JP2011057860A - Flame retardant resin composition and electric wire and cable using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant resin composition which includes a halogenated polymer and has characteristics excellent in both flame retardancy and processability at terminals, and to provide an electric wire and cable using the same. <P>SOLUTION: The flame retardant resin composition includes a halogenated polymer alone or a mixture containing other polyolefin-based resin. The composition includes, to 100 pts.mass of the polyolefin-based resin in which the amount of halogen is at least 10 mass% of the whole amount of the polymer, 3-20 pts.mass of an inorganic substance surface treated with a silane coupling agent and having an average particle diameter of at most 100 nm, 20-60 pts.mass of an antimony compound, and 20-60 pts.mass of a halogenated flame retardant. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a flame retardant resin composition having excellent flame retardancy and excellent terminal processability as an electric wire / cable, and an electric wire / cable using the same.

  Polyolefin resins such as polyethylene and ethylene copolymers have excellent electrical insulation properties and are therefore used as insulators for electric wires and cables. However, since the polyolefin resin itself is very flammable, it needs to be flame retardant. Flame retardant methods include adding halogen-based flame retardants, antimony compounds, etc., but especially in products that require high flame retardant properties such as vertical combustion tests, add a large amount of flame retardant. It is necessary to add. If the amount of flame retardant added is simply increased, problems such as a decrease in physical properties such as tensile strength and elongation, a poor appearance that makes the wire surface rough, and blooming of the flame retardant occur.

JP 2004-149635 A JP 2000-313775 A JP-A-5-255532

  Along with this increase in the amount of addition, which is a conventional technique, there are problems such as a decrease in physical properties such as tensile strength and elongation, a poor appearance that makes the surface of the wire rough, and the occurrence of blooming of flame retardants.

  Therefore, it has been generally studied to impart flame retardancy to the polymer itself and to reduce the amount of flame retardant added, and as shown in Patent Documents 1 to 3, it is proposed to use a halogenated polymer.

  In the study by the present inventors, it is most effective to use a halogenated polymer in order to impart flame retardance at a level that passes the vertical combustion test, and is particularly excellent when the halogen content in the entire polymer is 10 mass% or more. It was found to have flame retardancy. Taking chlorinated polyethylene, which is a kind of halogenated polymer, as an example, a polymer with a regular structure of chlorine, such as polyvinyl chloride, has an irregular structure in which some hydrogen in the polyethylene is replaced by chlorine. Compared with, heat resistance is also excellent.

  However, since halogenated polymers have lower crystallinity and softness compared to polyethylene, etc., when peeling off insulators such as electric wires and cables, some of them remain on the conductor as they are not removed cleanly. It has been found that problems that are likely to occur occur.

  When the uncut portion is generated, an insulator is sandwiched between the conductor and the connector when the connector is connected thereafter, causing a conduction failure.

  Accordingly, an object of the present invention is to solve the above-mentioned problems, use a halogenated polymer, and to achieve both excellent flame retardancy and terminal processability, and a flame retardant resin composition and an electric wire / cable using the same Is to provide.

  In order to achieve the above-mentioned object, the invention of claim 1 is based on 100 parts by mass of a polyolefin resin, which is a halogenated polymer alone or in a mixture with other polyolefin resin, and the halogen content in the whole polymer is 10 mass% or more. In contrast, 3 to 20 parts by mass of an inorganic substance having an average particle size of 100 nm or less, which was surface-treated with a silane coupling agent, 20 to 60 parts by mass of an antimony compound, and 20 to 60 parts by mass of a halogen-based flame retardant were contained. This is a flame retardant resin composition.

  Invention of Claim 2 is a flame-retardant resin composition of Claim 1 which used ethylene-vinyl acetate copolymer (EVA) individually or in combination with other polyolefin resin as other polyolefin resin.

  Invention of Claim 3 is a flame-retardant resin composition of Claim 1 or 2 whose oxygen index is 35 or more.

