JPS61296045A - Flame-retardant olefin polymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent mechanical strength and heat-resistance and suitable for electrical material, by adding a flame- retardant to a mixture of a specific ethylene-alpha-olefin copolymer and an olefin polymer modified with an unsaturated carboxylic acid (derivative). CONSTITUTION:(A) 100pts.(wt.) of a resin component composed of (i) 99-60(wt)% ethylene-alpha-olefin copolymer having a density of 0.86-0.91g/cm<3>, a boiling n-hexane-insoluble content of >=10% and the highest peak temperature of the differential scanning calorimetry of >=100 deg.C and (ii) 1-40% polymer produced by modifying an olefin polymer, preferably an ethylene-alpha-olefin copolymer having a density of 0.91-0.97g/cm<3> with an unsaturated carboxylic acid or its derivative (preferably maleic anhydride) is compounded with (B) 5-200pts. of a flame retardant, preferably hydrate of inorganic metallic compound (e.g. aluminum hydroxide, magnesium hydroxide, etc.).

Description

[Detailed description of the invention]

(a) Industrial application field The present invention has a density of 0.86 to 0.91'I/att
3. The boiling n-hexyl non-insoluble content is 10% by weight or more,
The maximum peak temperature of differential scanning calorific value is 100℃.
1- A flame-retardant olefin polymer composition with excellent heat resistance T11 and mechanical strength, which is based on a T tyrene-α-olefin copolymer and an olefin polymer modified with an unsaturated carboxylic acid or a derivative thereof. Regarding. (b) Prior Art Because polyethylene has excellent physical and chemical properties, it can be molded into films, sheets, pipes, containers, etc. using various molding methods such as extrusion molding, injection molding, and rotary molding. ■It is the most demanded general-purpose resin used in many passenger applications. Since polyethylene is easily flammable, many methods have been proposed to make it combustible. The most common method is to add a flame inhibitor containing halogen or phosphorus to the polyethylene.
It can be made flame retardant. The degree of flame retardation increases with the amount of flame retardant added. however,
An increase in the amount added not only leads to a decrease in mechanical strength, workability, etc.1, but also has the drawback of significantly impairing flexibility, cold resistance, etc. In addition, these conventional flame-retardant compositions are required to be more highly flame-retardant from a disaster prevention perspective, and in some cases, there is a tendency for such compositions to be made mandatory. Inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide meet these needs and are rapidly becoming popular as low smoke and non-polluting flame retardants. demand is increasing (for example, Japanese Patent Application Laid-Open No. 51-1322
Publication No. 54, Publication No. 56-136862, Publication No. 6113
832, etc.). However, conventionally commercially available polyethylene has poor receptivity to inorganic flame retardants and has low flame retardant effects. In addition, when the filling ID is increased, mechanical strength, flexibility, workability, etc. are reduced, and there is a drawback that it is not suitable for practical use. On the other hand, the above inorganic type! 1. Examples of using soft resins such as J-tyrene-vinyl acetate copolymer, 1-tyrene monoethyl acrylate copolymer, chlorinated polyethylene, and ethylene-propylene copolymer rubber are well known in order to increase the filling rate of fuel. However, it is inferior in mechanical strength and heat resistance. (c) Problems to be Solved by the Invention In view of the above points, the present invention aims to provide a flame retardant composition which is particularly highly filled with inorganic flame retardants and has superior mechanical strength and heat resistance. It is something. This flame-retardant composition is used for molding applications such as electric wires, cables, backings, sealing materials, hoses, noilms, injection molded products, etc., and as masterbatches. (d) Means for solving the problems The present invention provides a) a density of 0.86 to 0.919/cm3.
