TWI293081B - Flame-resistant ethylene series resin composition and the use thereof - Google Patents

Description

1293081 IX. Description of the invention: 'Technical field to which the invention pertains>> The present invention relates to a thermoplastic resin composition and a molded body thereof, and more particularly to a material which is particularly suitable as an insulator and a sheath of a wire. A thermoplastic resin composition, a polymer composition having high flame retardancy, and a molded body made of the same. [Prior Art] Conventionally, polyvinyl chloride olefin (PVC) has been used as the outer sheath material of a wire and a part of the insulating material, and the flexibility, flame retardancy, and insulation have been evaluated. PVC generally contains a lot of plasticizers, so it is easy to harden by heating plasticizers, and since chlorine gas is generated during combustion, it has been demanded in recent years to develop electric wires that replace PVC. In view of such a situation, for example, various flame retardant resin compositions having a vinyl polymer such as polyethylene as a substrate have been proposed.

In US Pat. No. 6,232,377, it is described that it contains a specific ethylene-based copolymer selected from an ethylene/vinyl ester copolymer, an ethylene/α, a stone-unsaturated carboxylic acid copolymer, and a low-density polyethylene, and further contains A flame retardant resin composition of a metal hydroxide, a tri-well compound, and a specific flame retardant compound. However, in the case of the above-mentioned ethylene-based polymer, when the amount of the inorganic compound such as metal hydroxide is increased in order to increase the flame retarding effect, there is a problem that flexibility and flexibility are easily lowered (Patent Document 1). Therefore, a resin composition which is excellent in flame retardant effect, is excellent in flexibility and flexibility, and is excellent in stretched physical properties, and a molded body composed of the composition, particularly an insulator and/or outer sheath of the electric wire are the present invention. The first purpose. 6 326\Patent specification (supplement)\94-09\94108564

1293081 On the other hand, a variety of thermal polymers and thermosetting polymers are used in household electrical products, buildings, interior decoration, interior wiring of automotive parts and electronic equipment. Most of these polymers (especially hydrocarbon polymers) are flammable. From the viewpoint of disaster prevention, the requirements for incombustibility and incombustibility of various facilities and structures are increased, and in particular, articles having a fire source such as household electrical products must be highly flame retardant. The flame retardancy standard of the internal wiring is determined, for example, by the U L specification (U n d e r w r i ^ Laboratories Inc.) of the United States, and is evaluated by a sag test called VW-1 test. Therefore, it is still required to be resistant to long-term use even when exposed to high heat, in order to impart high flame retardancy to many thermoplastics and thermosetting polymers, and to produce a molded article or a molded article. A method of adding a flame retardant is widely used. As the flame retardant, a metal hydroxide, a borate, an organic compound, a phosphorus compound such as a phosphate, a red phosphorus or an organic phosphorus compound, and a nitride or the like are used. Among them, an organic halogen compound, a compound or the like can exhibit excellent flame retardancy. However, these i-containing compounds thermally decompose and form hydrogen halide during the molding of the resin, which deteriorates the resin itself, causes coloration, and causes problems such as hydrogen halide generation in the event of fire. Conventionally, as a flame retardant containing no halogen, an inorganic flame retardant such as magnesium hydroxide hydroxide has been used. However, only such inorganicization has a low flame retarding effect, and if it is not added in a large amount, it does not exhibit sufficient effects. If it is added in a large amount, the original physical properties of the resin may be impaired, and the use of 326\patent specification (supplement)\94 may be used. -09\94108564 Products, plasticized for roasting, become materials ters Direct-fired fire-fighting polymer halogenated organic machine phosphorus and produce aluminum, compound, and range

