KR20070004811A - Flame-retardant ethylene resin composition and use thereof - Google Patents

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-alpha-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. ® KIPO & WIPO 2007

Description

Flame-retardant ethylene-based resin composition and its use {FLAME-RETARDANT ETHYLENE RESIN COMPOSITION AND USE THEREOF}

The present invention relates to a thermoplastic resin composition and a molded article thereof, and more particularly, to a thermoplastic resin composition suitable as an insulator of an electric wire and a sheath material, a polymer composition having a high flame retardancy, and a molded article made of them. will be.

Conventionally, polyvinyl chloride (PVC) is used for the sheath material and some insulating materials of electric wires, and its flexibility, flame retardancy, and insulation have been evaluated. Since PVC generally contains a large amount of plasticizer, it is easy to cure when the plasticizer disappears by heating and the like, and in order to generate chlorine-based gas during combustion, development of electric wires that can replace PVC has recently been required.

Under such circumstances, for example, various flame-retardant resin compositions based on ethylene polymers such as polyethylene have been proposed.

USP 6,232,377 contains ethylene / vinyl ester copolymers, ethylene / α, β-unsaturated carboxylic acid copolymers, specific ethylene copolymers selected from low density polyethylene, and the like, and also contains metal hydroxides, triazine compounds and certain flame retardants. Flame retardant resin compositions containing compounds have been described. However, these ethylene polymers have a problem in that flexibility and flexibility tend to be lowered when the amount of addition of inorganic compounds such as metal hydroxides is increased in order to increase the flame retardant effect. (Patent Document 1)

Accordingly, it is a first object of the present invention to provide a resin composition excellent in flame retardant effect, good flexibility and flexibility, and excellent tensile properties, a molded article made of the composition, in particular an insulator and / or sheath of an electric wire. .

On the other hand, various kinds of thermoplastic polymers and thermosetting polymers are used for internal wiring of household appliances, buildings, interior decoration, automobile parts, and electronic devices. Most of these polymers (particularly olefin polymers) are flammable.

From the standpoint of disaster prevention, there is a high demand for flame retardancy and flame retardancy of various facilities, structures, etc., and in particular, the possibility of becoming a ignition source such as household appliances. The criterion for the flame retardancy of the internal wiring material is determined by, for example, the American UL standard (Underwriters Laboratories Inc.) and the like, and is evaluated by a vertical combustion test called the VW-1 test. Therefore, there is a demand for a material that can withstand long-term use even when exposed to high heat or fire. In order to impart high flame retardancy to most thermoplastic polymers or thermosetting polymers, a method of adding a flame retardant to the manufacture of a polymer or a molded article This is widely adopted.

As a flame retardant, Metal hydroxide; Borate salts; Organic halides; Phosphorus compounds such as phosphate, red phosphorus and organophosphorus compounds; Many things, such as an organic nitrogen compound, are used. Among these, especially organic halogen compounds and organophosphorus compounds exhibit excellent flame retardant effects.

However, these halogen-containing compounds have problems such as thermal decomposition during resin molding to generate hydrogen halide, deterioration of the resin itself to cause coloring, and hydrogen halide upon fire.

Conventionally, inorganic flame retardants, such as aluminum hydroxide and magnesium hydroxide, are used as a flame-retardant which does not contain a halogen. However, these inorganic compounds alone have low flame retardant effects, so that sufficient effects cannot be exhibited if they are not added in a large amount, and in addition, the intrinsic physical properties of the resin may be impaired.

On the other hand, as a flame retardant which does not contain a halogen and a comparatively favorable flame retardant effect is obtained, there exist a specific organophosphorus compound, a specific organic nitrogen compound, etc., These are also often provided for practical use.

There is triphenyl phosphate (hereinafter referred to as 'TPP') as a representative of the conventional organic phosphate ester flame retardant, but this compound is not suitable as a resin to be molded at a high temperature because of its low heat resistance and high volatility. The use of the mold is limited due to mold contamination during molding.

Condensed phosphate esters described in JP-A-51-19858, JP-A-59-202240 and the like are used as low-volatility organic phosphorus and used as a flame retardant. These are superior in heat resistance and low volatility than TPP, but the flame retardant effect of phosphorus content does not exceed TPP, so it is necessary to add it in large quantities. Therefore, the thermal deformation temperature is greatly increased for the effect of plasticizer of resin. There existed problems, such as reducing (patent document 2, 3).