, boil! An ethylene-α-olefin copolymer with an n-hexane insoluble content of 10% by weight or more and a maximum peak temperature of 100°C or more as shown by differential scanning calorimetry [Combination 99-60]
% by weight, 1)) Olefin i modified with unsaturated carboxylic acid or its derivative [coalescence 1-. The present invention provides an olefin polymer composition containing C) 5 to 200 parts by weight of a flame retardant in 100 parts by weight of a resin component consisting of 40% by weight. This is a copolymer of an ethylene-α-olefin copolymer and t, L, ethylene, and an α-olefin having 3 to 12 carbon atoms, which is component a) of the present invention. Specific α-olefins include propylene, 1-tene-1,4-methylpentene-1
, Hexene-1, A Latin-1, De I? Examples include N-1, Dobsen-1, and the like. Particularly preferred among these are propylene and butene-1. Among them, Budene-1 is particularly preferred. The α-olefin content in the 1-dylene-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 one in which an organic aluminum compound is combined with a solid catalyst component containing magnesium and titanium.The solid catalyst components include, for example, metallic magnesium, magnesium hydroxide, magnesium carbonate,
Magnesium oxide, magnesium chloride, etc., as well as silicon,
Double salts, carbonates, carbon salts, chlorides, hydroxides, etc. containing a metal selected from aluminum and calcium and magnesium atoms, and furthermore, these inorganic solid compounds are converted into oxygen-containing compounds, sulfur-containing compounds, aromatic carbonization. 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 substance containing hydrogen or a halogen. Examples of the above oxygen-containing compounds include water, alcohol,
Inorganic oxygen-containing compounds such as phenol, alcohol, aldehyde, carboxylic acid, ester, polysilicone, organic oxygen-containing compound such as acid amide, metal compound, metal A1 chloride, etc. I can give an example. Examples of sulfur-containing compounds 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, Al]'F sites, 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 ri (OR)
X (where 4-n 1〈represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, X represents a halogen atom, and n represents 0
≦0≦4) -〇 - Titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, 1-rimethoxymonochlorotitanium, tetra Methoxybutane, monoethyl 4 ditrichlor[1 titanium, die]
Coconut dichlorotitanium, l-jJ I l-1-cymonochlorotitanium, tetraethoxybutane, t-noisoproboxytrichlorotitanium, shiitsubu[]boxydichlorotitanium

[]Titanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium,
Examples include dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, Schiff T-synchronicychlorotitanium, triphenoxydichlorotitanium, triphenoxytitanium, and tetraphenoxytitanium. Trivalent titanium compounds are obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide to hydrogen, aluminum, titanium, or organometallic compounds of metals from groups F to II of the periodic table. Examples include titanium trihalide. In addition, the general formula Ti(OR>X (here 1
So, to carbon number 1 - I114-Il1 20 Al 1 L bracket, 7 reel 1 or Aral, 1 L
1, × indicates Ha[l gene atom, mG, LO≦m
Examples include trivalent titanium compounds obtained by reducing tetravalent aluminum halide represented by the formula ≦4) with organometallic compounds of Group II metals in Tables 1 to 2. 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
M (IX. R2M!+ , RIvlo (OR) @ organomagnesium compound (where R is an organic residue having 1 to 20 carbon atoms,
X represents a halogen) and their ether 14 combinations, and these organomagnesium compounds are further combined with other organometallic compounds such as organosulfur, organolithium, organic potassium, organoboron, organic calcium,
It is possible to use denatured materials by adding various compounds such as Ili and saccharide. Examples of other catalyst systems include solid catalyst components, S
An example is a combination of a solid material obtained by contacting an inorganic oxide such as i 02 or Ag2O3 with a solid catalyst component containing at least magnesium and titanium, and an organoaluminum compound. can. In addition to SiO, AI) 203, Cab is used as an atom-free compound. Examples include B2O3, 5002, etc., and double oxides of these oxides can be used without any problem. These various inorganic oxides are brought into contact with a solid catalyst component consisting of magnesium and titanium. A known method can be adopted as the method. That is, the reaction is carried out 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.
The reaction can be carried out by a method of co-pulverization, a method of co-pulverization, or a suitable combination of these methods. But that's fine. 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. Furthermore, it is also possible in all cases to use catalyst systems prepared in the presence of organic carboxylic esters without any hindrance. Here, the organic carboxylic acid esters include various aliphatic,
Alicyclic or aromatic carboxylic acid esters are used, and aromatic carboxylic acid esters having 7 to 12 carbon atoms are preferably used. Specific examples include benzoic acid, anisic acid, methyl, ethyl, etc. of benzoic acid, anisic acid, and toluic acid. A specific example of an organoaluminum compound to be combined with the solid catalyst component described above is an organoaluminum compound having the general formula % RAl12X3 (where R is an alkyl group having 1 to 20 carbon atoms, an aryl group, or an aralkyl group, represents a cogen atom, R may be the same or different), and compounds represented by the following are preferred;
Delaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, di1delaluminum■
Examples thereof include toxide, ethylaluminum cess 1 chloride, 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'E per the amount of the titanium compound. In addition, by bringing the above-mentioned catalyst system into contact with an α-olefin and then using it in a polymerization reaction, this polymerization activity can be increased.
