WO2005092975A1

WO2005092975A1 - Flame-retardant ethylene resin composition and use thereof

Info

Publication number: WO2005092975A1
Application number: PCT/JP2005/002498
Authority: WO
Inventors: Hiroshi Uehara; Masayoshi Yamaguchi
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2004-03-25
Filing date: 2005-02-17
Publication date: 2005-10-06
Also published as: CN100567385C; TW200619291A; KR20070004811A; CN1934185A; KR100807764B1; JP4790606B2; JPWO2005092975A1; TWI293081B

Abstract

[PROBLEMS] Disclosed is a resin composition having good flexibility and pliability as well as excellent flame retardance. Also disclosed is a formed body made from such a resin composition. [MEANS FOR SOLVING PROBLEMS] A flame-retardant ethylene resin composition is characterized by containing 51-95 parts by weight of an ethylene-α-olefin copolymer (A) and 5-49 parts by weight of a copolymer (B) of an ethylene and a vinyl ester, and further containing 0.1-50 parts by weight of a graft modified ethylene polymer (C), 50-250 parts by weight of a metal hydroxide (D), 0.1-50 parts by weight of a triazine compound (E) and 0.1-40 parts by weight of a powder silicone (F) per 100 parts by weight of the total of (A) and (B). The flame-retardant ethylene resin composition is further characterized in that the weight ratio between (E) and (F), namely (E)/(F), is 1.2 or more.

Description

Specification

Flame-retardant ethylene resin composition and use thereof

Technical field

The present invention relates to a thermoplastic resin composition and a molded article thereof, and more particularly, to a thermoplastic resin composition suitable as a material for an insulator or a sheath of an electric wire, and has a high degree of flame retardancy. The present invention relates to a polymer composition and a molded article made of the same.

Background art

[0002] Conventionally, as a sheath material and a partial insulating material of an electric wire, polychlorinated butyl (PVC) has been frequently used, and its flexibility, flame retardancy, and insulating properties have been evaluated. In general, PVC contains a large amount of plasticizer, which makes it easier to cure if the plasticizer is removed by heating, etc., and generates chlorine-based gas during combustion. It has become required.

[0003] Under such circumstances, various flame-retardant resin compositions based on an ethylene-based polymer such as polyethylene have been proposed.

[0004] USP 6,232,377 includes ethylene Z-vinylester copolymer, ethylene Z a, J3-unsaturated carboxylic acid copolymer, low-density polyethylene, specific ethylene copolymer selected, and the like. Further, a flame-retardant resin composition containing a metal hydroxide, a triazine compound and a specific flame-retardant compound is described. However, these ethylene-based polymers have the problem that the flexibility and flexibility tend to decrease when the amount of addition of an inorganic compound such as a metal hydroxide is increased in order to enhance the flame retardant effect. There is. (Patent Document 1) Therefore, a resin composition having excellent flame retardancy and flexibility and excellent flexibility and excellent tensile properties, and a molded article made of the composition, particularly insulation of electric wires It is a first object of the present invention to provide a body and a Z or sheath.

[0005] On the other hand, various types of thermoplastic polymers and thermosetting polymers are used for household electrical appliances, buildings, interior decorations, automobile parts, internal wiring of electronic devices, and the like. Most of these polymers (especially olefinic polymers) are flammable.

[0006] From the viewpoint of disaster prevention, the demand for non-combustible and non-combustible facilities and structures has been increasing. Items that may be a fire source, such as household electric appliances, require a high degree of flame retardancy. The standard of the flame retardancy of the internal wiring material is defined, for example, in the United States UL standard (Underwriters Laboratories Inc.) and the like, and is evaluated by a vertical combustion test called a VW-1 test. Therefore, there is a need for a material that can be used for a long time even when exposed to high heat or fire.In order to impart high flame retardancy to many thermoplastic polymers and thermosetting polymers, heavy materials are required. A method of adding a flame retardant during the manufacture of a united product or a molded product is widely used.

[0007] As the flame retardant, many compounds such as metal hydroxides; borates; organic halides; phosphorus compounds such as phosphates, red phosphorus, organic phosphorus conjugates, and organic nitrogen compounds are used. ing. Among them, the organic halogenated compound, the organic phosphorus compound and the like exhibit an excellent flame retardant effect.

[0008] However, these halogen-containing compounds are thermally decomposed during resin molding to generate hydrogen halide, degrade the resin itself, cause coloring, and generate halogenated hydrogen in a fire. Problem.

