JPS61254646A - Flame-retardant ethylene polymer composition - Google Patents

Abstract

PURPOSE:The title composition that is obtained by adding a flame retardant to a polymer mixture of a high-pressure, low-density polyethylene and a specific ethylene-alpha-olefin copolymer, thus being suitable for used as an electrical material, because it shows high heat resistance, mechanical properties, electrical properties and flexibility. CONSTITUTION:100pts.wt. of the resin components consisting of (A) 10-90wt% of high-pressure, low-density polyethylene, (B) 90-10wt% of a copolymer from ethylene and an alpha-olefin, preferably propylene or butene-1 with a catalyst containing a solid component of Mg and Ti and an organoaluminum component, which has a density of 0.86-0.91g/cm<3>, having more than 10% of the fraction insoluble in boiling n-hexane and the maximum peak higher 100 deg.C in the differential scanning calorimetry, are combined with 5-200pts.wt. of at least one selected from flame retarders consisting of halogen retarders, and inorganic metal compound hydrates and, when necessary, 0-100pts.wt. of an inorganic filler.

Description

Detailed Description of the Invention (a) Industrial Application Field The present invention is based on high-pressure low-density polyethylene and a specific range of ethylene-α-olefin copolymers, and has flexibility, heat resistance, and mechanical properties. The present invention relates to a flame-retardant ethylene-based oak composite acid having excellent physical and electrical properties.

(b) Prior art Because polyethylene has excellent physical and chemical properties, it can be molded into films, sheets, vibrators, containers, etc. using various molding methods such as extrusion molding, injection molding, and rotary molding, and is used for household use. It is a general-purpose resin with the highest demand for use in many industrial applications.

Since the above-mentioned polyethylene is easily flammable, various methods for making it flame retardant have been proposed.

The most common method is to add a flame retardant containing halogen or phosphorus to the polyethylene.
! can be converted into The degree of flame retardation increases with the amount of flame retardant added. However, an increase in the amount added not only causes a decrease in mechanical strength, workability, etc., but also has the disadvantage of significantly impairing flexibility, cold resistance, etc. In addition, these conventional T1 combustible compositions are required to be highly flame retardant from the standpoint of disaster prevention, and in recent years, there is a tendency for this to be made mandatory. Magnesium hydroxide,
Inorganic flame retardants such as aluminum hydroxide meet these needs and are rapidly increasing in demand.
136832@, A60-13832, etc.)
.

However, conventionally commercially available polyethylene has poor receptivity to inorganic flame retardants and low flame retardant effects. In addition, when the filling amount is increased, mechanical strength, flexibility, workability, etc. are reduced, and there is a drawback that it cannot be put to practical use. On the other hand, in order to increase the filling rate of the inorganic flame retardant, ethylene-vinyl acetate copolymer or chlorinated polyethylene,
Examples of using soft resins such as ethylene-propylene copolymer rubber are well known, but they are inferior in terms of mechanical strength, heat resistance, oil resistance, etc.

(c) 12g Problems to be Solved by the Invention In view of the above points, the present invention provides a flame-retardant ethylene polymer composition having excellent heat resistance, mechanical strength, low-temperature properties, flexibility, etc. Because of its excellent electrical characteristics,
It can be crosslinked as needed and used as electrical materials such as insulation and sheathing for electric wires and cables, as well as backing, sealing materials, etc.
It is used for molding applications such as extrusion molded products such as hoses and films, and injection molded products, and as masterbatches.

(d) Means for Solving the Problems The present invention has been made as a result of intensive studies in view of the above points. That is, the flame-retardant ethylene polymer composition of the present invention is: a) 10 to 90% by weight of high-pressure low-density polyethylene, b) Density of 0.86 to 0.919/c weight 3, boiling point 1
The n-hexane insoluble content is 10% by weight or more, and the maximum peak temperature (T
100 parts by weight of an ethylene-α-olefin copolymer having a g+) of 100° C. or higher, C) 5 to 200 parts by weight of a tl refueling agent, and d) an optional inorganic filler O. 100
The present invention provides a flame-retardant ethylene-based polymer composition containing a polymeric moiety.