It also allows for more stable operation than in the case of no treatment. As the α-olefin used at this time, divine substances can be used, but preferably an α-olefin with a carbon number of 3
-12 α-olefins, more preferably α-olefins having 3 to 8 carbon atoms. These α−
Examples of olefins include propylene, butene, etc.
Examples include 1, pentene-1,4-metylpentene-1, hexene-1, oxygen-1, decene-1, dobcene-1, and mixtures thereof. The temperature and time during contact between the VA medium system and the α-olefin can be selected within a wide range, for example 0 to 200°C, preferably 0 to 200°C.
The contact treatment can be carried out at 110° C. for 1 minute to 24 hours. Although the amount of α-olefin to be contacted can be selected within a wide range, it is usually 1 to 50,000 per gram of the solid catalyst component.
7, preferably treated with about 5 to 30,000 g of α-A-renoin, and 1 to 50 g per 1 g of the solid catalyst component.
It is desirable to skip the reaction of 0 g of α-olefin. At this time, the pressure at the time of contact can be arbitrarily selected, but it is usually desirable to contact under a pressure of -1H-100K9/tri-G. During α-olefin treatment, the entire amount of the organoaluminum compound used may be brought into contact with the hα-olefin combined with the solid catalyst component, or a part of the organoaluminum compound used may be brought into contact with the solid catalyst component. Combined with 1! It is also possible to carry out the polymerization reaction by separately adding the remaining organoaluminum compound which is then contacted with the α-olefin during polymerization. Also,
At the time of contact between the catalyst system and the α-olefin, there is no problem even if hydrogen gas coexists, and there is no problem if other inert gases such as nitrogen, argon, helium, etc. coexist. The polymerization reaction is carried out in the same manner as the polymerization reaction of olefins using ordinary Ziegler type catalysts. That is, all the reactions are carried out in a gas phase, in the presence of an inert solvent, or in the presence of a solvent itself, in the absence of oxygen, water, etc. The polymerization conditions for olefin are temperature 20-3
00°C, preferably 40 to 200°C, and the pressure is normal pressure to 70% crIl-G, preferably 2% to 60 kg/ci-G. The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but this can be done effectively by adding hydrogen to the polymerization system. Of course, a two-stage VA or twin-stage multi-stage polymerization reaction with different polymerization regulations such as hydrogen concentration and polymerization temperature can be carried out without any problem. The ethylene-α-olefin copolymer which is component a) of the present invention produced in step 1 in this way has (a) a density of 0.8
6-0.91 g/cta3, (b) boiling l! n-hexane insoluble content is 10% by weight or more, (c) differential scanning calorimetry (
1) Maximum peak temperature (TI) indicated by SC) is 100
It is important that the temperature is above ℃. If the density exceeds 0.91 g/J, there is a concern that the composition will lose its flexibility, and if the density exceeds 0.86 g/J, the flexibility of the composition may be lost.