Conventionally, inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide have been used as halogen-free flame retardants. However, these inorganic compounds alone have low flame-retardant effects and cannot exhibit sufficient effects unless added in large amounts, and if added in large amounts, the inherent physical properties of the resin may be impaired. there were.

[0010] On the other hand, as a flame retardant which does not contain halogen and can obtain a relatively good flame retardant effect, there are a specific organic phosphorus compound, a specific organic nitrogen compound and the like, and these are often used in practice.

[0011] Triphenyl phosphate (hereinafter referred to as "TPP" t) is a typical example of a conventional organic phosphate ester-based flame retardant, but this compound has low heat resistance and high volatility. For

However, it is not suitable for resin molded at high temperature, and the range of use is particularly limited due to mold contamination during molding.

[0012] Condensed phosphoric esters described in JP-B-51-19858, JP-B-59-202240, etc., are used to reduce the volatilization of organic phosphorus and use it as a flame retardant. Although these materials have better heat resistance and lower volatility than TPP, their flame retardant effect per phosphorus content is higher than that of TPP. If P exceeds P, it must be added in a large amount, so that there is a problem that the heat distortion temperature is greatly reduced due to the effect of the resin as a plasticizer (Patent Documents 2 and 3).

[0013] Further, many formulations using a polyphosphate such as ammonium polyphosphate or a condensed phosphoric acid-based flame retardant such as polyphosphoramide have been proposed (JP-A-54-22450, JP-A-54-22450, and JP-A-54-22450). 9-316 250). Strengthening polyphosphoric acid is water-absorbing, and its electric resistance gradually decreases due to the water absorption. Therefore, its application is limited, for example, it is not suitable for insulating coating materials such as electric wires and cables. (Patent Documents 4 and 5)

Recently, there has been a demand for a formulation that replaces phosphorus-based flame retardants in order to suppress eutrophication in closed water systems such as lakes and marshes.

[0014] Organic nitrogen compounds such as melamine also exhibit a relatively high flame retardant effect (Japanese Patent Application Laid-Open No. 8-176343, etc.). However, in the past, in order to achieve a higher flame retardant effect, it was frequently used together with a phosphorus-based flame retardant. (Patent Document 6)

Accordingly, it is possible to provide a polymer composition having a high degree of flame retardancy without containing a halogen-based flame retardant or a phosphorus-based flame retardant, particularly a flame-retardant polymer composition suitable as a covering material for electric wires and a sheath. This is the second object of the present invention.

Recently, a resin composition containing an ethylene 'α-olefin copolymer, a graft-modified ethylene polymer and a metal hydroxide (WO03 / 10654), an ethylene α-olefin copolymer and a graft-modified ethylene polymer A resin composition containing styrene, ethylene, a butyl ester copolymer, and a metal hydroxide is also disclosed (Patent Documents 7, 8).

Patent Document 1: USP6, 232, 377

Patent Document 2: Japanese Patent Publication No. 51-19858

Patent Document 3: JP-A-59-202240

Patent Document 4: JP-A-54-22450

Patent Document 5: JP-A-9-316250

Patent Document 6: JP-A-8-176343

Patent Document 7: International Publication WO03 / 10654

Patent Document 8: JP-A-2000-239459

Disclosure of the invention Problems the invention is trying to solve

[0015] The present invention is to solve the above-mentioned problems, that is, to obtain a resin composition having excellent flexibility and flexibility and an excellent flame-retardant effect, and a molded article comprising the same. Means for solving the problem

[0016] Ethylene 'α-olefin copolymer consisting of ethylene and α-olefin having 3 to 10 carbon atoms (Α) 51 to 95 parts by weight

Copolymer of ethylene and butyl ester (Β) 5-49 parts by weight

(Α) Graft-modified ethylene polymer (C) O. 1—50 parts by weight based on 100 parts by weight of the total amount of (Β)

Metal hydroxide (D) 50-250 parts by weight

Triazine compound (E) O. 1-50 parts by weight

Powdered silicone (F) O. 1—40 parts by weight

And a weight ratio ((E) Z (F)) of (E) to (F) is 1.2 or more.

An electric cable coated with the flame-retardant ethylene resin composition described above.

The invention's effect

[0017] The resin composition of the present invention has good flexibility and flexibility and is excellent in the flame retardant effect.