The high-pressure low density polyethylene that is component a) of the present invention refers to ethylene or ethylene and α-olefin and/or
or may contain other monomers, and is produced by high-pressure radical polymerization. This α-olefin and unsaturation rate are propylene, butene-1,
Pentene-1, hexene-1, 4-methylpentene-1
, octene-1, decene-1, etc., and small amounts of vinyl acetate, ethyl acrylate, methacrylic acid or esters thereof, and mixtures thereof.

The content a of the unsaturated monomer in the above ethylene polymer is 0 to
It is preferably 3 mol% or less, particularly 1 mol% or less.

The above-mentioned radical polymerization method under high pressure means a polymerization pressure of 5
00 to 4000Kg/al, preferably 10
00 to 3500 cloth/aJ, reaction temperature 50 to 400°C, preferably 100 to 350°C, in the presence of a free radical catalyst and a chain transfer agent, and if necessary auxiliaries, in a tank wall or a tubular reaction vessel. A method in which ethylene and, if desired, other single substances are brought into contact and polymerized simultaneously or in stages.

The free radical catalysts include customary initiators such as peroxides, hydroheloxides, azo compounds, amine oxide compounds, oxygen, and the like.

In addition, as a chain transfer agent, hydrogen, propylene, butene-
Saturated aliphatic and halogen-substituted hydrocarbons of 1,01 to C2o or more, such as methane, ethane, propane, butane, isobutane, n-hexane, n-
Hebutane, cycloparaffins, chloroform and carbon tetrachloride, saturated aliphatic alcohols of 01 to C2° or higher, such as methanol, ethanol, propatool and impropatur, saturated aliphatic carbonyl compounds of 01 to C2o or higher , such as compounds such as acetone and methyl ethyl ketone.

The high-pressure low-density polyethylene produced in this manner has a density force in the range of 0.91 to 0.94 g/ax3, preferably 0.92 to 0.93 g/a3, and a melt index (hereinafter abbreviated as Ml). ) is 0.1 to 509/10 minutes,
Preferably 0.5 to 30 g/10 min, more preferably 1
．． It is in the range of 0 to 2 (1/10 minute).

The ethylene-α-olefin copolymer in a specific range, which is component b) of the present invention, refers to ethylene and an α-olefin copolymer having 3 to 12 carbon atoms.
- It is a copolymer of olefins.

Specific α-olefins include propylene, butene-1,4-methylpentene-1, hexene-1, octene-1, decene-1, dodecene-1, and the like. Particularly preferred among these are propylene and butene-1. The α-olefin content in the ethylene-α-olefin copolymer is preferably 5 to 40 mol%.

The method for producing the copolymer of ethylene and α-olefin used in the present invention will be explained below.

First, the catalyst system used is a combination of a solid catalyst component containing magnesium and titanium with an organoaluminum compound. Examples of the solid catalyst component include magnesium metal, magnesium hydroxide, magnesium carbonate,
Magnesium oxide, magnesium chloride, etc., as well as silicon,
Double salts, double oxides, carbon salts, chlorides, hydroxides, etc. containing a metal selected from aluminum and calcium and magnesium atoms, and furthermore, these inorganic solid compounds can be used as oxygen-containing compounds, sulfur-containing compounds, and aromatic compounds. Examples include those in which a titanium compound is supported by a known method on an inorganic solid compound containing magnesium, such as one treated or reacted with a hydrocarbon or halogen-containing substance.

Examples of the above oxygen-containing compounds include water, alcohol,
Organic oxygen-containing compounds such as phenols, ketones, aldehydes, carboxylic acids, esters, polysiloxanes, acid amides,
Examples include inorganic oxygen-containing compounds such as metal alkoxides and metal oxychlorides. Examples of the sulfur-containing compound include organic sulfur-containing compounds such as thiol and thioether, and inorganic sulfur compounds such as sulfur dioxide, sulfur trioxide, and sulfuric acid. Examples of aromatic hydrocarbons include various monocyclic and polycyclic aromatic hydrocarbon compounds such as benzene, toluene, xylene, anthracene, and phenanthrene. Examples of the halogen-containing substance include compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides.