  The invention of claim 4 is an electric wire / cable characterized in that the flame retardant resin composition according to any one of claims 1 to 3 is used for a conductor insulator or a sheath of a cable.

  According to the present invention, an excellent effect of providing a flame retardant resin composition exhibiting excellent terminal processability and an electric wire / cable using the same while maintaining high flame retardancy is exhibited.

It is sectional drawing of the electric wire and cable to which this invention is applied. It is sectional drawing of the electric wire to which this invention is applied.

  A preferred embodiment of the present invention will be described below in detail with reference to the accompanying drawings.

  First, with reference to FIG. 1 and FIG. 2, the flame retardant resin composition of the present invention and an electric wire / cable using the same as an insulator or sheath of the electric wire / cable will be described.

  FIG. 1 shows an electric wire / cable 20 in which three conductors of an electric wire 10 coated with an insulator 2 on a copper conductor 1 are twisted together with a paper interposition 4, a press-wound tape 5 is applied, and an outermost layer is extruded and covered with a sheath 3. It is a figure and the insulator 2 and the sheath 3 are produced with the flame-retardant resin composition of this invention.

  FIG. 2 shows an electric wire 10 in which an insulator 2 is coated on a copper conductor 1, and the insulator 2 is made of the flame retardant resin composition of the present invention.

  The flame-retardant resin composition of the present invention is based on 100 parts by mass of a polyolefin resin that is a halogenated polymer alone or a mixture with other polyolefin resin, and the halogen content in the entire polymer is 10 mass% or more. 3 to 20 parts by mass of an inorganic substance surface-treated with a silane coupling agent having an average particle size of 100 nm or less, 20 to 60 parts by mass of antimony trioxide, and 20 to 60 parts by mass of a flame retardant, respectively. It is characterized by. The flame retardant resin composition of the present invention is preferably a flame retardant resin composition obtained by adding an ethylene-vinyl acetate copolymer (EVA) alone or in combination with other polyolefin-based resin to a part of a polymer. Furthermore, it is preferable that the flame retardant resin composition has an oxygen index of 35 or more.

  Examples of the halogenated polymer used in the present invention include chlorinated polyethylene, chlorosulfonated polyethylene, chlorinated polypropylene, and the like, and these can be used alone or in combination of two or more.

  Examples of polyolefin resins include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), linear very low density polyethylene (VLDPE), high density polyethylene (HDPE), and ethylene-ethyl acrylate copolymer ( EEA), ethylene-vinyl acetate copolymer (EVA), ethylene-glycidyl methacrylate copolymer, ethylene-butene-1 copolymer, ethylene-butene-hexene terpolymer, ethylene-propylene-diene ternary copolymer Polymer (EPDM), ethylene-octene copolymer (EOR), ethylene copolymerized polypropylene, ethylene-propylene copolymer (EPR), poly-4-methyl-pentene-1, maleic acid grafted low density polyethylene, hydrogenated Styrene-butadiene copolymer (H-SBR), male Acid graft linear low density polyethylene, copolymer of ethylene and α-olefin having 4 to 20 carbon atoms, ethylene-styrene copolymer, maleic acid grafted ethylene-methyl acrylate copolymer, maleic acid grafted ethylene-acetic acid Vinyl copolymers, ethylene-maleic anhydride copolymers, ethylene-ethyl acrylate-maleic anhydride terpolymers, ethylene-propylene-butene-1 terpolymers based on butene-1 and the like. These may be used alone or in combination of two or more.

  Examples of the inorganic material treated with the silane coupling agent include silica, clay, talc, titanium oxide, zinc oxide, and the like. Although the average particle size is not particularly limited as long as it is 100 nm or less, from the viewpoint that silane treatment can be most easily performed. More preferably, it is silica.

  The reason why the average particle size is 100 nm or less is to improve the adhesion with the polymer and improve the terminal processability with a small addition amount. When the average particle size is larger than 100 nm, the same effect can be obtained. The terminal processability is poor.