BEST MODE FOR CARRYING OUT THE INVENTION

[0018] Ethylene 'α-olefin copolymer (A)

The ethylene'α-olefin copolymer (Α) used in the present invention is a copolymer of ethylene and α-olefin having 3 to 10 carbon atoms. Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene 1-otaten, 3-ethyl-1 -Hexene, 1-otene, 1-decene, etc., and a copolymer is composed of one or more of these and ethylene. Of these, at least one or more of propylene, 1-butene, 1-hexene and 1-otaten is preferably used. [0019] Among them, ethylene / 1-butene copolymer is more preferable because of excellent balance between flexibility and tensile properties at the same density.

[0020] The content of each structural unit in the ethylene'α-olefin copolymer is such that the content of the structural unit induced by ethylene is usually 75 to 95 mol%, preferably 80 to 95 mol%, and of 10 alpha - Orefuinka also at least one content usually 5 to 25 mol of structural units also derived compounds force selected ^_0/0, preferably a preferably 5- 20 mol%.

Further, the ethylene′-α-olefin copolymer (Α) used in the present invention preferably has the following properties. That is,

(i) Density force ^s 855- ^900kgZm ^3, preferably, 0. 857-0.890kgZm ^3,

(ii) The melt flow rate (MFR) at 190 ° C and 2.16 kg load is 0.1—100 g / 10

2

Minutes, preferably in the range of 0.1-20 g / 10 minutes, more preferably in the range of 0.1-0.9 g / 10 minutes,

(iii) Index of molecular weight distribution evaluated by GPC method: MwZMn is in the range of 1.5-3.5, preferably 1.5-3.0, more preferably 1.8-2.5,

(iv) the B value determined from the ¹³ C-NMR spectrum and the following formula is 0.9-1.5, preferably 0.9-1.2;

Value = [ΡΟΕ] / (2 · [ΡΕ] [ΡΟ])

(Where [ΡΕ] is the mole fraction of the structural unit derived from ethylene in the copolymer, and [ΡΟ] is the mole fraction of the structural unit derived from ex-olefin in the copolymer. [ΡΟΕ] is the ratio of the number of ethylene-α-olefin chains to all dyad chains in the copolymer.) Ο

[0022] The Β value is an index representing the distribution state of ethylene and α-olefin having 3 to 10 carbon atoms in the ethylene 'α-olefin copolymer. JC Randall (Macromolecules, 15, 35 3 ( 1982)), J. Ray (Macromolecules, 10, 773 (1977)) and others.

[0023] The larger the B value is, the shorter the block chain of the ethylene or a-olefin copolymer becomes, the more uniform the distribution of ethylene and α-olefin is, and the more the composition distribution of the copolymer rubber becomes. Indicates that it is narrow. The smaller the Β value is less than 1.0, the more ethylene. In some cases, the composition distribution of the polymer becomes wide, and there are some bad points such as poor handling.

More preferably, the (V) ¹³ C-NMR ^ vector has an intensity ratio of Ταβ to Taa (Ταβ / Τα0;) of 0.5 or less, preferably 0.4 or less, more preferably 0.5 or less. 3 or less. Here, Τα α and Τα β in the ¹³ C-NMR ^ vector are the peak intensities of CH in the constituent units induced by α-refining force having 3 or more carbon atoms, as shown below.

2

It means two kinds of CHs whose positions with respect to the element are different.

2

R R R R

I I I I

-CC H ₂ -CH ₂ -C- -CH ₂ -C-CH ₂ -C-

I I I I

H H H H

Ύ a β T aa Such To; β / Τα α intensity ratio can be obtained as follows. The ¹³ C-NMR spectrum of the ethylene 'a-olefin copolymer was measured by using, for example, i ^ EOL-GX270 of JEOL Ltd.

It is measured using an NMR measurement device. The measurement was carried out using a mixed solution of hexaclobutadiene / d6-benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight at 67.8 MHz, 25 ° C and d6-benzene ( 128 ppm). The measured ¹³ C-NMR spectrum was analyzed by Lindemann Adams (Analysis).

Analyze according to Chemistry, 43, pi 245 (1971)) and J. C. Randall (Review Macromolecular Chemistry Physics, C29, 201 (1989)) to determine the Tαβ / Taa intensity ratio.

As the ethylene.a-olefin copolymer of the present invention, those having the following properties in addition to the above properties are also preferably used.

(Vi) Melt flow rate (MFR) at 190 ° C, 10kg load and 190 ° C, 2,16kg load

Ten

Ratio to melt flow rate (MFR) in MFR / MFR satisfies the following relationship.