If it is less than /cm3, the melting point will be low and the heat resistance will be poor. In addition, ■ Boiling 11n- of tyrene-α-olefin copolymer
If the insoluble content is 10% by weight, the amorphous portion and low molecular weight components will increase, resulting in poor oil resistance and blight resistance. On the other hand, the maximum peak wettability Fl of differential scanning calorimetry (DSC)
A material with a Tm of less than 100° C. also has poor heat resistance. The melt index (hereinafter abbreviated as MI) of the ethylene-α-olefin copolymer is 0.05 to 50 g/10 minutes,
Preferably it is in the range of 0.1 to 20 g/10 minutes. In particular, when it is used as an electric material, a range of 0.3 to 5 g/10 minutes is preferable. In the present invention, the method for measuring the insoluble matter and I'SC is as follows. [Measurement method for boiling 1N-hexane insoluble matter] Using a heat press, mold a sheet I- with a thickness of 200/1 m, cut out three sheets each with a structure of 20111111X301+1111, and then press them into a double tube type. Using a Soxhlet extractor, boil Il! Extraction is carried out for 5 hours with n-hexylene. After taking out the insoluble matter into the n-1, and vacuum drying (7 hours under vacuum, 50° C.), the insoluble matter in the boiling n-1 was calculated using the following formula. Boiling @ n-hexane insoluble matter (Wii 1%) - (extracted flow sheet) - hanging/unextracted sea 1 - weight) x 100 (wt%) [r) S (], J: Measuring method 1 Heat press Approximately 5 mg of sample was weighed out from the molded film with a thickness of 1100I1, and each sample was placed in a SC device and heated to 170°C for 15 mL after being heated for 4 hours. Cool to 0°C at a rate of 2.5°C/min. Next, from this state, the stomach is thirsty at a rate of 0°C/min to 170°C, and measurement is performed. The temperature at the position of the maximum peak that appeared during 4 wet cycles from 0°C to 170°C is defined as TllJ. The -brene-α-olefin copolymer used in the present invention is clearly distinguished from the dylene-α-olefin copolymer obtained by using bafudium as a solid catalyst component. In other words, conventional J-blen propylene copolymers, etc. have almost no crystallinity, and even if a crystalline portion exists, it is in a very small amount, and r) the maximum peak temperature by SC (T l
1lHj at 100°C. This shows that it cannot be used for applications that require heat resistance f1, mechanical strength, etc. Unsaturated component b) of the present invention A-refin ffi compound modified with carboxylic acid or its derivative and 1511
, Additive modification of 10% of unsaturated carboxylic acid or its derivative 005 to olefin polymer in the presence of organic peroxide (1) The above-mentioned olefin polymers include polyethylene, polypropylene, polybutene-1, poly-4-methylene-bentene-1, and other olefins alone and 0-polymer, ethylene, propylene, butene-1,4-methylene-1, etc. Mutual copolymers of pentene-1, hel-1-1, octene-1, etc., ethylene and vinyl ester, unsaturated carboxylic acid, unsaturated carboxylic F
l! , T-sprue, etc. are used, but preferably polyethylene, polypropylene and T-sprue are used.
-[Brene and other α- of tyrene-butene-1 copolymer q
A copolymer with olefin! Preferably, pumpkin 0.
91 to 0.97 g/cm3 of ``-Brene homopolymer or (YoT tyrene-α-olefin copolymer or 1J:
and mixtures thereof are good. In addition, in the present invention, polypropylene, butyl rubber, L-ethylene propylene rubber, ethylene-propylene rubber, styrene-butane rubber, polybutadiene rubber, chloroprene rubber, urethane rubber, and Synthetic rubbers such as small polymer rubbers, solid rubbers such as natural rubber, or liquid rubbers such as liquid polybutadiene, natural rubbers, and mixtures thereof may be used in combination with the above-mentioned olenoine/polymer.On the other hand, as an unsaturated carboxylic acid, is a monosalt of acrylic acid, methacrylic acid, maleic acid, fumaric acid, lithonic acid, itaconic acid, citraconic acid, etc.3.
Mention may be made of tetraacids and dibasic acids. Examples of derivatives of unsaturated carboxylic acids include metal salts, amides, imides, esters, and anhydrides of the unsaturated carboxylic acids listed in item 11, and among these, maleic anhydride is most preferred. The amount of addition and modification of unsaturated carboxylic acids or derivatives thereof (hereinafter simply referred to as unsaturated carboxylic acids) to the olefin polymer is from 0.05 to 10% by weight, preferably from 0.1 to 5% by weight, and the amount of organic Heat the reaction in the presence of peroxide. The reaction described in 1-1 is carried out by melt-mixing in an extruder or a kneading machine such as Panbury Milly, etc. using solvent-free F, or using aromatic hydrocarbons such as benzene, xylene, and toluene, hexane, heptane, and octane. The method of heating and mixing in a solvent such as an aliphatic hydrocarbon to react is not particularly limited, but it is preferable to carry out the reaction in an extruder because it is easy to operate and has an excellent economy f1. When the amount of unsaturated carboxylic acid exceeds 10% by weight, there is a risk of decomposition and crosslinking reactions in addition to the addition reaction, and the effects of the present invention cannot be achieved at 0.05% by weight without vortexing. No. Examples of the above organic peroxides include penzoyl peroxide, lauryl peroxide, azobisisobutyronitrile, dicumyl peroxide, t-butyl hydroperoxide, α, α′- Bis(1-butylperoxydiisopropyl)benzene, di-t-butylperoF9ide, 2,5-di(t-butylperoxy)hexine/T are preferably used, and olefin hand coalescence 1
The 00 small hanging part is used in the range of 0005 to 2.0 small hanging part, preferably +1.01 to 1 fold R part. If the amount of organic peroxide added is less than 0.005%,
It is difficult to obtain any further effect even if added in excess of 2 parts by weight, and may cause excessive decomposition or crosslinking reactions. The reaction temperature described in -1- is under the usual hot stone conditions, i.e., resin deterioration, unsaturated carboxylic acid decomposition, and organic peroxide content.
