CN101080456A - Flame-retardant resin composition and formed article using the same - Google Patents
Flame-retardant resin composition and formed article using the same Download PDFInfo
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- CN101080456A CN101080456A CNA2005800434349A CN200580043434A CN101080456A CN 101080456 A CN101080456 A CN 101080456A CN A2005800434349 A CNA2005800434349 A CN A2005800434349A CN 200580043434 A CN200580043434 A CN 200580043434A CN 101080456 A CN101080456 A CN 101080456A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
- C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0853—Ethene vinyl acetate copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The present invention relates to a flame-resistant resin composition, characterized in that it comprises 100 parts by mass of (A) a resin component and 100 to 300 parts by mass of (B) magnesium hydroxide, wherein the resin component comprises 22 to 85 mass % of at least one resin (a) selected from the group consisting of (a-1) a polyolefin modified with an unsaturated carboxylic acid, (a-2) an ethylene-vinyl acetate copolymer modified with an unsaturated carboxylic acid, (a-3) an ethylene-(meth)acrylic acid ester copolymer modified with an unsaturated carboxylic acid, (a-4) a styrenic copolymer modified with an unsaturated carboxylic acid, (a-5) an ethylene-(meth)acrylic acid copolymer and (a-6) an ethylene-(meth)acrylic acid ester-(meth)acrylic acid copolymer, 10 to 75 mass % of (b) polypropylene, 0 to 65 mass % of (c) an ethylene-a-olefin copolymer, 0 to 20 mass % of (d-1) an ethylene-vinyl acetate copolymer and/or (d-2) an ethylene-(meth)acrylic acid ester copolymer, 0 to 40 mass % of (e) a styrenic elastomer and 0 to 20 mass % of (f) a softener for a rubber.
Description
Technical field
Do not need special equipment such as cross-linking apparatus when the present invention relates to forming process, and the flame retardant resin composition of mechanical characteristics and wearability, oil-proofness, excellent heat resistance and the formed article that uses it, in addition, the formed article that relates to excellent in flame retardance, for example, sheet, pipe, wiring material, optical fiber cable (light Off ア イ バ コ one De) wait other formed articles.
Say in more detail, do not need special equipment such as cross-linking apparatus after the present invention relates to process, and thermotolerance, wearability, anti-traumatic, oil-proofness excellent flame resin combination, and the insulated line, cable, cord (Electricity mood コ one De) or the formed articles such as optical fibre core, optical fiber cable that use in the inside of the electrical/electronic instrument of thermotolerance, wearability, anti-traumatic, oil-proofness, pressure contact excellent in workability or the outside wiring.Particularly, relate to when waste treatments such as landfill, burning, can not dissolve and separate out heavy metal compound or produce a large amount of cigarettes, obnoxious flavour, and the utilization again after being fit to use is handled, and solves the flame retardant resin composition and the formed article thereof of environmental problem.
Background technology
The insulated line that uses in the inside and outside wiring of electrical/electronic instrument, cable, insulated wire or light heart yearn, optical fiber cable etc. require flame retardant resistance, thermotolerance, mechanical characteristics various characteristicses such as (for example, tensile properties, wearabilitys).
In addition, sheet material requires thermotolerance, anti-traumatic, in addition, for pipe, requires thermotolerance, anti-traumatic, wearability, oil-proofness, flame retardant resistance.
Now, in such use, mainly use the polyolefin compound that contains halogen flame resistant that contains bromine atoms or chlorine atom in polyvinyl chloride (PVC) compound (コ Application パ ウ Application De) or the molecule.
But the discarded above-mentioned material that contains halogen without suitable processing is when landfill, softening agent that contains in the coating material or heavy metal stabilizer can dissolve separates out, in addition, and when burning, can produce obnoxious flavour by the contained halogen compounds of coating material, in recent years, this problem is being discussed.
Therefore, studying employing and can not dissolve and separate out deleterious softening agent or the heavy metal that environment is brought influence, or the non-halogen material that produces halogen gas etc. carries out moulding and the formed article, wiring material, cable, sheet, the pipe that obtain.