2 10 2

[0027] Mw / Mn + 4.7. 7≤ MFR / MFR

10 2

Here, if MFR, MFR, MwZMn do not satisfy the above relationship,

10 2

May decrease the material strength or both. [0028] [Method for producing ethylene / oc-olefin copolymer (A)]

Such an ethylene 'α-olefin copolymer (A) is at least one or more of ethylene in the presence of a Ziegler-based catalyst or a meta-aqueous catalyst comprising a V-conjugated compound and an organoaluminum compound. Can be produced by copolymerizing the compound with α-olefin having 3 to 10 carbon atoms, but a meta-opened catalyst is preferably used.

[0029] Such a meta-mouthed catalyst (a) reacts with the meta-mouthed polymer (a), the organoaluminumoxy compound (b) and Z or the meta-mouthed polymer (a) to form an ionic compound. And (a), (b) and Z or (c) together with the organoaluminum compound (d)! Yo! / ,.

Ethylene'α-olefin copolymerization can be carried out in the presence of the above catalyst, usually in a liquid phase using a hydrocarbon solvent, by any of batch, semi-continuous and continuous methods. When a metallocene catalyst comprising a metallocene compound (a) and an organoaluminumoxy compound (b) or an ionized ionic compound (c) is used, the metallocene compound in the polymerization system ( The concentration of a) is usually from 0.0005 to 0.1 mmol Z liter (polymerization volume), preferably from 0.0001 to 0.05 mmol Z liter. Further, the organoaluminum conjugated product (b) has a molar ratio of aluminum atom to the transition metal (A1Z transition metal) in the meta-terminated conjugated product in the polymerization system of 1-10000, preferably 10-5000. Supplied in quantity. In the case of the ionized ionic compound (c), the molar ratio of the ionized ionic compound (c) to the meta-mouth compound (a) in the polymerization system (ionized ionic compound (c) Z meta-mouth compound) (A)), supplied in an amount of 0.5-20, preferably 1-10. When an organoaluminum compound is used, the amount is usually about 0 to 5 mmol Z liter (polymerization volume), preferably about 0 to 2 mmol Z liter.

[0030] The copolymerization reaction usually has a reaction temperature of -20 to + 150 ° C, preferably 0 to 120 ° C, and more preferably 0 to 100. In C, 7. 8MPa (80kgfZcm ^2, gauge pressure) pressure of more than 0 or less, preferably more than 0 4. 9MPa (50kgfZcm ^2, gauge pressure) performed under the following conditions.

[0031] Ethylene and α-olefin are supplied to the polymerization system in such an amount that an ethylene'α-olefin copolymer (Α) having the above specific composition is obtained. In the copolymerization, a molecular weight regulator such as hydrogen may be used. [0032] Copolymer of ethylene and bullet ester (B)

The copolymer of ethylene and butyl ester used in the present invention is usually produced by a high-pressure radial polymerization method. Examples of the butyl ester monomer copolymerized with ethylene include butyl propionate, butyl acetate, butyl caproate, butyl laurate, butyl stearate, and trifluoroacetate. Of these, butyl acetate is preferably used. . The copolymer of ethylene and vinyl ester is characterized by a melt flow rate of 0.5 to 50 gZlO, preferably 0.5 to 10 g / 10 min, and a content of butyl monomer of 5 to 40% by weight. %, Preferably 10-35% by weight. If the melt is less than 0.5 gZlO, the workability decreases.If it exceeds 50 gZlO, mechanical properties such as tensile strength, elongation, hardness and impact strength of the obtained resin composition are obtained. It is not desirable because it decreases. Further, if the content of the butyl monomer is less than 5% by weight, the additivity is reduced, and it is difficult to uniformly disperse the flame retardant added as a filler.くない Undesirable because the mechanical properties of the resin composition are deteriorated.

[0033] Grafting: Tylene merging (C)

As the ethylene-based polymer used as a raw material of the graft-modified ethylene-based polymer in the present invention, an ethylene'α-olefin copolymer is preferable. The ethylene'α-olefin copolymer used as a raw material of the graft-modified ethylene polymer is preferably a copolymer of ethylene and α-olefin having 3 to 10 carbon atoms. Examples of the α-olefin having 3 to 10 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 1-otaten, 3-ethyl Examples include root hexene, ι_ otaten, and tridecene. These may be used alone or in combination of two or more. Of these, at least one or more of propylene, 1-butene, 1-hexene, and 1-year-old butene are particularly preferred.

[0034] The content of each structural unit in the ethylene-based copolymer is such that the content of the structural unit derived from ethylene is usually 75 to 95 mol%, preferably 80 to 95 mol%, and the number of carbon atoms is 3 to 95 mol%. 10 a-olefinka Power of at least one compound selected Induced content of constituent units Is usually 5 to 25 mol%, and preferably 5 to 20 mol%.