There is a limit on 1293081. On the other hand, as a flame retardant which does not contain a kerogen and which can obtain a relatively good flame retardant, there are specific organic phosphorus compounds, specific organic nitrides, and the like, which are generally practical. As a representative of the conventional organophosphate-based flame retardant, there is a phosphate triester (hereinafter referred to as "TPP"), but this compound is not suitable for molding at a high temperature because of its low heat resistance and volatility, especially during molding. The scope of use is limited due to mold contamination. In order to reduce the volatility of the organic phosphorus, the phosphatizing ester described in Japanese Patent Publication No. Sho. No. 5 1 - 1 9 8 8 8 and JP-A-59-200 2 2 4 0 or the like is used. Although such a substance has better heat resistance and low volatility than TPP, the non-flammable effect of the phosphorus unit content does not exceed TPP and must be greatly added. Therefore, the effect as a plasticizer of the resin has a decrease in the heat distortion temperature. Problems such as (Patent Documents 2 and 3). Further, many formulations using a condensed phosphate-based flame retardant such as polyphosphate such as ammonium polyphosphate or polyphosphonium have been proposed (Japanese Patent Laid-Open Publication No. Hei 5 4 - 2 2 4 5 0, JP-A 9- 3 1 6 2 5 0 bulletin, etc.). However, phosphoric acid is water-absorptive, and the electric resistance is gradually lowered by water absorption, so that it is not suitable for use as an insulating coating material such as a wire or a cable (Patent Documents 4 and 5). In addition, recently, in order to suppress the eutrophication of a closed water system such as a lake, it is also necessary to replace the formulation of a phosphorus-based flame retardant. The organic nitrogen compound such as melamine also exhibits a high flame retardant effect (Japanese Patent Laid-Open No. Hei 8 - 1 7 6 3 4 3, etc.). However, in the past, in order to pursue more 326\patent specification (supplement)\94-09\94108564 8 effect benzene 5 to make the special amount of large acid more than the demand for the high-altitude 1293081 fire-resistant effect, more difficult to phosphorus A fuel is used in combination (Patent Document 6). Therefore, it is possible to provide a polymer composition which is highly flame retardant even if it does not contain an i-based flame retardant and a phosphorus-based flame retardant, and is particularly suitable as a coating material for electric wires and a flame-retardant polymer composition of an outer sheath. The second purpose. Recently, resin compositions (W 0 0 3 / 1 0 6 5 4 ), ethylene·α-containing ethylene-α-olefin copolymers and graft-modified ethylene polymers and metal hydroxides have also been disclosed. a resin composition of a dilute hydrocarbon copolymer and a graft-modified ethylene-based polymer and a copolymer of a mother-in-law and a vinyl ester copolymer and a metal hydroxide (Patent Document 7)

Patent Document 1 ·· USP 6, 2 3 2, 3 7 7

Patent Document 2: Japanese Patent Publication No. Sho. No. 5 1 - 1 9 8 5 8 Patent Document 3: Japanese Patent Laid-Open No. 5 9 - 2 0 2 2 4 0 Patent Document 4: Japanese Patent Laid-Open No. 5 4 - Patent Document 5: Japanese Patent Laid-Open Publication No. Hei 9 - 3 1 6 2 5 0 Patent Document 6: Japanese Patent Laid-Open No. Hei 8 - 1 7 6 3 4 No. 3 Patent Document 7: International Publication 10 0 3 / 1 0 6 5 No. 4 Patent Document 8: Japanese Patent Laid-Open No. 2000-237----- The problem is that a resin composition excellent in flexibility, flexibility, and flame retardancy is obtained, and a molded body composed of the same. (Means for Solving the Problem) The present invention provides a composition comprising: ethylene and a carbon number of 3 to 10 alpha olefins. 9 326\patent specification (supplement)\94-09\94108564 1293081 analysis to find T a yS /Τ α α intensity ratio. The ethylene·α-olefin copolymer of the present invention is also suitably used insofar as it has the above characteristics plus the following characteristics. (ν i ) 1 90 ° C, melt flow rate (MFR ) at a load of 10 kg.) Ratio of melt flow rate (MFR2) at a load of 1 90 °C and 2.16 kg: MFR1 〇/MFR2 satisfies the 歹4 relationship.