  The addition amount is 3 to 20 parts by mass, and if it is less than 3 parts by mass, sufficient terminal processability cannot be obtained, and if it is more than 20 parts by mass, the elongation characteristics are remarkably lowered.

  The surface treatment amount of the silane coupling agent is preferably 0.3 mass% to 2 mass%.

  As the silane coupling agent, there are no particular limitations on the type and amount of addition as long as it is generally used as a silane coupling agent. Examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, aminopropyltrimethoxysilane, and aminopropyltriethoxysilane.

  Examples of the antimony compound include antimony trioxide, antimony tetroxide, antimony pentoxide, potassium antimonate, sodium antimonate, and the like, and more preferably antimony trioxide.

  When the addition amount is less than 20 parts by mass, sufficient flame retardancy cannot be obtained, and when it is more than 60 parts by mass, the elongation characteristics are remarkably deteriorated.

  Examples of the halogen flame retardant include ethylene bispentabromobenzene, tetrabromobisphenol A-bis (2,3-dibromopropyl ether), decabromodiphenyl oxide, octabromodiphenyl oxide, pentabromodiphenyl oxide, tetrabromobisphenol A, tetra Bromobisphenol A-bis (allyl ether), tetrabromobisphenol A-bis (2-hydroxyether), hexabromocyclodecane, bis (tribromophenoxy) ethane, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A carbonate oligomer, Ethylenebistetrabromophthalimide, poly-dibromophenylene oxide, 2,4,6-tribromophenol, tetrabromobisphenol Nord A-bis (acrylate), tetrabromophthalic amidolide, tetrabromophthalate diol, 2,3-dibromopropanol, tribromostyrene, tetrabromophenylmaleimide, poly (pentabromobenzyl) acrylate, tris (tribromoneo Pentyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromophenyl) phosphate, 1,2,3,4,7,8,9,10,13,13,14,14-dodecachloro-1,4,4a 5,6,6a, 7,10,10a, 11,12,12a-dodecabidro-1,4,7,10-dimethanodibenzo (a, e) cyclooctene, chlorinated paraffin, perchlorocyclopentadecane, tetrachloroanhydrous Phthalic acid, chlorendic acid, dodecachloro Kurookutan and the like, more preferably an ethylene bis-pentabromodiphenyl.

  When the addition amount is less than 20 parts by mass, sufficient flame retardancy cannot be obtained, and when it is more than 60 parts by mass, the elongation characteristics are remarkably deteriorated.

  If necessary, additives such as an antioxidant, a metal deactivator, a lubricant, a softener, a plasticizer, an inorganic filler, a compatibilizer, a stabilizer, carbon black, and a colorant can be added.

  Furthermore, it may be crosslinked by an organic peroxide or by radiation such as an electron beam.

  Examples and comparative examples of the present invention are shown in Tables 1 and 2.

  The resin composition and the electric wire were produced as follows.

  Various components were blended at the blending ratios shown in Table 1 and Table 2, and after kneading at a start temperature of 40 ° C. and an end temperature of 190 ° C. by a pressure kneader, the kneaded product was formed into pellets. The insulator 2 was extruded at a thickness of 0.41 mm and a set temperature of 200 ° C. When cross-linking, the produced electric wire 10 was irradiated with an electron beam. The irradiation dose was 100 kGy.

  The evaluation of the electric wire was determined by the following method.

(1) Tensile test The produced electric wire was subjected to a tensile test in accordance with JISC3005. The elongation was less than 300% × (failed), 300-400% was ○ (passed), and more than that was double ○ (passed with tolerance). Tensile strength of less than 13 MPa was evaluated as x (failed), 13 to 15 MPa was evaluated as ◯ (accepted), and more than double was evaluated as acceptable (passed with tolerance).