[0035] The ethylene'α-olefin copolymer used for the graft modification preferably has the following physical properties. That is,

(i) density force ^s 855—910 kgZm ³ , preferably 857—890 kgZm ³ ,

(ii) The melt flow rate (MFR) at 190 ° C and 2.16 kg load is 0.1—100 g / 10

2

Min, preferably in the range of 0.1-20 gZlO min,

(iii) Index of molecular weight distribution evaluated by GPC method: MwZMn is in the range of 1.5 to 3.5, preferably 1.5 to 3.0, more preferably 1.8 to 2.5, Preferably,

(iv) the B value determined from the ¹³ C-NMR spectrum and the following formula is 0.9-1.5, preferably 1.0-1.2;

Value = [ΡΟΕ] / (2 · [ΡΕ] [ΡΟ])

(Where [ΡΕ] is the mole fraction of the structural unit derived from ethylene in the copolymer, and [ΡΟ] is the mole fraction of the structural unit derived from ex-olefin in the copolymer. [ΡΟΕ] is the ratio of the number of ethylene / α-olefin chains to all dyad chains in the copolymer.) Ο

[0036] In addition, the ethylene 'α-olefin copolymer used as a raw material for the graft-modified ethylene polymer has the same characteristics as those described for the ethylene • α-olefin copolymer used in (に). The copolymer is preferably used, but the comonomer type, density, molecular weight, etc. of the copolymer may be the same as or different from (Α).

[0037] The graft-modified ethylene polymer according to the present invention can be obtained by graft-modifying the above-mentioned ethylene copolymer with a vinyl compound having at least one polar group. Examples of the polar compound having a polar group include vinyl compounds having an oxygen-containing group such as an acid, acid anhydride, ester, alcohol, epoxy, and ether as a polar group; vinyl compounds having a nitrogen-containing group such as isocyanate and amide; And other compounds having a silicon-containing group.

[0038] Of these, unsaturated epoxy monomers, unsaturated carboxylic acids and derivatives thereof, and the like, which are preferably vinyl compounds having an oxygen-containing group, are preferred.

As the unsaturated epoxy monomer, unsaturated glycidyl ether, unsaturated glycidyl ester (For example, glycidyl methacrylate).

[0040] Examples of unsaturated carboxylic acids include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, and nadic acid ™ (endo cis-bicyclo [2, 2, 1] Hept-5-ene-2,3-dicarboxylic acid) and the like.

Examples of the unsaturated carboxylic acid derivatives include, for example, the above-mentioned unsaturated carboxylic acid acid halide compounds, amido conjugates, imido conjugates, acid anhydrides, and ester compounds. Specific examples include maleic chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

[0042] Among these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferable, and maleic acid, nadic acid ™ and acid anhydrides thereof are particularly preferable. The position of the unsaturated carboxylic acid or its derivative to be grafted onto the unmodified ethylene-based copolymer is not particularly limited, and any carbon of the ethylene-based polymer constituting the graft-modified ethylene-based polymer is not particularly limited. An unsaturated carboxylic acid or a derivative thereof is bonded to an atom.

[0043] The above-mentioned graft-modified ethylene polymer (C) can be prepared by various conventionally known methods, for example, 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 above unmodified ethylene polymer is dissolved in a solvent, and an unsaturated carboxylic acid or the like is added to carry out graft copolymerization.

In any method, it is preferable to carry out the graft reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer such as the above unsaturated carboxylic acid.

[0045] As the above-mentioned radical initiator, organic peroxides, azoi conjugates and the like are used. Specific examples of such a radical initiator include organic peroxides such as benzoylperoxide, dichlorobenzoylperoxide and dicumylperoxide; azobisisobutyl nitrile, dimethylazoisobutyrate and the like. Azo compounds and the like. Among these, dicumylperoxide, di-tert-butylperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexine-1,3,2,5-dimethyl-2 , 5-di (tert-butylperoxy) (Ii) Dialkylperoxides such as hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

[0046] These radical initiators are usually added in an amount of 0 to 100 parts by weight of the unmodified ethylene-based polymer.

001-1 part by weight, preferably 0.003-0.5 part by weight, more preferably 0.05-0.3 part by weight.

[0047] The reaction temperature in the above-described graft reaction using a radical initiator or the graft reaction performed without using a radical initiator is usually 60 to 350 ° C, preferably 150 to 30 ° C.

It is set in the range of 0 ° C.