It is selected as appropriate, taking into account temperature, etc., but generally 150
Reaction temperatures ranging from 0C to 300C are used. The modified olefin polymer of the present invention is further mixed with unmodified A-refine polymer or unmodified rubber, etc., as appropriate.
You can also use The ratio of the modified olefin to the unmodified olefin polymer is arbitrary, but preferably 1:99/50:50 in terms of weight. In the present invention, the amount of component b) is 1 to 40% by weight, preferably 10 to 20% by weight, based on component a). %
is within the range of If the amount of component b) above is less than 1% by weight, the tensile strength is 1tI.
There is almost no improvement in t, and if it exceeds 40% by weight, the elongation decreases significantly and the tensile strength is inferior. As the flame retardant that is component C) of the present invention, additive flame retardants such as halogen flame retardants, phosphorus flame retardants, and inorganic flame retardants are used. A (TBA), to (Sabromo Bengen,
Decabromosif I ether, tetrabromoethane (
TBE>, tetrabromoethane (-1-B B')
, to V4j bromocyclodecane (+-I B Cr)
) and chlorine-based compounds such as chlorinated paraffin, chlorinated polyphenyl, chlorinated polyethyoneone, diphenyl chloride, park [10 pentacyclodecane, chlorinated naphthalene, etc., and are used with antimony trioxide, etc. By doing so, it becomes more effective. In addition, examples of phosphorus flame retardants include tricresyl phosphate, ]-su(]β-chlorotyl) phosphate-1-, tri(dichloropropyl) phosphate, tri(dibu[11
Main examples include phosphoric acid esters or halogenated phosphoric esters such as propyl phosphate, 2.3 to 1 copy of dibromob, and 2.3 to chloropropyl phosphate. Furthermore, the inorganic flame retardants of the present invention include aluminum hydroxide, magnesilate hydroxide, zirconium hydroxide, basic magnesium, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and tin oxide. hydrates, hydrates of inorganic metal compounds such as borax, zinc borate,
Zinc metaborate, barium metaborate, zinc carbonate, rA
Examples include magnesium-calcium, calcium carbonate, barium carbonate, magnesium oxide, 1-libdenum 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, at least one selected from the group consisting of magnesium hydroxide, aluminum hydroxide, basic bamboo magnesium carbonate, and hydrotalcite has a good flame retardant effect and is economically advantageous. Although the main fibers of these flame retardants vary depending on the type, the average particle size of magnesyl hydroxide, aluminum hydroxide, etc. is preferably 20 μm or less. The amount of flame retardant above is 5 to 200 per 100 of the resin.
Heavy parts, preferably in the range of 10 to 150 parts by weight. Especially when using only the above non-molecular flame retardant, 40
It is used in a range of parts by weight to 200 parts by weight. The flame retardant effect is small when the hanging part of the flame retardant is 5 or less, and the flame retardant effect is small.