In addition, many prescriptions using polyphosphates such as ammonium polyphosphate and flame retardants such as polyphosphates such as polyphosphate have been proposed (Japanese Patent Laid-Open No. 54-22450, Japanese Patent Laid-Open No. 9-316250, etc.). ). However, since polyphosphoric acid is absorbent and the electrical resistance gradually decreases due to absorption, its use is limited to insulation coating materials such as electric wires and cables, etc. (Patent Documents 4 and 5).

In recent years, in order to suppress eutrophication of closed water systems such as lakes and swamps, a prescription for replacing phosphorus-based flame retardants is also required.

Organic nitrogen compounds such as melamine also exhibit a relatively high flame retardant effect (Japanese Patent Laid-Open No. 8-176343 and the like). However, conventionally, in order to obtain a higher flame retardant effect, it was often used together with a phosphorus flame retardant. (Patent Document 6)

Accordingly, it is a second object of the present invention to provide a polymer composition having a high flame retardancy, in particular, a wire covering material and a flame retardant polymer composition suitable as a sheath without containing a halogen flame retardant or a phosphorus flame retardant.

Recently, a resin composition (WO 03/10654) containing an ethylene-α-olefin copolymer, a graft-modified ethylene polymer and a metal hydroxide, an ethylene-α-olefin copolymer, a graft-modified ethylene polymer, an ethylene and a vinyl ester copolymer And the resin composition containing a metal hydroxide are also disclosed (patent document 7,8).

<Patent Document 1> USP 6,232,377

<Patent Document 2> Japanese Patent Application Publication No. 51-19858

<Patent Document 3> Japanese Unexamined Patent Publication No. 59-202240

<Patent Document 4> Japanese Patent Application Laid-Open No. 54-22450

<Patent Document 5> Japanese Unexamined Patent Publication No. 9-316250

<Patent Document 6> Japanese Patent Application Laid-Open No. 8-176343

<Patent Document 7> International Publication WO 03/10654

<Patent Document 8> Japanese Unexamined Patent Publication No. 2000-239459

<Start of invention>

Problems to be Solved by the Invention

The present invention has been made in order to solve the above problems, that is, to obtain a resin composition having a good flexibility and flexibility and excellent flame retardant effect and a molded article formed therefrom.

Means for solving the problem

51 to 95 parts by weight of an ethylene-α-olefin copolymer (A) composed of ethylene and an α-olefin having 3 to 10 carbon atoms,

5-49 parts by weight of copolymer (B) of ethylene and vinyl ester,

0.1-50 weight part of graft modified ethylene polymers (C) with respect to 100 weight part of total amounts of (A) (B),

50 to 250 parts by weight of the metal hydroxide (D),

0.1-50 parts by weight of triazine-based compound (E),

A flame retardant ethylene-based resin composition comprising 0.1 to 40 parts by weight of powdered silicon (F), wherein the weight ratio ((E) / (F)) of (E) and (F) is 1.2 or more.

An electric wire and a cable which coat | cover the flame-retardant ethylene resin composition of the above description.

Effect of the Invention

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

<Best mode for carrying out the invention>

Ethylene-α-olefin copolymer (A)

The ethylene-α-olefin copolymer (A) used in the present invention is a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms. As this C3-C10 alpha-olefin, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1- butene, 3-methyl-1- pentene, 3-ethyl-1- Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene-1-octene, 3-ethyl-1-hexene, 1- Octene, 1-decene, etc. are mentioned, A copolymer is comprised by these, single or 2 types, and ethylene. Of these, at least one or more of propylene, 1-butene, 1-hexene and 1-octene is preferably used.

Among them, the ethylene-butene copolymer is more preferable because the balance of flexibility and tensile properties at the same density is particularly excellent.

The content of each structural unit in the ethylene-α-olefin copolymer is 75 to 95 mol%, preferably 80 to 95 mol%, of the structural unit derived from ethylene, It is preferable that the content of the structural unit derived from the at least one compound selected is usually 5-25 mol%, preferably 5-20 mol%.