[0048] Metal hydroxide (D)

Examples of the metal hydroxide used in the present invention include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, manganese hydroxide, zinc hydroxide, zinc oxide, talcite, and mixtures thereof. Among them, a mixture containing magnesium hydroxide alone and a mixture containing magnesium hydroxide alone and a mixture containing magnesium hydroxide alone and aluminum hydroxide are particularly preferable.

[0049] Triazine compound (E)

The triazine ring-containing compound (E) used in the present invention may be any compound generally known as a flame retardant, such as melamine, ammeline, melam, benzguanamine, acetguanamine, phthalodiguanamine, melamine cyanurate. Melamine pyrophosphate, butylene diguanamine, norbornene diguanamine, methylene dimelamine, ethylene dimelamine, trimethylenedimelamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimelamine, and the like. . Of these, melamine cyanurate is preferably used. The compounding amount of the triazine ring-containing compound is 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of the above-mentioned ethylene 'olefin copolymer (A) and the copolymer of ethylene and butyl ester (B). Parts, preferably 5-40 parts by weight. When the compounding amount is less than 1 part by weight, generation of a combustion inert gas (nitrogen gas) from this compound is not significant, and does not exhibit a synergistic effect with other flame retardants. On the other hand, if it exceeds 50 parts by weight, the effect of flame retardancy is not so high, but rather, it may adversely affect the moldability and the mechanical properties of the obtained molded product, which is not desirable. [0050] Powdered silicone

Examples of the powdered silicone (also referred to as silicone powder) of the present invention include organic organopolysiloxane powder, such as dimethylpolysiloxane powder. The powdered silicone of the present invention has a molecular weight (Mn) power measured by GPC of OOOOO-100,000,000, and preferably <500000-500000.

[0051] Other additives

In addition to the above, the polymer composition according to the present invention may further include, if necessary, an antioxidant, an ultraviolet absorber, a weather stabilizer, a heat stabilizer, an antistatic agent, a flame retardant, a pigment, a dye, a lubricant, and the like. Additives can be blended. It is more preferred that the polymer composition according to the present invention contains a boric acid conjugate, preferably zinc borate, as a flame retardant auxiliary.

[0052] Polymer composition

The polymer composition according to the present invention is

Ethylene 'α-olefin copolymer (A) 51-95 parts by weight

Copolymer of ethylene and butyl ester (B) 5-49 parts by weight

(A) For the total amount of (B) 100 parts by weight

Graft-modified ethylene polymer (C) 0.1-50 parts by weight

Metal hydroxide (D) 50-250 parts by weight

Triazine compound (E) 0.1-50 parts by weight

Powdered silicone (F) 0.1-40 parts by weight

Wherein the weight ratio of (E) to (F) ((E) Z (F)) is 1.2 or more.

[0053] More preferably, ethylene-α-olefin copolymer (A) 51 to 85 parts by weight

Copolymer of ethylene and butyl ester (B) 15-49 parts by weight

(A) For the total amount of (B) 100 parts by weight

Graft-modified ethylene polymer (C) 0.1-40 parts by weight

Metal hydroxide (D) 50-250 parts by weight

Triazine compound (E) 1-40 parts by weight

Powdered silicone (F) 0.1-26 parts by weight

And the weight ratio of (E) to (F) ((E) Z (F)) is 1.5 or more. Still more preferably, ethylene-α-olefin copolymer (A) 55-85 parts by weight Copolymer of ethylene and butyl ester (B) 15-45 parts by weight

(A) For the total amount of (B) 100 parts by weight

Graft-modified ethylene polymer (C) 0.1-30 parts by weight

Metal hydroxide (D) 50-250 parts by weight

Triazine compound (E) 5-40 parts by weight

Powdered silicone (F) 0.1-26 parts by weight

And the weight ratio of (E) to (F) ((E) Z (F)) is 1.5 or more.

Most preferably, ethylene-α-olefin copolymer (A) 55-75 parts by weight

Copolymer of ethylene and butyl ester (B) 25-45 parts by weight

(A) For the total amount of (B) 100 parts by weight

Graft-modified ethylene polymer (C) 0.1-30 parts by weight

Metal hydroxide (D) 50-250 parts by weight

Triazine compound (E) 5-40 parts by weight

Powdered silicone (F) 0.1-26 parts by weight

And the weight ratio of (E) to (F) ((E) Z (F)) is 2.0 or more.

As a flame retardant aid, the boric acid conjugate is obtained by mixing the ethylene 'α-olefin copolymer (A) and the copolymer of ethylene and butyl ester (Β) with (A) (Β). 0.

It is more preferable that the content be 1 to 30 parts by weight, preferably 0.1 to 20 parts by weight.

