be provided with a high degree of flame retardancy, flame resistance, etc.

X-凰一体 Examples are given below to further clarify the present invention.

In addition, the characteristics of the samples obtained in the following examples were tested by the following method.

<Flame retardancy test> After uniformly kneading the composition of the present invention using a roll mill, hot press molding (pressure 100-150K (J/cm2,
Temperature: 180°C, time: 10 minutes) and thickness: 3. Create a sample sheet of Qmm, and use JIS K for this sample sheet.
According to 7201 (oxygen index method), the MM index (LOI>
Evaluate flame retardancy by determining

<Mechanical Properties> A sample sheet with a thickness of 1 mm is prepared by kneading and molding in the same manner as above, and each characteristic of this sample sheet is examined.

(1) 100% modulus (k (1/ml 2 ) AS
According to TM D882.

(2) Tensile b (kg/mm 2) According to ASTM D882.

(3) Elongation (%) According to ASTM 0882.

Electrical properties (room temperature) The composition of the present invention was uniformly kneaded using a roll mill, and then hot press molded (pressure 100 to 150 KO/cm2, temperature 180°C, time 10 minutes) to form a sample sheet with a thickness of 1 mm. For this sample sheet, JIS C212
3, find ρ (ohm-cm).

<Aging characteristics> Regarding the same sample sheet used in the above electrical property test,
Tensile strength retention (%) and elongation retention (%) after 100°C XIO days are determined according to ASTM D573.

In addition, the symbols of each component in each example below indicate the following.