Moreover, it is preferable that the ethylene-alpha-olefin copolymer (A) used by this invention has the following properties. In other words,

(Ⅰ) a density of 855 ~ 900kg / m ^3, preferably 0.857 ~ 0.890kg / m ^3,

(Ii) Melt flow rate (MFR ₂ ) at 190 ° C. and 2.16 kg load is in the range of 0.1 to 100 g / 10 minutes, preferably 0.1 to 20 g / 10 minutes, more preferably 0.1 to 0.9 g / 10 minutes. And

(Iii) The index of the molecular weight distribution evaluated by the GPC method: Mw / Mn is in the range of 1.5 to 3.5, preferably 1.5 to 3.0, more preferably 1.8 to 2.5,

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

B value = [POE] / (2, [PE] [PO])

(Wherein [PE] is the molar fraction of the structural unit derived from ethylene in the copolymer, [PO] is the molar fraction of the structural unit derived from α-olefin in the copolymer, and [POE] is the total in the copolymer) Ratio of ethylene-α-olefin chain numbers to dyad chains.).

This B value is an index indicating the distribution state of ethylene and an α-olefin having 3 to 10 carbon atoms in the ethylene-α-olefin copolymer, JCRandall (Macromolecules, 15, 353 (1982)) and J. Ray (Macromolecules, 10). , 773 (1977)).

The larger the value of B, the shorter the block chain of the ethylene or alpha -olefin copolymer, the more uniform the distribution of ethylene and alpha -olefin, and the narrower the composition distribution of the copolymer rubber. Moreover, as B value becomes smaller than 1.0, there exists a case that the composition distribution of an ethylene-alpha-olefin copolymer becomes wide, and handleability worsens.

More preferably, the intensity ratio (Tαβ / Tαα) of Tαβ to Tαα in the (V) ¹³ C-NMR spectrum is 0.5 or less, preferably 0.4 or less, and more preferably 0.3 or less. Here, T α α and T α β in the ¹³ C-NMR spectrum are the peak intensities of CH ₂ in the structural unit derived from an α-olefin having 3 or more carbon atoms, and as shown below, two kinds of positions having different positions with respect to tertiary carbon are shown. CH ₂ means.

This Tαβ / Tαα intensity ratio can be obtained as follows. The ¹³ C-NMR spectrum of the ethylene-α-olefin copolymer is measured using, for example, a JEOL-GX270 NMR measuring apparatus manufactured by Nippon Denshi Corporation. The measurement was performed on a 67.8 MHz, 25 ° C., d6-benzene (128 ppm) basis using a mixed solution of hexachlorobutadiene / d6-benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight. The measured ¹³ C-NMR spectra are analyzed according to Lindemann Adams' proposal (Analysis Chemistry, 43, p1245 (1971)) and JCRandall (Review Macromolecular Chemistry Physics, C29,201 (1989)) to obtain Tαβ / Tαα intensity ratios. .

In addition to the above properties, the ethylene-α-olefin copolymer of the present invention is also suitably used.

(Iii) The ratio of melt flow rate (MFR ₁₀ ) at 190 ° C. and ₁₀ kg load and melt flow rate (MFR ₂ ) at 190 ° C. and 2.16 kg load: MFR ₁₀ / MFR ₂ satisfies the following relationship.

Mw / Mn + 4.7≤MFR ₁₀ / MFR ₂

Here, if _{MFR 10, MFR 2, Mw /} Mn do not satisfy the above relationship, there is a case in which the moldability or strength materials, or both decreases.

[Method for producing ethylene-α-olefin copolymer (A)]

The ethylene-α-olefin copolymer (A) is an ethylene and at least one C3-C10 α- in the presence of a Ziegler catalyst or a metallocene catalyst composed of a V compound and an organoaluminum compound. Although it can manufacture by copolymerizing an olefin, a metallocene type catalyst is used suitably.

Such a metallocene catalyst may be formed from the metallocene compound (a), the compound (c) which reacts with the organoaluminumoxy compound (b) and / or the metallocene compound (a) to form an ion pair. And may be formed from an organoaluminum compound (d) together with (a), (b) and / or (c).