[0056] The polymer composition according to the present invention comprises the above components (A), (B), (C), (D), (F) and (F), and additives optionally blended. It is prepared by melt mixing by various conventionally known methods.

For example, in the polymer composition according to the present invention, the above components are charged simultaneously or sequentially into, for example, a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, and the like, and mixed. After that, it is obtained by melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like.

[0058] Among these, when an apparatus having excellent kneading performance such as a multi-screw extruder, an Ader, and a Banbury mixer is used, a high-quality polymer composition in which each component is more uniformly dispersed can be obtained. The

[0059] In addition, at any of these stages, the above additives, for example, an anti-oxidation agent, may be added as necessary.

[0060] Molded article containing flame-retardant ethylene resin composition

The molded article according to the present invention uses the flame-retardant ethylene-based resin composition according to the present invention, and is prepared by a conventionally known melt molding method such as extrusion molding, rotational molding, calender molding, injection molding, compression molding, transfer molding. It can be formed into various shapes by a method such as powder molding, blow molding, vacuum molding and the like.

[0061] The flame-retardant ethylene resin composition according to the present invention can be suitably used for wire coating applications such as wire sheaths and wire insulators. Further, the molded article according to the present invention is a coating layer such as an electric wire sheath and an insulator of an electric wire. The coating layer such as the electric wire sheath and the insulator of the electric wire is formed by a conventionally known method such as extrusion molding. Formed around.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[0063] The physical properties of the ethylene'α-olefin copolymer were evaluated as follows.

(1) Density

The strand after MFR measurement at 190 ° C and a load of 2.16 kg was heat-treated at 120 ° C for 1 hour, gradually cooled to room temperature over 1 hour, and measured by a density gradient tube method.

(2) a-olefin content, T a j8 ΖΤ α α, B value

It was determined by 1 ³ C-NMR ^ vector.

(3) Mw / Mn

The measurement was performed at 140 ° C. in an orthodichlorobenzene solvent using GPC (gel permeation chromatography).

(4) MFR / MFR

10 2

According to ASTM D-1238, MFR at 190 ° C at 10kg load and 2.16kg load

Ten

Was measured and the ratio was calculated. If this ratio is large, the flow of the polymer when it melts

2

It shows that the processability is excellent, that is, the processability is high! [0064] Ethylene-a-olefin copolymer, copolymer of ethylene and butyl ester, graft-modified ethylene-based polymer, metal hydroxide, triazine-based compound, powdered silicone and silicone resin used in Examples and the like Is as follows.

[0065] Ethylene-at-olefin copolymer (A):

This is an ethylene′-butene copolymer A-1 prepared in Production Example 1 below.

[Production Example 1]

(Preparation of ethylene / 1-butene copolymer A-1)

18.4 mg of trifluorocarbamate (tetrakispentafluorophenol) borate was taken, and 5 ml of toluene was added and dissolved to prepare a toluene solution having a concentration of 0.004 mM Zml. [Dimethyl (t-butylamide) (tetramethyl-7} 5-cyclopentagel) silane] Take 1.8 mg of titanium dichloride, dissolve in 5 ml of toluene, and dissolve in toluene at a concentration of 0.000 lmM / ml. A solution was prepared. At the start of the polymerization, 0.38 ml of a toluene solution of triphenylcarbamate (tetrakispentafluorophenyl) borate was added at the beginning of the polymerization, and [dimethyl (t-butylamide) (tetramethyl-7} 5- Take 0.38 ml of a toluene solution of cyclopentagel) silane] titanium dichloride, add 4.24 ml of toluene for dilution, and add triphenylcarbane (tetrakispentafluorophenol). Prepare 5 ml of a toluene solution in which borate is 0.002 mMZL in terms of B and [dimethyl (t-butylamide) (tetramethyl-7} 5-cyclopentagel) silane] titanium dichloride is 0.0005 mMZL in terms of Ti. did.