Examples of the titanium compound include titanium halides, alkoxy halides, alkoxides, and halogenated oxides. As the titanium compound, a tetravalent titanium compound and a trivalent titanium compound are suitable, and the tetravalent titanium compound specifically has the general formula Ti(OR).
X (where 4-n R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents O≦
titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, Jetoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium,
Monoisopropoxytrichlorotitanium, Shiitsubu 0boxydichlorotitanium, triisoproboxymonocontitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxy Examples include dichlorotitanium, triethoxymonochlorotitanium, and tetraphenoxytitanium.

Trivalent titanium compounds include trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of group metals of the periodic table. Titanium is mentioned. In addition, the general formula Ti(OR) )
Tetravalent alkoxy titanium halide shown in the periodic table I-Ill /#! Examples include trivalent titanium compounds obtained by reduction with organometallic compounds of the genus.

Among these titanium compounds, tetravalent titanium compounds are particularly preferred.

Another example of a catalyst system is a catalyst system in which a reaction product of an organomagnesium compound such as a so-called Grignard compound and a titanium compound is used as a solid catalyst component, and an organoaluminum compound is combined therewith. As the organomagnesium compound, for example, the general formula R
MoX.

Organomagnesium compounds such as R2Mg, RM, (OR) (where R is an organic residue having 1 to 20 carbon atoms, and X is a halogen), ether complexes thereof, and other organomagnesium compounds For example, organic metal compounds modified by adding various compounds such as organic sodium, organic lithium, organic potassium, organic boron, organic calcium, and organic zinc can be used.

In addition, as an example of another catalyst system, as a solid catalyst component, 5
i02,Aj! An example is a combination of a solid material obtained by contacting an inorganic oxide such as 203 with the solid catalyst component containing at least magnesium and titanium, and an organoaluminum compound. Nothing! Examples of 1M compounds include caO in addition to 5i02 and Ag2O3.

B2O3, 5no2, etc. can be mentioned, and double oxides of these oxides can also be used without any problem. Any known method can be used to bring these various inorganic oxides into contact with the solid catalyst component containing magnesium and titanium.

That is, a method of reacting in the presence or absence of an inert solvent at a temperature of 20 to 400°C, preferably 50 to 300°C for usually 5 minutes to 20 hours, a method of co-pulverization, or a combination of these methods as appropriate. It may be possible to do so.

In these catalyst systems, a titanium compound can be used as an adduct with an organic carboxylic acid ester, or the above-described magnesium-containing inorganic solid compound can be used after being brought into contact with an organic carboxylic acid ester. Moreover, there is no problem in using an organoaluminum compound as an adduct with an organic carboxylic acid ester.

Moreover, in all cases it is also possible to use catalyst systems prepared in the presence of organic carboxylic esters without any hindrance.

Here, the organic carboxylic acid esters include various aliphatic,
An aromatic carboxylic acid ester is used, preferably an aromatic carboxylic acid ester having 7 to 12 carbon atoms. Specific examples include alkyl esters of benzoic acid, anisic acid, toluic acid, such as methyl and ethyl.

A specific example of an organoaluminum compound to be combined with the solid catalyst component described above is an organoaluminum compound of the general formula % R3AJ2x3 (where R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, and X is (representing a halogen atom, R may be the same or different) Compounds represented by triethylaluminum, triisobutylaluminum, trihexylaluminum, triethylaluminum, diethylaluminium chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride are preferred. and mixtures thereof.

The amount of the organoaluminum compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound.

In addition, by bringing the catalyst system into contact with an α-olefin and then using it in the polymerization reaction, the polymerization activity can be greatly improved and the system can be operated more stably than in the case of no treatment. Various α-olefins can be used at this time, but preferably those having 3 to 1 carbon atoms are used.
α-olefin having 2 carbon atoms, more preferably 3 carbon atoms
-8 alpha-olefins are preferred. Examples of these α-olefins include propylene, pudene-1, pentene-1,4-methylpentene-1, hexene-1,
Mention may be made of octene-1, decene-1, dodecene-1, etc. and mixtures thereof. The temperature and time during contact between the catalyst system and the α-olefin can be selected within a wide range, for example, the contact treatment can be carried out at 0 to 220°C, preferably 0 to 0°C by weight, for 1 minute to 24 hours. The amount of α-olefin to be contacted can be selected within a wide range, but usually
1 to 50.000 g per 1 g of the solid catalyst component, preferably 5 to 30.00 g (treated with about 1 α-olefin, 1 to 50.000 g per 1 g of the solid catalyst component)
It is desirable to react an α-olefin of ˜5009. At this time, the pressure at the time of contact can be arbitrarily selected, but it is usually desirable to bring them into contact under a pressure of -1 to 100 Nf/dG. In the α-olefin treatment, all of the organoaluminum compound used may be combined with the aS solid catalyst component and then brought into contact with the α-olefin, or a part of the organoaluminum compound used may be combined with the solid catalyst component. After combining with α-olefin, the remaining organoaluminum compound may be added separately during polymerization to carry out the polymerization reaction. Further, when the catalyst system and the α-olefin are brought into contact, there is no problem even if hydrogen gas coexists, and there is no problem even if other inert gases such as nitrogen, argon, helium, etc. coexist.