Ethylene-α-olefin copolymerization can be performed in any of batch, semi-continuous, and continuous modes in the liquid phase using a hydrocarbon solvent in the presence of the catalyst. When a metallocene catalyst composed of a metallocene compound (a) and an organoaluminumoxy compound (b) or an ionizing ionic compound (c) is used, the concentration of the metallocene compound (a) in the polymerization system is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.05 mmol / liter. The organoaluminumoxy compound (b) is supplied in an amount of 1 to 10,000, preferably 10 to 5000, in a molar ratio of aluminum atoms to transition metals in the metallocene compound in the polymerization system (Al / transition metal). . In the case of the ionizing ionic compound (c), the molar ratio (ionizing ionic compound (c) / metallocene compound (a)) of the ionizing ionic compound (c) to the metallocene compound (a) in the polymerization system , 0.5 to 20, preferably in an amount of 1 to 10. In addition, when using an organoaluminum compound, it is normally used in the quantity used as about 0-5 millimoles / liter (polymerization volume), Preferably it is about 0-2 millimoles / liter.

The copolymerization reaction usually has a reaction temperature of -20 ° C to + 150 ° C, preferably 0 ° C to 120 ° C, more preferably 0 ° C to 100 ° C, and a pressure of more than 0. 8 MPa (80 kgf / cm ² , gauge pressure). ), Preferably greater than 0 and under 4.9 MPa (50 kgf / cm ² , gauge pressure) or less.

Ethylene and alpha-olefin are supplied to a polymerization system in the quantity from which the ethylene-alpha-olefin copolymer (A) of the said specific composition is obtained. In the case of copolymerization, molecular weight regulators, such as hydrogen, can also be used.

Copolymer of ethylene and vinyl ester (B)

The copolymer of ethylene and vinyl ester used in this invention is normally manufactured by the high pressure radical polymerization method. Examples of vinyl ester monomers copolymerized with ethylene include vinyl propionate, vinyl acetate, vinyl caprate, vinyl laurate, vinyl stearate, and vinyl trifluoroacetate. Among these, vinyl acetate is suitably used. In addition, the copolymer of ethylene and a vinyl ester has a melt flow rate of 0.5 to 50 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes, and the content of the vinyl monomer is 5 to 40% by weight, Preferably it is 10-35 weight%. If melt flow rate is less than 0.5g / 10min, workability will fall, whereas if it exceeds 50g / 10min, mechanical properties, such as tensile strength, elongation, hardness, and impact strength, of the resin composition obtained will fall. This is undesirable. Moreover, when content of a vinyl monomer is less than 5 weight%, workability will fall, and uniform dispersion of the flame retardant added as a filler will become difficult. On the other hand, when it exceeds 40 weight%, since the mechanical property of the resin composition obtained falls, it is preferable. Not.

Graft  Modified Ethylene Polymer (C)

As the ethylene polymer used as a raw material of the graft-modified ethylene polymer in the present invention, an ethylene-α-olefin copolymer is preferable. As for the ethylene-alpha-olefin copolymer used as a raw material of a graft modified ethylene polymer, the copolymer of ethylene and a C3-C10 alpha-olefin is preferable. As this C3-C10 alpha-olefin, specifically, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1- butene, 3-methyl-1- pentene, 3-ethyl-1- Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 1-octene, 3-ethyl-1-hexene, 1- Octene, 1-decene, etc. are mentioned. These may be individual or 2 or more types may be sufficient as them. Of these, at least one or more of propylene, 1-butene, 1-hexene and 1-octene is particularly preferred.

The content of each structural unit in the ethylene-based copolymer is usually 75 to 95 mol%, preferably 80 to 95 mol%, and is selected from α-olefins having 3 to 10 carbon atoms. The content of the structural unit derived from the at least one compound is usually 5 to 25 mol%, preferably 5 to 20 mol%.

The ethylene-α-olefin copolymer used for the graft modification preferably has the following physical properties. In other words,

(i) a density of 855 ~ 910kg / m ^3, preferably 857 ~ 890kg / m ^3,

(ii) the melt flow rate (MFR ₂ ) at 190 ° C. and 2.16 kg load is in the range of 0.1-100 g / 10 minutes, preferably 0.1-20 g / 10 minutes,

(iii) The index of the molecular weight distribution evaluated by the GPC method: Mw / Mn is in the range of 1.5 to 3.5, preferably 1.5 to 3.0, more preferably 1.8 to 2.5, still more preferably

(iv) B value calculated | required from ¹³ C-NMR spectrum and following formula is 0.9-1.5, Preferably it is 1.0-1.2;

B value = [POE] / (2, [PE] [PO])

(Wherein [PE] is the molar fraction of the structural unit derived from ethylene in the copolymer, [PO] is the molar fraction of the structural unit derived from α-olefin in the copolymer, and [POE] is the total in the copolymer) Ratio of ethylene-α-olefin chain numbers to dyad chains.).