Mw/Mn + 4. MFR10/MFR2

Here, when M F R 1 〇, M F R 2, and M w / η η do not satisfy the above relationship, formability or material strength or both are lowered. [Method for producing ethylene·α-olefin copolymer (Α)] Such an ethylene·α-olefin copolymer (A) can be made by a Ziegler-based catalyst or a metallocene system composed of a V compound and an organic compound. In the presence of a medium, ethylene is produced by copolymerizing at least one or more α-olefins having 3 to 10 carbon atoms, but a metallocene-based catalyst is preferably used. Such a metallocene-based catalyst may be formed by reacting a metallocene compound (a) with an organic hydroxy compound (b) and/or a metallocene compound (a) to form an ion pair compound (c), and may also be Formed by (a), (b) and/or (c) and the organic Ilu compound (d). The ethylene·α-olefin copolymerization can be carried out by any of a batch type, a semi-continuous type, and a continuous type in the presence of the above-mentioned catalyst in a liquid phase using a usual hydrocarbon solvent. In the case of using a metallocene catalyst composed of a metallocene compound (a) and an organic hydroxyaluminum compound (b) or an ionized ionic compound (c), the concentration of the metallocene compound (a) in the polymerization system is usually 0.00005~0.1 millimoles/liter (polymerization volume), preferably 0.0001~0.05 13 326\patent specification (supplement)\94-09\94108564 1293081 millimoles/liter. Further, the organic hydroxyaluminum compound (b) is preferably 1 to 1 0 to 0 0 0 with respect to the molar ratio (A1/transition metal) of the aluminum atom of the transition metal in the metallocene compound in the polymerization system. It is supplied in a quantity of 1 0 to 5 0 0 0. In the case of ionizing the ionic compound (c), the molar ratio of the ionized ionic compound (c) of the metallocene compound (a) in the polymerization system (ionized ionic compound (c) / metallocene compound ( a)) is supplied in an amount of from 0. 5 to 2 0, preferably from 1 to 10. Further, in the case of using an organic compound, it is usually used in an amount of about 0 to 5 mmol/liter (polymerization volume), preferably about 0 to 2 mmol/0 liter. The copolymerization reaction is usually carried out at a reaction temperature of -20 to + 150 ° C, preferably 0 to 120 ° C, more preferably 0 to 100 ° C, a pressure exceeding 0 and 7.8 MPa (80 kgf / cm 2 , gauge pressure) or less. It is preferably carried out under conditions of more than 0 and 4.9 MPa (50 kgf/cm 2 , gauge pressure) or less.

The ethylene and the α-olefin are supplied to the polymerization system in the amount of the ethylene·α-olefin copolymer (A) which can obtain the above specific composition. When copolymerizing, a molecular weight modifier such as hydrogen can also be used. [Copolymer of ethylene and vinyl ester (B)] The copolymer of ethylene and vinyl ester used in the present invention is usually produced by a high pressure radical polymerization method. Examples of the vinyl ester monomer copolymerized with ethylene include vinyl propionate, vinyl acetate, vinyl hexanoate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. Among them, vinyl acetate is used. Suitable for use. Further, the copolymer of ethylene and vinyl ester has a melt flow rate of 0.5 to 5 0 / 10 minutes, preferably 0. 5 to 1 0 g / 1 0 minutes, vinyl single. The content of the body is 5 to 40% by weight, preferably 10 to 3 5 326. Patent Specification (Replenishment)\94-09\94108564 14 1293081 (i) The density is 855 to 910 kg/m3, preferably 857. 〜890公斤/m3; (ii) The melt flow rate (MFR2) at 190 ° C and 2.6 kg load is 0.1 to 1.0 g / 10 min, preferably 0. 1~2 0 g (1) The index of the molecular weight distribution evaluated according to the GPC method: Mw/Mn is 1. 5 to 3. 5, preferably 1. 5 to 3. 0, more preferably 1. 8 a range of 〜2 · 5 ; more preferably, the B value of the (iv) 13C-NMR spectrum and the following formula is 0.9 to 1.5, preferably 1. 0 to 1. 2 ;