The halogen-free flame-retardant material is to show flame retardant resistance by contain not halogen-containing fire retardant in resin, for example, can in wiring material, use the material of metal hydrates such as the aluminium hydroxide that in ethene copolymers such as ethene/butene-1 copolymer, ethylene/propene copolymer, ethylene/vinyl acetate multipolymer, ethylene/ethyl acrylate multipolymer, ethylene/propylene/diene hydrocarbon terpolymer, contains in a large number as fire retardant, magnesium hydroxide.
The standard of the desired flame retardant resistance of the wiring material of electrical/electronic instrument, thermotolerance, mechanical characteristics (for example, tensile properties, wearability) etc. is existing regulation in UL, JIS etc.Particularly, about flame retardant resistance, benchmark (its purposes) etc. as requested, its test method also changes.But, in fact, can have at least and require the corresponding flame retardant resistance of benchmark.For example, can enumerate respectively, qualified flame retardant resistance etc. in the hydraulic test of the testing vertical flammability (Vertical Flame Test) of regulation regulation (VW-1) or among the JISC 3005 (rubber/plastic insulated wire cord test method) or the inclining experiment in the UL1581 (relevant criterion (Reference Standard for Electrical Wires, Cables and Flexible) that is used for electric wire, cable and flexible electric wire)
Up to now, when the halogen-free flame-retardant material being given in VW-1 or inclining experiment qualified such high flame retardancy, must contain with respect to 100 parts by weight resin compositions be 150～200 weight parts as the metal hydrate of fire retardant (for example, open the 2001-135142 communique with reference to the spy), as its result, there are mechanical characteristics, the significantly reduced problems of wearability such as the tensile properties of coating material or wearability.
Particularly, during the heavy addition metal hydrate, wearability, anti-traumatic reduction are remarkable, in order to prevent these situations, have proposed for example to implement crosslinked method or have used the method for polypropylene as body material.But, in these methods, when improving flame retardant resistance, have problems such as wearability or intensity, the remarkable reduction of pressure contact performance.
In addition, during the heavy addition metal hydrate, oil-proofness significantly reduces, and can not use in the part of needs oil.
Summary of the invention
The objective of the invention is to, a kind of flame retardant resin composition is provided and uses its formed article, described flame retardant resin composition can address the above problem, flame retardant resistance, thermotolerance, mechanical characteristics, oil-proofness, wearability, pressure contact excellence, and, when landfill, burning etc. are discarded, can not dissolve and separate out heavy metal compound or produce a large amount of cigarettes, obnoxious flavour, can solve present environmental problem.In addition, the objective of the invention is to, provide and satisfy these characteristics, and can utilize again owing to the fusion again of formed article, even bending can albefaction yet, in addition, easy damaged not particularly has both the formed article such as resin combination, wiring material, optical fibre core, optical fiber cable, sheet, pipe of flame retardant resistance or wearability, oil-proofness, the wiring material of pressure contact excellence.
In order to solve above-mentioned problem, the invention provides:
(1) a kind of flame retardant resin composition wherein, with respect to (A) resinous principle of 100 mass parts, contains (B) magnesium hydroxide of 100 mass parts～300 mass parts, and described (A) resinous principle comprises:
The resin (a) of 22 quality %～85 quality %, this resin (a) be selected from (a-1) by unsaturated carboxylic acid-modified polyolefine, (a-2) by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer, (a-3) by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer, (a-4) by unsaturated carboxylic acid-modified styrene copolymer, (a-5) ethene-(methyl) acrylic copolymer and (a-6) at least a in ethene-(methyl) acrylate-(methyl) acrylic copolymer;
(b) polypropylene of 10 quality %～75 quality %;
(c) ethene-alpha-olefin copolymer of 0 quality %～65 quality %;
(d-1) ethylene-vinyl acetate copolymer of 0 quality %～20 quality % and/or (d-2) ethene-(methyl) acrylate copolymer;
(e) styrenic elastomerics of 0 quality %～40 quality %; And
(f) softener of rubber of 0 quality %～20 quality %,