[0067] 750 ml of heptane was inserted at 23 ° C into a 1.5-liter SUS autoclave equipped with a stirring blade and having a capacity of 1.5 L. 10 g of 1-butene and 100 ml of hydrogen were inserted into the autoclave while rotating the stirring blade and cooling with ice. Next, the autoclave was heated to 100 ° C. and further pressurized with ethylene so that the total pressure became 6 kg. When the internal pressure of the autoclave became 6 kg, 1.OmMZml hexane solution of triisobutylaluminum (TIBA) 1.Oml was injected with nitrogen. Subsequently, 5 ml of the catalyst solution prepared as described above was injected into the autoclave with nitrogen to initiate polymerization. After that, the temperature of the autoclave was adjusted to 100 ° C for 5 minutes, and ethylene was directly supplied so that the pressure became 6 kg. Five minutes after the start of the polymerization, 5 ml of methanol was inserted into the autoclave by a pump to stop the polymerization, and the auto-tarve was depressurized to atmospheric pressure. Inject 3 liters of methanol into the reaction solution with stirring. . The obtained polymer containing the solvent was dried at 130 ° C. for 13 hours at 600 torr to obtain 10 g of an ethylene-butene copolymer A-1. Table 1 shows the properties of the obtained ethylene / 1-butene copolymer.

[table 1]

[0069] Copolymer of ethylene and bullet ester (B):

Ethylene-vinyl acetate copolymer trade name EVAFLEX EV360 (manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.) (hereinafter abbreviated as EVA).

[0070] Graft-modified ethylene polymer (C):

The maleic anhydride graft-modified ethylene / 1-butene copolymer prepared in Production Example 2 below.

[Production Example 2]

(Preparation of maleic anhydride graft-modified ethylene / 1-butene copolymer)

10 kg of the above ethylene / 1-butene copolymer A-I and a solution of 50 g of maleic anhydride and 3 g of di-tert-butylperoxide dissolved in 50 g of acetone were blended in a Henschel mixer.

[0072] Next, the blend obtained as described above was charged from the hopper of a single-screw extruder having a screw diameter of 40 mm and L / D = 26, and a resin temperature of 260 ° C and an output of 6 kgZ hours. In strand shape And cooled with water, and then pelletized to obtain a maleic anhydride graft-modified ethylene / 1-butene copolymer C-1.

[0073] The obtained graft-modified ethylene '1-butene copolymer C-1 strength After extracting unreacted maleic anhydride with acetone, the amount of grafted maleic anhydride in this graft-modified ethylene' 1-butene copolymer As a result, the amount of the graft was 0.43% by weight.

[0074] Metal hydroxide (D):

Magnesium hydroxide trade name Kisuma 5B (manufactured by Kyowa Chemical Co., Ltd.)

Triazine compound (E):

Melamine cyanurate brand name MC-440 (manufactured by Nissan Chemical Co., Ltd.)

Powdered silicone (F):

Polyorganosiloxane trade name DC4-7081 (manufactured by Toray Dow Co. Ltd.)

Number average molecular weight (Mn) measured by GPC method: 1000000

The preparation and evaluation of the insulated wire sample were performed by the following method.

(Production of Insulated Wire Sample)

Using a polymer extruder having the composition shown in Table 2, a melt extruder (manufactured by Toyo Seiki Co., Ltd., product name: Lab Blast Mill) equipped with an electric wire coating die, die temperature: 190 ° C, screw rotation: 30 rpm , Extrusion rate: 1.6-1.8kg / h, wire diameter

The periphery of a seven-stranded conductor (outer diameter: about 1.35 mm) of 0.45 mm soft copper wire was covered with a 0.8 mm thick polymer composition to obtain an insulated wire sample with a finished diameter of 3.0 mm.

(5) Strength at Break and Elongation at Break

Conduct tensile test at 20mm span, 200mmZ tensile speed in accordance with JIS K6301

V ヽ, strength at break and elongation at break were measured.

(0077) Torsional rigidity

The torsional stiffness at a temperature of 23 ° C was measured using a Crashberg type flexibility tester manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K6745.

(7) Flame retardancy (combustion test)

Based on the vertical combustion test specified in UL Standard VW-1, the test was performed using the insulated wire sample prepared above. Table 2 shows the evaluation results.

[0080] [Table 2]

Industrial applicability

Since the resin composition of the present invention has excellent flexibility and flexibility and is excellent in flame retardancy, it can be suitably used for, for example, wire sheath applications such as wire sheaths and wire insulators.

Claims

The scope of the claims

[1] Ethylene 'α-olefin copolymer (A) 51-95 parts by weight

Copolymer of ethylene and butyl ester (B) 5-49 parts by weight

(A) For the total amount of (B) 100 parts by weight

Graft-modified ethylene polymer (C) 0.1-50 parts by weight

Metal hydroxide (D) 50-250 parts by weight

Triazine compound (E) 0.1-50 parts by weight

Powdered silicone (F) 0.1-40 parts by weight

And a weight ratio ((E) Z (F)) of (E) to (F) is 1.2 or more.

[2] An electric cable coated with the flame-retardant ethylene resin composition according to claim 1.