B value = [ΡΟΕ] / (2 · [PE] [PO]) (wherein, [PE] is the molar content of the constituent unit derived from ethylene in the copolymer, and [PO] is in the copolymer The molar content of the constituent unit derived from the α-olefin, [Ρ0Ε] is the ratio of the ethylene-α-bake hydrocarbon chain of the total dyad chain in the copolymer. In addition, the ethylene·α-olefin copolymer which is used as a graft-modified ethylene-based polymer raw material is preferably used in the same manner as those described in the ethylene·α-olefin copolymer used in (A), but is preferably used. The comonomer type, density, molecular weight, and the like of the copolymer may be the same as or different from (A). The graft-modified ethylene-based polymer of the present invention can be obtained by graft-modifying a vinyl compound having at least one polar group in the above-mentioned ethylene-based copolymer. Examples of the vinyl compound having a polar group include a vinyl compound having an oxygen group as an acidic group such as an acid, an acid anhydride, an ester, an alcohol, an epoxy or an ether; and a vinyl group having a nitrogen group such as an isocyanate or a guanamine. A compound; a thiol-containing vinyl compound having a vinyl decane or the like. Among them, a vinyl compound having an oxy group is preferred, and the unsaturated ring is 16 326\patent specification (supplement)\94-09\94108564

1293081 Oxygen monomer, unsaturated carboxylic acid and derivatives thereof are preferred. The unsaturated epoxy monomer may, for example, be an unsaturated glycidyl ether or a glycidyl ester (e.g., glycidyl thioglycolate). Examples of the unsaturated carboxylic acid include acrylic acid, maleic acid, butenedioic acid, tetrahydrofurfuric acid, itaconic acid, pyrocitric acid, crotonic acid, isophthalic acid, and Nadic AcidTM (internal cis- Bicyclo[2, 2, 1 ]hept-5-ene-2, dicarboxylic acid) and the like. Further, examples of the derivative of the unsaturated carboxylic acid include an acid halide compound of the above unsaturated carboxylic acid, a guanamine compound, a ruthenium compound, an acid and an ester compound. Specific examples thereof include maleic chloride, maleic amine, maleic anhydride, pyroic acid anhydride, maleic acid monodecyl ester, dibutyl phthalate, and maleic acid shrinkage. Glycerides and the like. Among these, an unsaturated dicarboxylic acid or an anhydride thereof is suitably used, and particularly, butenedioic acid, Nad i c Ac i dTM or an anhydride thereof is suitable. Further, the graft position of the unsaturated carboxylic acid grafted in the unmodified ethylene copolymer or the grafting position thereof is not particularly limited as long as it is a vinyl polymer constituting the graft-modified ethylene polymer. An unsaturated carboxylic acid or a derivative thereof may be bonded to any carbon atom. The graft-modified ethylene-based polymer (C) as described above can be prepared by various methods previously known, for example, by the following methods. (1) A method in which the unmodified ethylene-based polymer is melted by an extruder or the like and an unsaturated carboxylic acid or the like is added to carry out graft copolymerization. (2) A method in which the unmodified ethylene-based polymer is dissolved in a solvent and a saturated carboxylic acid or the like is added to carry out graft copolymerization. 326\patent specification (supplement)\94-09\94108564 17 saturating anti-bar 3 - and anhydride subsequences are acid and not