Base polymer> A-1... Linear polyethylene [manufactured by Mikata Petrochemical Co., Ltd.
Ultsex 202OL, VFR- 2.1, density = 0.920) A-2...Linear polyethylene [manufactured by Mitsubishi Yuka Co., Ltd., Mitsubishi Polyethylene LLF30F, MFR = 1.0, density = 0.920) A -3...Linear polyethylene [manufactured by Mikata Petrochemical Co., Ltd.,
Ultopics 3010F, MFR = 1.3, density = 0.930) A-4...Linear polyethylene [manufactured by Mitsubishi Yuka Co., Ltd., Mitsubishi Polyethylene LLH20E, MFR = 0.5, density = 0.918) A -5...Linear polyethylene [manufactured by Nippon Unicar Co., Ltd.]
NUCG-5651, MFR=0.9, density=0.92
0) A-6...Linear polyethylene [manufactured by Idemitsu Petrochemical Co., Ltd.,
Idemitsu polyethylene-LO134H, MFR=1.0. Density = 0.92) A-7... Poly-α-olefin [manufactured by Mikata Petrochemical Co., Ltd., Tafmer A4090. MFR = 3.6, density = 0.89) A-8... Poly-α-olefin [manufactured by Mikata Petrochemical Co., Ltd., Tafmer PO480, MFR = 1.2, density = 0.88) A-9.・Polypropylene [manufactured by Mitsubishi Yuka Co., Ltd., BG-8
D) A-10...Polypropylene [manufactured by Mitsubishi Yuka Co., Ltd., BC-
5G) A-11...Polypropylene [manufactured by Mitsubishi Yuka Co., Ltd., 5B-
210) A-12...Polypropylene C manufactured by Idemitsu Petrochemical Co., Ltd., E
250] A-13...EVA (Mikata, manufactured by DuPont Polychemical Co., Ltd., Evaflex V527-4, MFR=0.8,
VA content - 17% by weight) A-14...EVA (manufactured by Nippon Unicar Co., Ltd., NLIC-8450, VFR = 2, VA
Content = 15% by weight) A-15...EVA (manufactured by Mitsubishi Yuka Co., Ltd., Yuka O-EVA V401S, MFR = 15, VA content = 20 heavy assembly parts) A-16-EEA (manufactured by Nippon Unicar Co., Ltd., DPDJ-6
182, VFR = 1.5, EA content = 15% by weight] A-11・-EEA (manufactured by Nippon Petrochemical Co., Ltd., A270, M
FR = 1.2, EA content = 15.6% by weight] A-18... EEA (manufactured by Mikata DuPont Polychemical Co., Ltd., A710, VFR = 0.5, EA content = 15% by weight) Flame retardant> B-1...MCI (OH)2 (manufactured by Kyowa Chemical Co., Ltd.,
Kisuma 5B) B-2・-vq (OH)2 (manufactured by Asahi Glass Co., Ltd., KX-4
8] 8-3・”AQ (OH)a (manufactured by Wa Light Metal Co., Ltd. in 2008,
Hisilite H42M) B-4...A9 (OH)a (manufactured by Showa Light Metal Co., Ltd.,
B1B-5・”3M(jcO3・Mg(OH)2・3
H2O B-6...6MgO・Al2O3・H20 additive> C-1...Red phosphorus...[Manufactured by Rin Kagaku Co., Ltd., Tsubared #
120] C-2...Zinc octate Manufactured by C Borax, zinc borate #C
-3... Titanium dioxide [manufactured by Sakai Chemical Industry Co., Ltd., Titone A150] C-4... Silane coupling agent [manufactured by Nippon Unicar Co., Ltd., A172, Ni-tris (β-methoxyethoxysilane) C-5] ... Silane coupling agent [manufactured by Nippon Unicar Co., Ltd., Al 74, γ-methacryloxypropyltrimethoxysilane] C-6... Titanium coupling agent [manufactured by Kenrich Co., Ltd.,
KR38S, isopropyl tris(dioctyl pyrophosphate) titanate] C-7... Titanium coupling agent (manufactured by Kenrich, KR138S, bis(dioctyl pyrophosphate) oxyacetate titanate) C-8... Chelate type titanium coupling agent [manufactured by Kenrich Co., Ltd., KRlol, diinstearoyloxyacetate titanate] C-9・-F E F carbon [manufactured by Tokai Electrode Co., Ltd., GEST 5o] C-10・-1 (A F carbon (manufactured by Mitsubishi Kasei Co., Ltd., Dia Black H ) C-11・-HA F carbon [manufactured by Cabot, ■u
lcan-3) C-12...Stearic acid C-13...Zinc stearate C-14...Polyethylene wax [manufactured by Nippon Petrochemical Co., Ltd., 8 Stone Uniwax] C-15... Anti-aging agent [manufactured by Ciba Geigy, Irganox 1035, (3,5-di-tert-butyl-4-hydroxyphenol) propionate] C-16... Anti-aging agent [manufactured by Iruuchi Shinko Co., Ltd., Tsukuraku White, N,N'-di -β-naphthyl-p-phenylenediamine] C-17... Antioxidant (manufactured by DuPont, Antioxidant No. 23, N, N'-diisopropyl-p
-phenylenediamine) C-18... Seenox 412S (manufactured by Shiraishi Calcium Co., Ltd.) C-19... Anti-aging agent [manufactured by Ciba Geigy Co., Ltd., Irganox 10101 Tetrakis (methylene-5-(3,
5-tert-butyl-4-hydroxyphenyl)
propionate tumethane] C-20...Copper damage inhibitor (N,N'-bis[3-(
3', 5'-di-tert-butyl-4'-hydroxyphenyl)propionyl]hydrazine] C-21...Copper damage inhibitor (N,N'-dibenzyloxalyl hydrazide) C-22...Copper damage inhibitor Agent (N,N'-disalicylidene oxalyl hydrazide) C-23...Anti-aging agent [manufactured by Irinai Shinko Co., Ltd., Tsukuraku 300.4.4'-dihydroxy-3°3'-Gt
ert-butyl-5,5'-dimethyl-diphenyl sulfide] C-24...Organic flame retardant [Mitsubishi Yuka Co., Ltd., Planelon DB-100, decabromodiphenyl ether] C-25...I flame retardant [Hooka - Chemical Co., Ltd., Dechlorane Plus 25, aliphatic polycyclic chlorine compound] C-26... Filler [Honjo Chemical Co., Ltd., activated zinc white No. 1, zinc oxide] C-27... Filler [ Kyowa Kagaku Kogyo Co., Ltd., Kiyowa Mag ioo, magnesium oxide] C-28... Filler (R, T, Vanderhilt Co., Ltd.,
Dixie clay] C-29... Filler [manufactured by Ueya Chikara Orin Kogyo Co., Ltd., graphite] C-30... Filler [manufactured by Sakai Chemical Industry Co., Ltd., Litopon, barium sulfate] Example 1 Table 1 below A composition of the present invention was obtained by mixing predetermined amounts (by weight) of each component shown in the following manner. That is, a base polymer and a flame retardant were uniformly mixed in a roll mill at a temperature of 130 to 140°C, and then a sheet-like composition was prepared.

This composition was tested for flame retardancy and elongation according to the methods described above. The results are also shown in Table 1.

For comparison, the following A-19,
Compositions were prepared in the same manner as above using A-20 and A-21, and the flame retardance and elongation of these compositions were investigated, and the results are also shown in Table 1.

A-19...Low density ethylene homopolymer [Mitsubishi Yuka Co., Ltd., Yucalon HE-30. Density = 0.920. VFR=0.30) A-20...Medium density ethylene homopolymer [manufactured by Mikata Petrochemical Co., Ltd., Hi-Zex 6300M, density=0.952,
VFR=0.11) A-21...High-density ethylene homopolymer [manufactured by Mikata Petrochemical Co., Ltd., Hi-Zex 52003. Density = 0.964,
VFR=0.30) Table 1 Composition No.