In addition, although the ethylene-alpha-olefin copolymer used as a raw material of a graft modified ethylene-type polymer has a characteristic as described in the ethylene-alpha-olefin copolymer used for (A), it is used suitably. The comonomer species, density, molecular weight and the like may be the same as or different from (A).

The graft modified ethylene polymer according to the present invention is obtained by graft modification of the ethylene copolymer with a vinyl compound having at least one polar group. As a vinyl compound which has a polar group, it has silicon containing groups, such as a vinyl compound which has nitrogen-containing groups, such as a vinyl compound which has oxygen-containing groups, such as an acid, an acid anhydride, ester, alcohol, an epoxy, an ether, an isocyanate, an amide, as a polar group, vinylsilane, etc. Vinyl compounds; and the like.

Among these, vinyl compounds having an oxygen-containing group are preferable, and unsaturated epoxy monomers, unsaturated carboxylic acids, derivatives thereof, and the like are preferable.

Unsaturated glycidyl ether, unsaturated glycidyl ester (for example, glycidyl methacrylate) etc. are mentioned as an unsaturated epoxy monomer.

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 ^TM (endosis-bicyclo [2,2,1] hept-5 -Ene-2,3-dicarboxylic acid) etc. are mentioned.

Moreover, as a derivative of unsaturated carboxylic acid, the acid halide compound, the amide compound, the imide compound, the acid anhydride, ester compound, etc. of the said unsaturated carboxylic acid are mentioned, for example. Specific examples include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like.

Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, in particular maleic acid and nadic acid ^TM Or acid anhydrides thereof. In addition, there is no restriction | limiting in particular in the graft position of the unsaturated carboxylic acid or its derivative graft | grafted to the said unmodified ethylenic copolymer, unsaturated carboxyl to arbitrary carbon atoms of the ethylene polymer which comprises this graft modified ethylene polymer An acid or its derivative should just be bonded.

The graft-modified ethylene polymer (C) as described above can be produced using various conventionally known methods, for example, the following methods.

(1) A method in which the unmodified ethylene polymer is melted with an extruder or the like to add graft copolymer by adding an unsaturated carboxylic acid or the like.

(2) A method of dissolving the unmodified ethylene polymer in a solvent and adding graft copolymer by adding unsaturated carboxylic acid or the like.

In any method, it is preferable to perform a graft reaction in the presence of a radical initiator in order to efficiently graft copolymerize graft monomers such as the unsaturated carboxylic acid.

As the radical initiator, organic peroxides, azo compounds and the like are used. Specific examples of such radical initiators include organic peroxides such as benzoyl peroxide, dichlorobenzoyl peroxide and dicumyl peroxide, and azo compounds such as azobisisobutyronitrile and dimethyl azoisobutyrate. In these, dicumyl peroxide, di-tert- butyl peroxide, 2, 5- dimethyl- 2, 5- di (tert- butyl peroxy) hexyn-3, 2, 5- dimethyl- 2, 5- di ( Dialkyl peroxides such as tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferably used.

These radical initiators are usually used in an amount of 0.001 to 1 part by weight, preferably 0.003 to 0.5 part by weight, and more preferably 0.05 to 0.3 part by weight based on 100 parts by weight of the unmodified ethylene polymer.

The reaction temperature in the graft reaction using the radical initiator or the graft reaction performed without using the radical initiator is usually set to 60 to 350 ° C, preferably 150 to 300 ° C.

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, hydrotalcite and the like, or a mixture thereof. Particular preference is given to mixtures containing magnesium or mixtures containing aluminum hydroxide alone and aluminum hydroxide.

Triazine system  Compound (E)

The triazine ring-containing compound (E) used in the present invention may be any known compound as a flame retardant in general, and examples thereof include melamine, ammeline, melam, benzoguanamine, acetoguanamine, and phthalodigua. Namin, melamine cyanurate, melamine pyrophosphate, butylenediguanamine, norbornenediguanamine, methylenedimelamine, ethylenedimelamine, trimethylenedimelamine, tetramethylenedimelamine, hexamethylenedimelamine, 1,3-hexylene Dimelamine etc. can be illustrated. Of these, melamine cyanurate is suitably used. The compounding quantity of a triazine ring containing compound is 0.1-50 weight part with respect to 100 weight part of total amounts of said ethylene-alpha-olefin copolymer (A), and the copolymer (B) of ethylene and a vinyl ester, Preferably it is 5- 40 parts by weight. When the compounding amount is less than 1 part by weight, generation of combustion inert gas (nitrogen gas) from this compound is meaningless, and does not exhibit a synergistic effect with other flame retardants. On the other hand, even if it exceeds 50 weight part, the effect of a flame retardance does not rise so much, but it may be adversely produced in the moldability, the mechanical characteristics of the molded article obtained, etc., and is not preferable.