1293081 Any one of the methods is the same, and in order to facilitate the graft copolymerization of the above unsaturated carboxylic acid or the like, it is preferably carried out in the presence of a radical initiator. As the radical initiator, an organic peroxide, a compound or the like can be used. Specific examples of such a radical initiator include a peroxide such as benzoquinone, dichlorobenzidine peroxide or dicumyl peroxide; azobisisobutyronitrile and dimethylazo A compound such as butyrate or the like. Wherein, dicumyl peroxide, di-Φ-peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3 dimercapto-2, a dialkyl peroxide such as 5_bis(t-butylperoxy)hexane or 1,4-bis(peroxyisopropyl)benzene is suitable for use as such a radical initiator, With respect to the unmodified ethylene-based polymer component, it is usually used in an amount of from 0.01 to 1 part by weight, preferably from 0. 0 0 3 to 0, more preferably from 0. 0 5 to 0. Serving amount. In the graft reaction using a radical initiator such as the above or a grafting reaction which is not carried out using an initiator, the reaction temperature is usually set to a range of °C, preferably from 150 to 300 °C. [Metal hydroxide (D)] Examples of the metal hydroxide used in the present invention include magnesium hydroxide, calcium hydroxide, barium hydroxide, manganese hydroxide, and wollastonite alone or The mixture is preferably a mixture of magnesium hydroxide alone containing magnesium hydroxide, or aluminum hydroxide alone and a mixture containing ruthenium. [Three-well well compound (E)] 326\patent specification (supplement)\94-09\94108564 18 branch monomer grafting reverse azo-peroxidation organic azo third-butyl '2,5- three Butyl 1 00 weight 5 weight free radical 60 to 350 aluminum, zinc hydride, singly and 1293081 'boronic acid compound, preferably zinc borate is more preferred. * [Polymer Composition] The polymer composition of the present invention is characterized by comprising: acetamidine·α-dilute hydrocarbon copolymer (A) 5 1 to 9 parts by weight; copolymer of ethylene and ethylene ester (B) 5 to 49 parts by weight; and 100 parts by weight of the graft-modified ethylene-based polymer (C) with respect to the total of (A) and (B) 0.1 to 500 parts by weight, metal hydroxide (D) 5 0 to 2 5 parts by weight, φ tri-grain compound (E ) 0 · 1 to 5 0 parts by weight, powder polyoxyalkylene (F) 0 · 1 to 40 parts by weight, and (E) The weight ratio ((E)/(F)) to (F) is 1.2 or more. Preferably, it comprises: ethylene to olefin copolymer (A) 51 to 85 parts by weight; copolymer of ethylene and vinyl ether (B) 15 to 49 parts by weight; and total amount of (A) and (B) 1 0 0 parts by weight of the graft-modified ethylene-based polymer (C) 0.1 to 40 parts by weight,

Metal hydroxide (D) 5 0 to 250 parts by weight, three σ well system compound (E) 1 to 40 parts by weight, powder polyoxyalkylene (F) 0 · 1 to 2 6 parts by weight, and The weight ratio of (Ε) to (F) ((E) Λ F)) is 1.5 or more. Further preferably, it comprises: acetamidine·α-glycol copolymer (Α) 55 to 85 parts by weight; copolymer of ethylene and vinyl ester (Β) 15 to 45 parts by weight; and relative to (A) and (Β) Total amount of 10 parts by weight 20 326\Patent specification (supplement)\94-09\94108564 1293081 Graft-modified 6-olefin polymer (C) 0 · 1~3 〇 Wide weight. Metal hydroxide ( D) 50 to 250 parts by weight, 3 ϋ well compound (E) 5 to 40 parts by weight, powder polyoxyalkylene (F) 0.1 to 26 parts by weight, and weight ratio of (E) to (F) (( E) / (F)) is preferably 15 or more containing: ethylene·α-olefin copolymer (A) 55 to 75 parts by weight · copolymer of ethyl and ethyl ester (B) 25 to 45 dandan eight to Lithium; and 100 parts by weight of the graft-modified vinyl polymer (c) 0 · 1 to 3 〇 by weight of the total of (A) and (B) ^ metal hydroxide (D) 50 to 250 weight份份三三井系化合物(E) 5~40 parts by weight, powder polysulfide (F) 〇.l~26 parts by weight, and weight ratio of (E) to (F) ((E) / (F)) is 2 〇,,, • υ Μ. Further, as a boric acid compound which is a flame retardant auxiliary agent, it is known that a copolymer of ethylene/copolymer (yttrium) and ethylene and a vinyl ester is obtained.