(2) Flame retardance test The produced electric wire was subjected to a vertical combustion test (VW-1) based on ULsubject758. Judgment was made with a double combustion test with a combustion time of less than 30 seconds.

(3) Appearance test Observe the surface and cross-section of the produced electric wire with a 50x optical microscope, and indicate that the surface is rough, bloom is seen on the surface, and foam is present on the cross-section x (fail) And those having no abnormalities in the surface and cross section were evaluated as ◯ (passed).

(4) Terminal workability The terminal of the produced electric wire was peeled off with a wire stripper, and the uncut portion was evaluated as x (failed), and the uncut portion was evaluated as ○ (passed).

  As shown in Table 1, Examples 1 to 11 all show good characteristics.

  In Examples 1 to 3, the chlorine content in the polymer was changed to 12, 10, 14 mass%. If the chlorine content in the polymer was 10 mass% or more, the chlorine content in the polymer was changed. However, the flame retardancy is good, and the flame retardance is improved as the chlorine content increases.

  Moreover, even if the addition of the silane-treated inorganic substance is changed to 3 parts by mass (Example 4) and 20 parts by mass (Example 5), the average particle size is changed to 16 nm (Example 3) and 100 nm (Example 6). Even if it is in the range of 3 to 20 parts by mass and an average particle size of 100 nm or less, the terminal processability is good.

  As other polyolefin-based resins, Example 3 using EVA and Example 7 using EEA have good characteristics, and the use of EVA is superior in flame retardancy, and EVA addition is preferable.

  When antimony trioxide is used as the antimony compound and the addition amount is changed to 20 parts by mass (Example 8) and 60 parts by mass (Example 9), the flame retardancy is further improved by increasing the addition amount.

  When the addition amount is changed to 20 parts by mass (Example 10) and 60 parts by mass (Example 11) using ethylene pentabisdibromobenzene as the halogen flame retardant, the flame retardancy is further improved by increasing the addition amount. To do.

  On the other hand, as shown in Table 2, the amount of chlorine in the polymer is less than specified, 9 mass% of Comparative Example 1, the amount of antimony compound added is less than specified, 15 parts by weight of Comparative Example 5, and the halogenated flame retardant In Comparative Example 7 in which the addition amount was less than the standard of 15 mass%, the oxygen index was 35 or less, and the flame retardancy was insufficient.

  In Comparative Example 2 in which 2 parts by mass of the addition amount of the silane-treated inorganic material was less than the specified value and Comparative Example 4 in which the average particle size of the silane-treated inorganic material was 150 nm larger than the specified value, the terminal processability was unacceptable.

  Comparative Example 3 with 25 parts by mass of silane-treated inorganic added more than specified, Comparative Example 6 with 70 parts by mass of added antimony compound more than specified, 70 parts by mass of added halogenated flame retardant than specified In Comparative Example 8, the elongation characteristics were all 300% or less and were not acceptable. Moreover, the appearances of Comparative Examples 6 and 8 were also unacceptable.

1 Copper Conductor 2 Insulator 3 Sheath 10 Electric Wire 20 Electric Wire / Cable

Claims (4)

  The average particle which surface-treated with the silane coupling agent with respect to 100 mass parts of polyolefin resin which is halogenated polymer individually or in mixture with other polyolefin resin and the halogen amount which occupies for the whole polymer is 10 mass% or more. A flame-retardant resin composition comprising 3 to 20 parts by mass of an inorganic substance having a diameter of 100 nm or less, 20 to 60 parts by mass of an antimony compound, and 20 to 60 parts by mass of a halogen-based flame retardant.   The flame retardant resin composition according to claim 1, wherein ethylene-vinyl acetate copolymer (EVA) is used alone or in combination with other polyolefin resin as other polyolefin resin.   The flame retardant resin composition according to claim 1 or 2, wherein the oxygen index is 35 or more.   An electric wire / cable, wherein the flame retardant resin composition according to any one of claims 1 to 3 is used for a conductor insulator or a cable sheath.

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