The polymerization reaction is carried out in the same manner as a typical olefin polymerization reaction using a Ziegler type catalyst. That is, all reactions are carried out in a gas phase, in the presence of an inert solvent, or using the monomer itself as a solvent in a state substantially free of oxygen, water, etc. Olefin polymerization conditions are temperature 20-300
C, preferably 40 to 200 C, and the pressure is normal pressure to 70 Kl/ci-G, preferably 2 to 9 Kl/ci-G to 60 Kl/ci-G. Although the molecule m can be adjusted to a certain degree by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, it is effectively carried out by adding hydrogen to the polymerization system. Of course, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can also be carried out without any problem.

The ethylene-α-olefin copolymer which is component b) of the present invention produced in this way is (a) W! degree is 0.8
6 to 0.91 g1013, (b) Boiling n-hexane insoluble matter is 10% by weight or more, (c) Maximum peak temperature (TI> shown by differential scanning calorimetry (DSG)) is important to be 100°C or more It is.

If the density exceeds O-91'j/am3, there is a concern that the composition will lose its flexibility, and the density will be 0.8
If it is less than 69/cML'', the melting point will be low and the heat resistance will be poor.

Furthermore, if the boiling n-hexane insoluble content of the ethylene-α-olefin copolymer is less than 10% by weight, the amorphous portion and low molecular weight components will increase, resulting in poor oil resistance and strength.

On the other hand, the maximum peak temperature of differential scanning calorimetry (DSC) (
If Tm ) is less than 100°C, the heat resistance will be poor.

Ml of the ethylene-α-olefin copolymer is 0.05
~50 g/10 minutes, preferably 0.1 to 2 (1/10 minutes).

In addition, in the present invention, the mn-hexane insoluble matter and D
The method for measuring SC is as follows.

[Boiling! Measurement method for n-hexane insoluble matter] A sheet with a thickness of 200 μm is formed using a heat press, and three sheets of 20# x 30 weight I are cut vertically and horizontally from the sheet, and the sheets are subjected to double-tube Soxhlet extraction. Extraction is carried out for 5 hours with boiling weight n-hexane using a vessel. The n-hexane insoluble matter was taken out and dried under vacuum (7 hours, under vacuum, 50°C), followed by boiling I! Calculate the In-hexane insoluble content.

Boiling fi! n-Hexane insoluble content (weight %) = (extracted sheet weight gi/unextracted sheet weight) xloo (weight %) [Measurement method by DSC] Approximately 5 I
Weigh a 1 g sample, set it in the DSC device,
After raising the temperature to 170°C and maintaining it at that temperature for 1510 minutes, the temperature decrease rate is reduced to 0°C at a rate of 5°C/min. Next, from this state, the temperature is raised to 170°C at a rate of 10°C/min and measurements are taken. The temperature at the position of the maximum peak that appears during the temperature increase from 0°C to 170°C is defined as T■.

The ethylene-α-olefin copolymer used in the present invention is clearly distinguished from the ethylene-α-olefin copolymer obtained by using one containing vanadium as a solid catalyst component.

In other words, conventional ethylene propylene copolymers, etc., have almost no crystallinity, and even if a crystal part exists, it is in a very small amount, and the maximum peak temperature (Ta +
) is also less than 100℃.

This indicates that it cannot be used in applications that require heat resistance, mechanical strength, etc.