If it exceeds parts by weight, mechanical strength and elongation will decrease, flexibility will be lost, the product will become brittle, and low-temperature properties will also deteriorate. 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. In addition, in the present invention, inorganic t! ! By using 'lt4 and a flame retardant together, the amount of flame retardant added can be reduced and other properties can be imparted. The composition of the present invention has a) microbial density of 0.86 to 0.919/c;
I13, boiling 11 Ethylene-α-olefin copolymer 99 = 60% by weight, which has an n-hexane insoluble content of 10% by weight or more and a maximum peak temperature shown by differential scanning calorimetry of 100°C or more; 1 to 40% by weight of olefin polymer modified with saturated carboxylic acid or its derivatives
C) Flame retardant 5 to 2 to 100 parts of resin component + fi parts
This is a flame retardant composition with excellent mechanical strength and heat resistance, containing 0.00 parts by weight, and in particular, by combining component a) with an inorganic flame retardant, the amount of flame retardant that can be received is increased. The flame retardant effect can be enhanced. In addition, a) component b
b) by applying an A reflex polymer modified with an unsaturated carboxylic acid or a derivative thereof of component (b).
The component acts as a coupling agent for component a) and component C), increasing mutual compatibility and significantly improving mechanical strength and heat resistance. This means that the material can be suitably used as electrical materials such as insulating materials for electric wires, cables, etc., and jacket materials, which require materials with higher heat resistance, that is, materials with a smaller thermal deformation rate. Examples of the inorganic filler as an optional component used in the present invention include powder-like, tabular, scaly, 11-shaped, spherical or hollow, and fibrous, and specifically, calcium sulfate, 11-sand calcium, etc. , clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, nitride bow rope, aluminum nitride, carbon black, etc. Powder and granular filling H1 cloud R1, glass plate , Serisai]・,Pyrophilai】・,
Metal foils such as aluminum flakes, flat or scaly fillers such as graphite, hollow fillers such as whitebait balloons, metal balloons, glass balloons, eaves stones, glass miN,
carbon, graphite, whiskers,
Examples include metal fibers, silicon carbide fibers, asbestos, minerals such as wollastonite, etc. These addition amounts are applied up to a culm degree of 100 fJ per hanging part of the composition of the present invention. If the above-mentioned addition amount exceeds 100 tungsten, the mechanical strength such as impact strength of the molded product will decrease, which is not preferable. In addition, in the present invention, when the inorganic flame retardant or inorganic filler is used, the surface of the inorganic material is coated with fatty acids such as stearic acid, oleic acid, palmitic acid, or their metal salts, paraffin wax, polyethylene wax, etc. Or with their modified products, organic silanes, organic borane, organic titanates, etc.! ! It is preferable to perform a surface treatment such as coating. The composition of the present invention is prepared by mixing an ethylene-α-olefin copolymer in a specific range, a flame retardant, optionally an inorganic filler, additives, etc. using a Banbury mixer-1 pressure kneader 1 kneading extruder, twin-screw extruder, etc. It is melt-kneaded using a commonly used mixer such as a roll, pelletized, etc., and provided as a molded product or a masterbatch. It can also be used as a tri-blend of the above resin components, flame retardants, additives, etc. In the present invention, other synthetic rJA fats, antioxidants, lubricants, various organic and inorganic pigments, ultraviolet inhibitors, dispersants, copper damage inhibitors, neutralizing agents, blowing agents, plasticizers, anti-foaming agents, etc. Additives such as crosslinking agents, crosslinking agents, flowability improvers, thread strength improvers, and nucleating agents may be added to the extent that they do not significantly impair the effects of the present invention. (E) Example Next, an example will be described. <Resin used> a) Component (A) Ethylene-butene-1 copolymer (M 1 = 1.09/10 min, density = 0.905