And (B) and (B 100 parts by weight, more preferably 30 parts by weight, more preferably 〇b parts. The polymer composition of the present invention is the above (A), (B), (C (E) and (F) component ' can be prepared by melt-mixing with other various methods as needed. For example, the polymer composition of the present invention sequentially packs the above components. After entering, for example, a Hanschel mixer, a v-type pick-up machine, a machine, a ribbon doping machine, etc., and mixing, a single-axis extruder, 326\patent specification (supplement)\94-09\94108564 21 〜~妇经) Total measurement 2 〇 weight), (D), : previously known at the same time or ^ drum mixed multi-axis

1293081 The machine can be obtained by melt-kneading, such as a machine, a kneader, or a Bunbury mixer. In this case, if a multi-axis extruder, a kneader, a Bunbury mixer, etc. are used, the kneading performance is excellent. In this way, a high-quality polymer composition in which the components are more evenly dispersed can be obtained. Further, the aforementioned additives such as an antioxidant or the like may be added at any of these stages as needed. [Molded article containing a flame retardant ethylene resin composition] The molded system of the present invention uses the flame retardant ethylene resin composition of the present invention, and is formed by extrusion molding, calendering, and injection according to a conventionally known melt molding method. Forming, compression molding, transfer molding, powder molding, blow molding, vacuum forming, and the like can be formed into various shapes. The flame retardant vinyl resin composition of the present invention can be suitably used, for example, for wire coating applications such as an outer sheath and a wire insulator. Further, the form of the present invention is a coating layer such as a wire sheath and a wire insulator, and the coating layer such as the wire sheath wire insulator is formed around the wire by a conventionally known method such as extrusion molding. [Examples] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the examples. Further, the physical properties of the ethylene·α-olefin copolymer were evaluated as follows (1) The strands after the MFR was measured at a density of 1 90 ° C and 2.1 kg, and heat-treated at 1 ° C for 1 hour. After 1 hour of cold cooling to room temperature, the measurement was carried out by a density ladder method. 326\Patent specification (supplement)\94-09\94108564 22 Combined with the example of Chengcheng and Chengming 20 degrees 1293081 (2) α-dilute hydrocarbon content, Τα cold/Τα α, B value according to 13C-NMR Spectral decision. (3) Mw/Mn was measured at 140 °C using G P C (colloidal permeation chromatography) in an o-diphenyl solvent. (4) MFRi〇/MFR2

According to A S T M D - 1 2 3 8, M F R ! 于 under a load of 1 0 0 °C and M F R 2 under a load of 2.16 kg were measured, and the ratio was calculated. When this ratio is large, it shows that the fluidity at the time of melting of the polymer is excellent, that is, the workability is high. Ethylene·α-baked hydrocarbon copolymer used in the examples and the like, a copolymer of B-baked and B-baked ester, a graft-modified vinyl polymer, a metal hydroxide, a tri-well compound, a powder polysecond oxygen burning And the polysecond oxygen resin is as follows. Ethylene·α-diene copolymer (Α): The ethylene·1-butene copolymer A-1 prepared in the following Production Example 1. [Production Example 1] (Preparation of ethylene·1-butene copolymer A-1) 13.4 mg of triphenylcarbon rust (nonylpentafluorophenyl) borate was added, and 5 ml of toluene was added to dissolve it, and the concentration was adjusted to 0. . 0 0 4 m M / m 1 of benzene solution. Take dimethyl [dimethyl (t-butyl decylamine) (tetradecyl-7 / 5 - cyclopentadienyl) decane] titanium 1.8 mg, add 5 ml of toluene and dissolve it, prepare A concentration of 0. 0 0 1 m M / ml of a solution of toluene. At the beginning of the polymerization, 0.38 ml of a solution of triphenylcarbenium (p-pentafluorophenyl) borate in benzene was obtained, and gasification [didecyl (t-butyl decylamino) (tetramethyl-7? 5) -cyclopentadienyl) decane] titanium ruthenium benzene solution 0.38 ml, then added toluene benzene 4.24 ml, prepared 23 326\patent specification (supplement)\94-09\94108564 1293081 'triphenyl Carbon radium (p-pentafluorophenyl) borate is 0.002 mM / L in terms of B • Dichloro (t-butyl decylamino) (tetradecyl-5 -cyclopentadienyl) decane 5 ml of a toluene solution of titanium with a T i of 0 · 0 0 5 m M / L was placed in a SUS autoclave with a stirrer with a capacity of 1.5 liters fully substituted with nitrogen, and loaded under 23 Heptane 750 ml. The stirring blade was rotated in this autoclave, and 10 g of 1-butene and 100 liters of hydrogen were charged while being bathed in an ice bath. Next, the autoclave was heated to 100 ° C, and further, the pressure of ethylene was 6 kg. When the pressure in the autoclave was 6 kg, 1000 ml of a 1.0 m m / m 1 hexane solution of triisobutyl aluminum (T I B A ) was pressed in with nitrogen. 5 ml of the above-mentioned catalyst solution was pressurized with nitrogen into a autoclave and polymerization was started. Thereafter, the autoclave temperature was adjusted to an internal temperature of 100 ° C in 5 minutes, and ethylene was directly supplied as a pressure of 6 kg. Five minutes after the start of the polymerization, 5 liters of sterol was charged in a pressure cooker and the polymerization was stopped, and the autoclave was depressurized to atmospheric pressure. 3 liters of sterol was injected while stirring in the reaction. The obtained solvent-containing compound was dried under the conditions of 1 30 ° C, 13 hours, and 600 ° 〇 r r to obtain 100% ethylene·butene copolymer A-1. The properties of the obtained ethylene·1-butene copolymer are shown in Table 1. 326\Patent specification (supplement)\94-09\94108564 24 〇 〇 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 129 C-1. The unreacted maleic anhydride was extracted from the obtained graft-modified ethylene·1-butene copolymer C-1 by acetone, and then the graft-modified ethylene·1-butene copolymer was measured. The graft amount of the butylene dianhydride was 0. 4 wt%. Metal hydroxide (D): Hydroxide town, trade name K i s m a 5 B (manufactured by Xiehe Chemical Co., Ltd.) Three-well well compound (E):