Powder silicone

Examples of the powdered silicone (also called silicon powder) of the present invention include organic organopolysiloxane powders such as dimethylpolysiloxane powder. Moreover, as powder silicon of this invention, the molecular weight (Mn) measured by GPC is 100000-10 million, Preferably it is 500000-5000000.

Other additives

In addition to the above, additives, such as antioxidant, a ultraviolet absorber, a weather stabilizer, a heat stabilizer, an antistatic agent, a flame retardant, a pigment, a dye, and a lubricating agent, can be mix | blended with the polymer composition by this invention as needed. The polymer composition according to the present invention more preferably contains a boric acid compound, preferably zinc borate, as flame retardant preparation.

Polymer composition

The polymer composition according to the present invention,

51 to 95 parts by weight of an ethylene-α-olefin copolymer (A),

5-49 parts by weight of copolymer (B) of ethylene and vinyl ester,

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

0.1-50 parts by weight of graft-modified ethylene polymer (C),

50 to 250 parts by weight of the metal hydroxide (D),

0.1-50 parts by weight of triazine-based compound (E),

Powder silicon (F) 0.1 to 40 parts by weight, characterized in that the weight ratio ((E) / (F)) of (E) and (F) is 1.2 or more.

More preferably, 51-85 weight part of ethylene / alpha-olefin copolymers (A),

15 to 49 parts by weight of copolymer (B) of ethylene and vinyl ester,

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

0.1-40 parts by weight of graft-modified ethylene polymer (C),

50 to 250 parts by weight of the metal hydroxide (D),

1 to 40 parts by weight of triazine-based compound (E),

It contains 0.1-26 weight part of powder silicon (F), and the weight ratio ((E) / (F)) of (E) and (F) is 1.5 or more.

More preferably, 55 to 85 parts by weight of the ethylene-α-olefin copolymer (A),

15 to 45 parts by weight of copolymer (B) of ethylene and vinyl ester,

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

0.1-30 weight part of graft modified ethylene polymers (C),

50 to 250 parts by weight of the metal hydroxide (D),

5 to 40 parts by weight of triazine-based compound (E),

It contains 0.1-26 weight part of powder silicon (F), and the weight ratio ((E) / (F)) of (E) and (F) is 1.5 or more.

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

25 to 45 parts by weight of copolymer (B) of ethylene and vinyl ester,

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

0.1-30 weight part of graft modified ethylene polymers (C),

50 to 250 parts by weight of the metal hydroxide (D),

5 to 40 parts by weight of triazine-based compound (E),

It contains 0.1-26 weight part of powder silicon (F), and the weight ratio ((E) / (F)) of (E) and (F) is 2.0 or more.

In addition, 0.1-30 weight of boric acid compounds are 100 weight part of total amounts of (A) (B) of the ethylene-alpha-olefin copolymer (A) and the copolymer (B) of ethylene and a vinyl ester as flame retardant manufacture. It is more preferable if it contains 0.1-20 weight part preferably.

The polymer composition by this invention is manufactured by melt-mixing said (A) (B) (C) (D) (E) and (F) component and the additive mix | blended as needed by various conventionally well-known methods. do.

For example, the polymer composition according to the present invention may be charged at the same time or sequentially, for example, by a Henschel mixer, a V-type blender, a tumbler mixer, a ribbon blender, or the like, followed by a single screw extruder, a multi-screw extruder, It is obtained by melt kneading with a kneader, a Banbury mixer or the like.

Among these, when the apparatus excellent in kneading performance, such as a multi-screw extruder, a kneader, and a Banbury mixer, is used, the high quality polymer composition in which each component disperse | distributed more uniformly is obtained.

Further, in these optional steps, the above additives such as antioxidants and the like may be added as necessary.