A-1100 ^-2l00 A-3100 ^-4100 A-5100 ^-6l00 A-19100 ^-2010O A-21100 B-11001001001001001001001
00100 Flame retardant 27.2 27.6 27.2 2
6゜8 27,2 27.6 25,2 25,6 2
6.2 (LOI) Elongation 450 410 405 510 550 4
15 93 75 50 (%) From Table 1 above, it can be seen that when linear polyethylene is used as the pace polymer, a resin composition with excellent flame retardancy and mechanical properties (elongation) can be obtained.

Example 2 A composition of the present invention was obtained by mixing predetermined amounts (parts by weight) of each component shown in Table 2 below using the following method. That is, the pace polymer, flame retardant and other additives are rolled in a roll mill for 13 minutes.
After uniformly mixing at a temperature of 0 to 180°C, a sheet-like composition was prepared.

Table 2 Table 2 (continued) Table 2 (continued) A-17 Table 2 (continued) Table 2 (continued) Table 2 (continued) Table 2 (continued) -jυ 10th Table 2 (continued) The properties of the composition of the present invention obtained above are shown in Table 3 below.

Table 3 Characteristics Group composition No.

Flame retardant 29.430.131.729.431.3
32.528.9 (LOI) (1) 0.920.8B 0.940.950.
870.860.98 (2> 1.651°761
．． 661.921.751.661.88ρotm-c
m O, 50, 81, 22, 00, 80, 50, 8 (
X1015) 100°C, 10-day tensile strength retention (%) 95 96 95 91
88 92 89 Remaining elongation rate (%) 88
89 91 39 87 B&9
2 Table 3 (continued) Properties Composition No.

Flame retardant 30.329.833.433.432.0
31.431.6 (LOI) (1) 0.900.700.800.860,9
00.580.96(2) 1.350.961.
301.381.111.151.38ρohm-cm
6.0 B, 00.50.70.61.56.0(
X1015) 100°C, 10-day tensile strength retention (%) 100 99 89 96
97 101 101 Remaining elongation rate (%) 95
105 99 92 94 96 96 Table 3 (continued) Properties Composition No.

Flame retardant 30.334.634.633.435.1
34.633.4 (LOI) (1) 0.720.810.840.930.6
50.720.79 (2> 1.021.401.
431.211.111.141.25 (3),
440550405495505420410, ooh
m-cm 7.00.40.60.51.25.55
．． 4 (xlO''') 100℃, 10-day tensile strength retention (%) 100 92 94 98
105 94 96 Remaining elongation rate (%) 100
89 91 96 94 92 93Table 3 (continued) Properties Composition No.

100℃, 10 days Table 3 (continued) Characteristics Composition N00 flame retardant
29. B 32.031.432.031.4 (LOI
) (1) 0.790.860.910.800.8
8 (2> 1.211.301.381,291.
40ρohm-cm 1.50.94.54.98.
0 (xio”) 100°C, 10-day tensile strength retention (%) 92 100 101 105
111 Remaining elongation rate (%) 92 94 89
88 91 From Table 3 above, it can be seen that the sheet obtained using the composition of the present invention has excellent properties.

(that's all)

Claims (11)

[Claims] (1) A flame-retardant resin composition comprising (A) about 100 parts by weight of a base polymer containing linear polyethylene, and (B) about 50 to 300 parts by weight of a metal oxide hydrate. (2) The composition according to claim 1, wherein linear polyethylene is used as the base polymer. (3) A patent claim in which a mixture of linear polyethylene and at least one member selected from the group consisting of poly-α-olefin, polypropylene, ethylene-vinyl acetate copolymer, and ethylene-ethyl acrylate is used as the base polymer. A composition according to scope 1. (4) The linear polyethylene has a density of about 0.91 to about 0.94 as measured by ASTM D1505, and AST
Melt index measured with MD1238 is approximately 0.
4. A composition according to any one of claims 1 to 3, wherein the composition has a molecular weight of 1 to about 10. (5) Hydrates of metal oxides include hydrated alumina, hydrated magnesia, 3MgCO_3・Mg(OH)_2・3H_2O
and 6MgO.Al_2O_3.H_2O. The composition according to any one of claims 1 to 4. (6) Approximately 7 parts of component (B) per 100 parts by weight of component (A)
A composition according to any one of claims 1 to 5, containing from 0 to about 200 parts by weight. (7) The composition according to any one of claims 1 to 6, which contains a flame retardant aid. (8) The composition according to any one of claims 1 to 7, which contains an anti-aging agent. (9) The composition according to any one of claims 1 to 8, which contains a higher fatty acid or a metal salt thereof as a processing aid. (10) The composition according to any one of claims 1 to 9, which contains carbon black. (11) Claim 1 containing a coupling agent
The composition according to any one of Items 1 to 10.