Melamine cyanurate, trade name MC - 4 4 0 (manufactured by Seiko Chemical Co., Ltd.) Powder polyoxyl (F): polyorganic oxygen, trade name DC4-7081 (Dongli Dowconing) The number average molecular weight (Mn) measured by the GPC method: 1 0 0 0 0 0 0 Further, the production of the insulated wire sample and its evaluation were carried out by the following methods. (Production of the sample of the insulated wire) The polymer composition of the composition shown in Table 2 was placed in a mold for a covered electric wire using a melt extruder (product name: Raboplastomill, manufactured by Toyo Seiki Co., Ltd.) at a die temperature of 19 0 °C, screw rotation: 30 rpm, the amount of extrusion ··1. 6~1 . 8 kg / h 7 torsion conductors of soft copper wire with a diameter of 0.45 mm (outer diameter of about 1. 3 5 Mm ) was coated with a polymer composition of 0.8 mm thick to obtain a sample of insulated wire with a finished diameter of 3.0 mm. (5) Breaking point strength and elongation at break point According to J I S K 6 3 0 1, a tensile test was carried out at a span of 20 m m and a tensile speed of 200 m m /min, and the breaking point strength and the elongation at break were measured. (6) Twisted rigidity 26 326\Patent specification (supplement)\94-09\94108564

Claims (1)

1293081 Patent Application No. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> A non-flammable vinyl resin composition characterized by containing: ethylene-α-baked hydrocarbon copolymer (Α) 51 to 95 parts by weight ; copolymer of ethylene and ethylene ester (Β) 5 to 49 parts by weight; and 100 parts by weight of the graft-modified vinyl polymer (C) with respect to the total of (A) and (Β) 1 to 50 parts by weight, metal hydroxide (D) 5 0 to 2,500 parts by weight, three-calling compound (E) 0 · 1 to 50 parts by weight, powder polyoxyl (F) 0 · 1 ～40 parts by weight, the weight ratio of (E) to (F) ((E ) / ( F )) is 1-2 or more. 2. A wire or cable characterized by coating a flame retardant vinyl resin composition of the first application of the patent scope. 326\Total file\94\94108564\94108564 (replace)-1 28 0 ώ-,·5 Whether to change the original substance after one