As the flame retardant which is component C) of the present invention, additive flame retardants such as halogen flame retardants, phosphorus flame retardants, and inorganic flame retardants are used. Examples of the halogen flame retardants include tetrabromobisphenol A (TBA). ), hexabromobenzene,
Decabromodiphenyl ether, tetrabromoethane (
Brominated and chlorinated paraffins such as TBE), tetrabromobutane (TBB), hexabromocyclodecane (HBCD), chlorinated polyphenyl, chlorinated polyethylene,
Examples include chlorine-based compounds such as diphenyl chloride, perchloropentacyclodecane, and chlorinated naphthalene, which are more effective when used in combination with antimony trioxide and the like.

In addition, phosphorus-based flame retardants include tricresyl phosphate, tri(dichloropropyl) phosphate, tri(β
-chloroethyl)bosphate, tri(dibromopropyl)phosphate, 2,3-dibromopropyl-2,3
- Phosphate esters such as chloropropyl phosphate, halogenated phosphate esters, etc. are mainly mentioned.

1゜Furthermore, the NM-free fuel of the present invention includes aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite,
Calcium hydroxide, barium hydroxide, tin oxide hydrate, hydrate of inorganic metal compounds such as borax, zinc borate, zinc metaborate, barium metaborate, zinc carbonate, magnesium-calcium carbonate, calcium carbonate, carbonic acid Examples include barium, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, antimony oxide, red phosphorus, and the like. These may be used alone or in combination of two or more. Among these, magnesium hydroxide, aluminum hydroxide,
At least one selected from the group consisting of basic magnesium carbonate and hydrotalcite has a good flame retardant effect and is economically advantageous. Further, the coarse particle size of these flame retardants varies depending on the type, but for magnesium hydroxide, aluminum hydroxide, etc., the average particle size is preferably 20 μm or less.

The grade of the above flame retardant is 5 to 200 parts per 100 parts by weight of the resin.
It is a heavy suspension, preferably in the range of 10 to 150 heavy suspensions.

If the amount of the flame retardant is less than 5-type seedlings, the flame retardant effect will be small, and if it exceeds 1 part of 200'1fff, the mechanical strength and elongation will decrease, flexibility will be lost, the seedling will become brittle, and the low-temperature properties will also deteriorate. Getting worse.

In the present invention, at least one of the above-mentioned additive flame retardants is used, and especially when a halogen flame retardant is used, it is preferably used in combination with antimony trioxide. Further, in the present invention, by using an inorganic filler and a flame retardant in combination, the amount of flame retardant added can be reduced and other properties can be imparted.

Examples of the inorganic filler as an optional component used in the present invention include powder-like, tabular, scaly, needle-like, spherical or hollow, and fibrous, and specifically, calcium carbonate, magnesium carbonate, Powders such as calcium sulfate, calcium silica sand, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, antimony trioxide, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon black, etc. Granular filler, '1
ffl, glass plates, metal foils such as sericite, pyrophyllite, and aluminum flakes, flat or scaly fillers such as graphite, hollow fillers such as shirasu balloons, metal balloons, glass balloons, and pumice, glass J! fibers, carbon m miscellaneous, graphite fibers, whiskers, metal fibers, silicon carbide III.

Examples include mineral fibers such as asbestos and wollastonite.

The amount of these additives to be added is approximately 100 parts by weight per 10 parts by weight of the composition of the present invention.

If the above-mentioned addition m exceeds 100 parts by weight, the mechanical strength such as WJ impact strength of the molded article decreases, which is not preferable.

The composition of the present invention comprises the above-mentioned a) high-pressure low-density polyethylene 1
0-90% by weight and b) density 0.86-0.91'j
/lx3, boiling n-hexane insoluble content of 10% by weight or more,
And the maximum peak temperature (T■) shown by differential scanning lapse measurement (DSC) is 100''cg.

The above ethylene-α-olefin copolymer 90-10
C)
5 to 200 parts by weight of flame retardant and optionally inorganic filler O
It is a combustible ethylene polymer composition blended with 100 to 100 weight percent, and when component a) in the resin component exceeds 90% by weight, mechanical strength such as tensile strength decreases.