SF/ci3) (B) ■Dylene-butene-1 copolymer (M r = 0.8 g/10 min, density -0.900 g
/ CIl+3) (C) Ethylene-propylene copolymer (M I = 0.5 g/Io min, density -0,890
9/cta 3) In the case of comparative example (D) Ethylene-butene-1Jt polymer (M T =
4 g/10 min, density -0,887 g/ctn") (Product name: Tafmer A 4085.311 manufactured by Petrochemical ■) (E) Ethylene [1-pyrene copolymer (M I =
1.9g/10kimachi a-0,869/cttt 3)
(Product name: EP(')2p, made by Japan Synthetic Rubber ■?1) b
z, i''2<unsaturated carboxylic acid or derivative thereof +
l Refine polymer〉 ('') ■Brene-butene-1jt polymer (density -0,9
359/cttr", Mr-0.8g/10 min) (Product name: 1 stone Nirex AM1720, Japan Petrochemical Co., Ltd.?t IIJ) (Gel-Brene-Butene-1 copolymer (Dense 1ff=
0.922g/cm3, Mr = 1.0g/1
0 minutes) (Product name: 1 stone Sunilex [: 2320, Nippon Petrochemical Co., Ltd. Kikune I ¥J) (l-1>-T thylene-butene-1,1 polymer (density-
0,9564? /cm3, M I = 1.6g/10
) (Product name: Futani Seki Stafrene F715, manufactured by Kuchimoto Petrochemical Kyokuchi) - Magnesium hydroxide as a flame retardant to 100 parts of the resin component consisting of specified amounts of a) component J: and b) component. (
Table 1 shows the results of adding a predetermined amount of Kisuma 5B (trade name: Kisuma 5B, manufactured by Kyowa Kagaku Co., Ltd.) and evaluating the physical properties. Addition of an unmodified olefin polymer and a modified olenoin copolymer using a diethylene-alpha-olefin copolymer (A) as a component; I noticed that. As a result, if the amount of modified polyolefin added is less than the range of the present invention, the tensile strength will be low, the thermal deformation rate will be low, and the heat resistance will be poor. On the other hand, if the amount is too high, mechanical strengths such as tensile strength and elongation will decrease, and the improvement effect will be small. In comparison, the material of the present invention has significantly improved mechanical strength such as tensile strength and elongation, and heat resistance (heat deformation rate). Furthermore, when component b) is unmodified, the tensile strength, elongation and heat resistance are not significantly improved. Example 5-6 Example 4
In Examples 6 to 5, the effect of changing the ethylene-α-olefin as component a) and changing the modified olefin polymer as component b) was observed in Examples 2 and 5. Like Nibi 3, it has been greatly improved. On the other hand, in Comparative Examples 5 and 6, as a result of using a rubber-based ethylene-α-olefin copolymer instead of component a) of the present invention, the tensile strength, elongation, and heat resistance were significantly inferior. Met. 17-8 In Example 8 and Comparative Examples 7-8, the influence of the amount of flame retardant (magnesium hydroxide) added was observed. As a result, if the amount of flame retardant added is less than the range of the present invention, the oxygen index value will be small and the flame retardant effect will be poor, and if it is too much, mechanical strength such as tensile strength and elongation will be significantly reduced. . -1 series, the compositions of the present invention all have tensile strength,
It is clear that improvements in mechanical strength such as elongation, heat resistance and twist resistance have been achieved in a well-balanced manner. Bottle 11 (-2) Same as Example 2 except that aluminum hydroxide (product name: Hygilite 42M, manufactured by Nippon Light Metal Company)>130ffl hanging part was used instead of magnesium hydroxide, which is the flame retardant in Example 2. The results are shown in Table 1. As a result, the tensile strength, elongation, J: and heat resistance are significantly improved. Examples 10-11 Comparative Examples Examples 10-11 is a halogen flame retardant, a derivative of tetrabromobisphenol (trade name: Fire Guard 3), instead of magnesium hydroxide, the flame retardant in Example 2.
000, manufactured by Teijin Kasei NE1) and 30 parts by weight of antimony trioxide 15-j, and the evaluation results were evaluated in the second test.