Containing a flame-retardant ethylene-based resin composition Molded body

The molded article according to the present invention, using the flame-retardant ethylene-based resin composition according to the present invention, conventionally known melt molding method, such as extrusion molding, rotational molding, calender molding, injection molding, compression molding, transfer molding, powder molding, It can shape | mold in various shapes by methods, such as blow molding and vacuum molding.

The flame-retardant ethylene-based resin composition according to the present invention can be suitably used for application of electric wire coating such as electric wire sheath and electric wire insulator. Moreover, the molded object by this invention is a coating layer, such as an electric wire sheath and an insulator of an electric wire, and this coating layer, such as an electric wire sheath and an electric insulator of an electric wire, is made around a wire by a conventionally well-known method, for example, extrusion molding. Is formed.

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples at all.

In addition, the physical property of the ethylene-alpha-olefin copolymer was evaluated as follows.

(1) density

The strand after MFR measurement at 190 degreeC and a 2.16 kg load was heat-processed at 120 degreeC for 1 hour, and after slow cooling to room temperature over 1 hour, it measured by the density gradient piping method.

(2) α-olefin content, Tαβ / Tαα, B value

^It was determined by ¹³ C-NMR spectrum.

(3) Mw / Mn

It measured at 140 degreeC with the ortho-dichlorobenzene solvent using GPC (gel permeation chromatography).

(4) MFR ₁₀ / MFR ₂

In accordance with ASTM D-1238, by measuring the MFR MFR ₂ of from ₁₀ and a load of 2.16kg at 10kg load at 190 ℃ it was calculated ratio. When this ratio is large, it shows that the fluidity | liquidity at the time of melting of a polymer is excellent, ie, workability is high.

The ethylene-α-olefin copolymer, copolymer of ethylene and vinyl ester, graft-modified ethylene polymer, metal hydroxide, triazine compound, powder silicone and silicone resin used in Examples and the like are as follows.

Ethylene-α-olefin copolymer (A):

Ethylene 1-butene copolymer A-1 manufactured by Production Example 1 below.

<Manufacture example 1>

(Production of ethylene-1-butene copolymer A-1)

18.4 mg of triphenylcarbenium (tetrakispentafluorophenyl) borate was taken and 5 ml of toluene was added to dissolve to prepare a toluene solution having a concentration of 0.004 mM / ml. 1.8 mg of [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium dichloride was added and 5 ml of toluene was added to dissolve to prepare a toluene solution having a concentration of 0.001 mM / m1. At the start of the polymerization, 0.38 ml of a toluene solution of triphenylcarbenium (tetrakispentafluorophenyl) borate and [dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane] titanium dichloride 0.38 ml of toluene solution was taken, and 4.24 ml of dilution toluene was added, and triphenylcarbenium (tetrakispentafluorophenyl) borate was 0.002 mM / L in terms of B, [dimethyl (t-butylamide) (tetra 5 ml of a toluene solution in which methyl-η5-cyclopentadienyl) silane] titanium dichloride was 0.0005 mM / L in terms of Ti was prepared.

750 ml of heptane was inserted at 23 degreeC into the autoclave made from SUS with the stirring blade of 1.5 liter of volumes which carried out the nitrogen substitution sufficiently. In the autoclave, 10 g of 1-butene and 100 ml of hydrogen were inserted while rotating the stirring blade and cooling with ice. Next, the autoclave was heated to 100 degreeC, and also pressurized with ethylene so that the total pressure might be 6KG. When the internal pressure of the autoclave became 6KG, 1.0 ml of 1.0 mM / ml hexane solution of triisobutylaluminum (TIBA) was pressurized with nitrogen. Subsequently, 5 ml of the catalyst solution prepared as described above was press-fitted into the autoclave with nitrogen to initiate polymerization. Then, the autoclave was temperature-controlled so that it might become internal temperature 100 degreeC for 5 minutes, and ethylene was directly supplied so that a pressure might be 6KG. 5 minutes after the start of the polymerization, 5 ml of methanol was inserted into the autoclave with a pump to terminate the polymerization, and the autoclave was depressurized to atmospheric pressure. 3 liters of methanol was injected into the reaction solution with stirring. The polymer containing the obtained solvent was dried at 130 degreeC, 13 hours, and 600 torr, and 10 g of ethylene butene copolymers A-1 were obtained. Table 1 shows the properties of the obtained ethylene-1-butene copolymer.