If the content of component b) exceeds 90% by weight, there is a concern that n-points may occur in processability. , it is possible to improve heat resistance and the filling rate of flame retardant or inorganic filler without losing flexibility. In addition, it is possible to maintain the good workability that is a characteristic of high-pressure low density polyethylene.

In particular, when using it as a composition for electrical materials such as insulation and sheathing for electric wires and cables, in order to take advantage of the good processability of high-pressure low-density polyethylene, a) high-pressure low-density polyethylene 50~ 90% by weight b) Specific range of ethylene-α-olefin copolymer It is desirable to have a resin composition in the range of 10 to 50% by weight.

In addition, in the present invention, when using the non-tiit fuel or inorganic filler, the surface of the inorganic material is coated with fatty acids such as stearic acid, oleic acid, palmitylic acid, or their metal salts, paraffin, wax, polyethylene, etc. Waxes or their modified products, organic silanes,
It is preferable to perform surface treatment such as coating with organic borane, organic titanate, or the like.

The composition of the present invention is prepared by mixing a specific range of ethylene-α-olefin copolymer resins, flame retardants, optionally inorganic fillers, additives, etc. in a Banbury mixer, a pressure kneader, a 1U kneading extruder, and a two-way extruder. It is melt-kneaded using a commonly used kneading machine such as a screw extruder or roll, and subjected to pelletization, etc., and then provided as a molded product or masterbatch, or it is tri-blended with the above resin components, flame retardants, additives, etc. It can be anything.

In the present invention, other synthetic resins, antioxidants, lubricants, organic
Addition of various inorganic pigments, UV inhibitors, dispersants, copper damage inhibitors, neutralizing agents, foaming agents, plasticizers, antifoaming agents, crosslinking agents, flowability improvers, weld strength improvers, nucleating agents, etc. Agents may be added within a range that does not significantly impair the effects of the present invention.

(e) Examples Examples will be described below.

Examples 1 to 6 and Comparative Examples 1 to 6 Resin used> a) Component High pressure process low density polyethylene
1,09/10 minutes, d = 0.920g/α3) a) Product name: 0 stone Xuron W 330G (MI-
3,09/10 min, d = 0.925 g/cm3) b) Component A solid catalyst component obtained from substantially anhydrous magnesium chloride, 1,2-dichloroethane and titanium tetrachloride;
Using a catalyst consisting of triethylaluminum, ethylene, propylene, and butene-1 are polymerized to produce various types (A), (B), (C), and (D) as shown below.
An ethylene-α-olefin copolymer was obtained.

(A) Ethylene-butene-1 copolymer (M I -3,09/10 min, d -0,900
g/cm3) (B) Ethylene-butene-1 copolymer (M l = 1.09/10 min, d = 0
．． 9059/cIR3) (C) Ethylene-propylene copolymer (M I = 5.09/10 min, d-0,8909
/33) (D) Ethylene-butene-1 copolymer (M I -0,8f?/10 min, d -0,90
0Si! /α3) The resins used in Comparative Examples 4 to 6 are also shown below.

(E) Ethylene-butene-1 copolymer (M I -2, 09/10 min, d = 0.922 g
/33) (Product name Nippon Seki Sunilex A F 332G
, manufactured by Nippon Petrochemical Co., Ltd.) (F) Ethylene-butene-1 copolymer (M I -4,0 g/10 min, d -0,887
9/cm3) (Product name: Tafmer A 4085, manufactured by Mitsui Petrochemicals) (G) Ethylene-propylene copolymer (Ml-1,99/10 min, d-0,869/c weight 3) (Product Name: EPO2, manufactured by Nippon Synthetic Rubber Company) Resin component 100f consisting of specified amounts of the above components a) and b)
A predetermined amount of decabromodiphenyl ether as a flame retardant and antimony trioxide as an auxiliary agent was kneaded into 1 part of fi using a Prabender Plastograph for 8 times, and after forming into a sheet, it was pounded into a desired shape and the physical properties were evaluated. Shown in the table.

Tomo Naotan J 100 parts by weight of magnesium hydroxide (trade name: Kiss 75B1 manufactured by Kyowa Kagaku Co., Ltd.) as a weight M agent was added to 100 parts by weight of the resin component used in Example 1, and the physical properties were evaluated. As a result, the tensile strength was 1, 10Kg/J, the heating deformation rate was 8%,
The oxygen index (ASTM D2863) was 26, and the workability was also good.