Shown in the table. Comparative Example 9 was carried out in the same manner as in Example 10 using the resin (D) used in Comparative Example 5, and the results are shown in Table 2. As a result, all of the products of the present invention have been significantly improved. The test method is as follows. <Test method> 1. Tensile strength and strength were measured by punching out No. 3 dumbbells from a sheet with a thickness of 1 m/m using a Tensilon at a tensile speed of 200 mm/min. 2. Ili [lfl workshop - 1 support ■ A cylinder with a thickness of 6 m/m and a diameter of 10 m/H was pressurized with a load of 2.64 kg in an oil bath at 100°C, and the deformation rate after 30 minutes was determined 1c0 3.Flame retardancy (0,1) Compliant...0, 2863~ ASTM test combustion time continues to burn for 3 minutes or more, or combustion length is 50
Minimum oxygen concentration required for continuous burning of more than m/m. Based on V-2 of the U L-standard published by L1. (In other words, the average self-extinguishing time is 25 seconds or less, and the maximum extinguishing time is 30 seconds or less.) (f) Effects of the Invention As mentioned above, the combustible M composition of the present invention has a ) α is 0.86 ~ O, QI SJ ctn3, boiling @
n-1-1 non-insoluble content is 101F amount % or more, and the maximum peak temperature shown by differential scanning calorimetry is 100 ° C
J tyrene-α-olefin J (in combination with a polymer and especially an inorganic flame retardant, Ia-free
By blending an appropriate amount of A reflex compound modified with unsaturated carboxylic acid Mb or its derivative, which is the component b), the mechanical It can significantly improve strength and heat resistance. In addition, by using a hydrate of an inorganic metal compound such as aluminum hydroxide or magnesium hydroxide as a flame retardant, a flame-retardant F111 composition that does not generate gas during combustion and is low smoke and pollution-free can be obtained. This meets the recent needs for high Ti combustion. Furthermore, since the composition of the present invention has excellent commercial characteristics, it can be used with or without crosslinking to be used as electrical insulation houses, sheathing materials, etc. for electric wires, cables, etc. ′
C can be used. In particular, cables for each scale power generation plan 1~, including the original squid research institute that stipulates corrosive gas M, for chemical, steelmaking, and petroleum plants - pull, fireproof electric wire, and general house wiring, etc. It is suitable for use in places where bamboo is required. It is also used for molding applications such as extrusion molded products such as films, sheets, pipes, etc., master badges, etc., and is used for fiber assembly, electricity, electronics, automobiles, ships, etc.
It is used in various fields such as aircraft, architecture, and civil engineering as panels, packaging materials, furniture, household goods, etc. Patent applicant 1 Petrochemical Co., Ltd. 1 procedure? rli
iE Book July 31, 1985

Claims (11)

[Claims] (1)a) Density is 0.86 to 0.91 g/cm^3, boiling n-hexane insoluble content is 10% by weight or more, and maximum peak temperature shown by differential scanning calorimetry is 100°C
The above ethylene-α-olefin copolymer 99-6
0% by weight, b) Resin component 10 consisting of 1 to 40% by weight of an olefin polymer modified with an unsaturated carboxylic acid or its derivative
0 parts by weight, c) 5 to 200 parts by weight of a flame retardant. (2) The olefin polymer of component b) has a density of 0.91
The flame-retardant olefin polymer composition according to claim 1, which is an ethylene-α-olefin copolymer of ~0.97 g/cm^3. (3) The flame-retardant olefin polymer composition according to claim 1 or 2, wherein the unsaturated carboxylic acid or its derivative as component b) is maleic anhydride. (4) The flame retardant olefin polymer composition according to any one of claims 1, 2 and 3, wherein the flame retardant of component c) is a hydrate of an inorganic metal compound. thing. (5) The flame-retardant olefin polymer composition according to claim 4, wherein the hydrate of the inorganic metal compound is aluminum hydroxide or magnesium hydroxide. (6) a) Density is 0.86 to 0.91 g/cm^3, boiling n-hexane insoluble content is 10% by weight or more, and maximum peak temperature shown by differential scanning calorimetry is 10
Ethylene-α-olefin copolymer 99 with a temperature of 0°C or higher
~60% by weight, b) 100 parts by weight of a resin component consisting of 1 to 40% of an olefin polymer modified with an unsaturated carboxylic acid or its derivative, and c) 5 to 200 parts by weight of a flame retardant. An electrical material made of a polyolefin polymer composition. (7) The electrical material according to claim 6, wherein the ethylene-α-olefin of component a) has a melt index of 0.3 to 5 g/10 min and an α-olefin having 4 to 10 carbon atoms. (8) The olefin polymer of component b) has a melt index of 0.1 to 5 g/10 min and a density of 0.91 to 0.97.
The electrical material according to claim 6 or 7, which is an ethylene-α-olefin copolymer of g/cm^3. (9) The electrical material according to any one of claims 6, 7 and 8, wherein the unsaturated carboxylic acid or its derivative as component b) is maleic anhydride. (10) The electrical material according to any one of claims 6, 7, and 9, wherein the flame retardant of component c) is a hydrate of an inorganic metal compound. (11) The electrical material according to claim 10, wherein the hydrate of the inorganic metal compound is aluminum hydroxide or magnesium hydroxide.