A-1 Polymer Properties Density (kg / m ³ ) MFR-190 ° C (g / 10min) Mw / Mn I ₁₀ / I ₂ B Value T _αβ / T _αα 885 0.5 2.1 10.0 1.05 0.3

Copolymer of ethylene and vinyl ester (B):

Ethylene-vinyl acetate copolymer brand name EVAFLEX EV360 (made by Mitsui Dupont Poly Chemical Co., Ltd.) (it abbreviates as EVA hereafter).

Graft modified ethylene polymer (C):

It is maleic anhydride graft modified ethylene 1-butene copolymer adjusted by the following manufacture example 2.

[Production Example 2]

(Production of Maleic Anhydride Graft Modified Ethylene-butene Copolymer)

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

Next, the blend obtained as described above was introduced from a hopper of a single screw extruder with a screw diameter of 40 mm and L / D = 26, extruded into a strand shape at a resin temperature of 260 ° C and an extrusion amount of 6 kg / hour, followed by water cooling. And pelletizing to obtain maleic anhydride graft modified ethylene 1-butene copolymer C-1.

After extraction of the unreacted maleic anhydride with acetone from the obtained graft-modified ethylene 1-butene copolymer C-1, the amount of maleic anhydride in the graft-modified ethylene 1-butene copolymer was measured. The amount was 0.43 wt%.

Metal hydroxides (D):

Magnesium hydroxide brand name KISUMA 5B (product of Kyogawa Chemical Co., Ltd.)

Triazine Compound (E):

Melamine cyanurate brand name MC-440 (product made by Nissan Chemical Industries, Ltd.)

Powder Silicone (F):

Polyorganosiloxane brand name DC4-7081 (product made in Toray Dow Corning)

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

In addition, preparation of the insulated wire sample and its evaluation were implemented with the following method.

(Production of insulated wire sample)

A die temperature: 190 ° C, screw rotation: 30 rpm, extrusion amount: 1.6 to 1, using a polymer composition having the composition shown in Table 2 provided with a wire coating die in a melt extruder (manufactured by Toyo Seiki Co., Ltd., product name LaboPlus Mill). Insulated wire with a finished diameter of 3.0 mm, with a 0.8 mm-thick polymer composition covering the periphery of a stranded conductor with a diameter of 0.45 mm and a strand of 7 strands (approximately 1.35 mm) at 1.8 kg / h. A sample was obtained.

(5) Break strength and elongation at break

In accordance with JIS K6301, a tensile test was performed at a span interval of 20 mm and a tensile speed of 200 mm / min, and the breaking strength and breaking elongation were measured.

(6) torsional rigidity

Torsional stiffness of the temperature of 23 degreeC was measured based on JISK6745 using the Clash-Berg softness tester by Toyo Seki Co., Ltd.

(7) Flame retardancy (combustion test)

Based on the vertical combustion test established by UL specification VW-1, it carried out using the insulated wire sample produced above.

Table 2 shows the results of the above evaluation.

Example Comparative Example-1 Comparative Example-2 Comparative Example-3 Comparative Example-4   Furtherance A-1 60 60 60 60 60 EV 360 40 40 40 40 40 B-1 3 3 3 3 3 Kisuma 5B 180 180 180 180 180 MC-440 20 20 40 DC4-7081 10 10 30 Breaking strength MPa 11 12 8 12 9 Breakpoint Shinto % 600 600 500 620 520 Torsional rigidity MPa 30 27 34 25 31 Combustion test VW-1 pass fail fail fail fail

Since the resin composition of this invention has favorable flexibility and flexibility, and is excellent in a flame retardant effect, it can be used suitably for the use of wire coating, such as an electric wire sheath and an insulator of an electric wire, for example.

Claims (2)

51 to 95 parts by weight of an ethylene-α-olefin copolymer (A), 5-49 parts by weight of copolymer (B) of ethylene and vinyl ester, About 100 parts by weight of the total amount of (A) (B), 0.1-50 parts by weight of graft-modified ethylene polymer (C), 50 to 250 parts by weight of the metal hydroxide (D), 0.1-50 parts by weight of triazine-based compound (E), A flame retardant ethylene-based resin composition comprising 0.1 to 40 parts by weight of powdered silicon (F), wherein the weight ratio ((E) / (F)) of (E) and (F) is 1.2 or more. An electric wire and a cable which coat | cover the flame-retardant ethylene-type resin composition of Claim 1.