220 parts by weight of the same magnesium hydroxide as in Example 7 was added as a flame retardant to 100 parts by weight of the resin component used in Example 1, and the physical properties were evaluated. As a result, the tensile strength is 0.60!
I/jI weight 2, heat deformation rate 5%, oxygen index 35, good heat deformation rate and flame retardance 1,
The tensile strength and workability were poor.

Test Method> Test specimens were prepared by punching out No. 3 dumbbells from a sheet with knee weight and thickness of in/m, and were measured using a Tensilon at a tensile speed of 200 shoes/min.

2. Heat La ratio A cylinder with a thickness of 6 m/m and a diameter of 10 m/m was pressurized with a load of 12.64 KI in an oil bath at 100°C, and the deformation ratio was determined after 30 minutes.

3. Based on flame retardant UL-standard V-2. (In other words, the average self-extinguishing time is 25 seconds or less, and the maximum extinguishing time is 30 seconds or less.) 4. Using a processable blow molding machine (screw diameter 25 m/mφ),
Using a die with an inner diameter of 9m/mφ and an outer diameter of 10m/mφ,
The surface condition was visually judged when extruded at a set temperature and weight of 150° C. and a screw rotation speed of 50 rpm.

5. Oxygen index (0,1)...ASTM D 2863 The combustion time of the sample continues to burn for 3 minutes or more, or the combustion length is 50
The minimum oxygen concentration required to continue burning at rrt/m or more.

(f) Effects of the Invention As mentioned above, the flame-retardant composition of the present invention uses a specific ethylene-α-olefin copolymer, so it has excellent heat resistance and resistance without losing flexibility. By using hydrates of inorganic metal compounds such as aluminum hydroxide, magnesium hydroxide, etc. as flame retardants, no harmful gases are generated during combustion and the smoke is low. This results in a non-polluting flame retardant composition that meets the recent needs for highly flame retardant properties.

In addition, the composition of the present invention contains high-pressure low-density polyethylene with good processability and has excellent electrical properties, so it can be used with or without crosslinking for electrical insulating materials such as electric wires and cables, and external materials. It can be used as an electrical material such as a covering material. In particular, a high degree of flame retardancy is required for cables for various power generation plants, including nuclear power research institutes, which have regulations governing corrosive gas heat, cables for chemical, steel, and petroleum plants, fire-resistant electrical wires, and general household wiring. It is suitable for use in places where

It is also used for molding purposes such as extrusion molded products or injection molded products such as films, sheets, and pipes, and as master badges, etc., and is used in various fields such as textiles, electricity, electronics, automobiles, ships, aircraft, architecture, and civil engineering. It is used for panels, packaging materials, furniture, household goods, etc.

Claims (4)

[Claims] (1) a) High pressure low density polyethylene 10-90% by weight
, b) Density 0.86-0.91g/cm^3, boiling n-
The hexane insoluble content is 10% by weight or more, and the maximum peak temperature (Tm) shown by differential scanning calorimetry (DSC) is 1.
Ethylene-α-olefin copolymer 9 having a temperature of 00°C or higher
A flame-retardant ethylene polymer composition comprising: c) 5-200 parts by weight of a flame retardant in 100 parts by weight of a resin component consisting of 0-10% by weight. (2) The flame-retardant ethylene polymer composition according to claim 1, wherein the flame retardant is at least one selected from the group consisting of halogen flame retardants and hydrates of inorganic metal compounds. . (3) a) High pressure low density polyethylene 50-90% by weight
, b) Density 0.86-0.91g/cm^3, boiling n-
The hexane insoluble content is 10% by weight or more, and the maximum peak temperature (Tm) shown by differential scanning calorimetry (DSC) is 1.
Ethylene-α-olefin copolymer 5 having a temperature of 00°C or higher
A composition for electrical materials comprising a flame-retardant ethylene polymer composition comprising 100 parts by weight of a resin component of 0-10% by weight and c) 5-200 parts by weight of a flame retardant. (4) The composition for electrical materials according to claim 3, wherein the flame retardant is at least one selected from the group consisting of halogen flame retardants and hydrates of inorganic metal compounds.