(2) a kind of flame retardant resin composition wherein, with respect to (A) resinous principle of 100 mass parts, contains (B) magnesium hydroxide of 100 mass parts～300 mass parts, and described (A) resinous principle comprises:
The resin (a) of 25 quality %～85 quality %, described resin (a) be selected from (a-1) by unsaturated carboxylic acid-modified polyolefine, (a-2) by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer, (a-3) by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer, (a-4) by unsaturated carboxylic acid-modified styrene copolymer, (a-5) ethene-(methyl) acrylic copolymer and (a-6) at least a in ethene-(methyl) acrylate-(methyl) acrylic copolymer;
(b) polypropylene of 10 quality %～75 quality %;
(c) ethene-alpha-olefin copolymer of 0 quality %～65 quality %;
(d-1) ethylene-vinyl acetate copolymer of 0 quality %～20 quality % and/or (d-2) ethene-(methyl) acrylate copolymer;
(e) styrenic elastomerics of 0 quality %～40 quality %; And
(f) softener of rubber of 0 quality %～20 quality %,
(3) a kind of flame retardant resin composition, wherein, with respect to (A) resinous principle of 100 mass parts, it is above and be lower than (B) magnesium hydroxides of 100 mass parts to contain 75 mass parts, and described (A) resinous principle comprises:
The resin (a) of 35 quality %～100 quality %, described resin (a) be selected from (a-1) by unsaturated carboxylic acid-modified polyolefine, (a-2) by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer, (a-3) by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer, (a-4) by unsaturated carboxylic acid-modified styrene copolymer, (a-5) ethene-(methyl) acrylic copolymer and (a-6) at least a in ethene-(methyl) acrylate-(methyl) acrylic copolymer;
(b) polypropylene of 0 quality %～60 quality %;
(c) ethene-alpha-olefin copolymer of 0 quality %～65 quality %;
(d-1) ethylene-vinyl acetate copolymer of 0 quality %～20 quality % and/or (d-2) ethene-(methyl) acrylate copolymer;
(e) styrenic elastomerics of 0 quality %～40 quality %; And
(f) softener of rubber of 0 quality %～20 quality %,
(4) according to any described flame retardant resin composition in (1)～(3), wherein, above-mentioned (B) magnesium hydroxide is (B-1) the untreated magnesium hydroxide and/or (B-2) magnesium hydroxide of silane treatment,
(5) according to any described flame retardant resin composition in (1)～(4), wherein, in above-mentioned (A) resinous principle, content (a) is 45 quality %～80 quality %,
(6) according to any described flame retardant resin composition in (1)～(5), wherein, in above-mentioned (A) resinous principle, the content of unsaturated carboxylic acid composition (a) is 1.3 quality %～6.0 quality %,
(7) according to any described flame retardant resin composition in (1)～(6), wherein, in above-mentioned (A) resinous principle, the content of unsaturated carboxylic acid composition (a) is 2.0 quality %～5.5 quality %,
(8) according to any described flame retardant resin composition in (1)～(7), wherein,, contain at least by (methyl) acrylic acid modified polypropylene as (a),
(9) according to any described flame retardant resin composition in (1)～(8), wherein,, contain at least by (methyl) acrylic acid modified polypropylene with by unsaturated carboxylic acid-modified styrene copolymer as (a),
(10) a kind of formed article, it has in (1)～(9) any described flame retardant resin composition as coating layer in conductor or optical fiber wire rod (plain Line) and/or the outside of optical fibre core, and
(11) a kind of formed article, it obtains by any described flame retardant resin composition in moulding (1)～(9).
The flame retardant resistance of flame retardant resin composition of the present invention, thermotolerance, mechanical characteristics, oil-proofness, wearability, pressure contact excellence, and when landfill, burning etc. are discarded, can not dissolve and separate out heavy metal compound or produce a large amount of cigarettes, obnoxious flavour, can solve present environmental problem.Above-mentioned effect is at the magnesium hydroxide that uses untreated magnesium hydroxide and/or silane treatment during as magnesium hydroxide, and is effective especially.
In addition, when the content of (a) in the resinous principle was 45～80 quality %, above-mentioned effect was excellent especially.
In addition, when the content of the unsaturated carboxylic acid in the resinous principle was 1.3 quality %～6.0 quality %, thermotolerance, mechanical characteristics, oil-proofness, wearability, pressure contact were excellent especially, and be when 2.0 quality %～5.5 quality %, remarkable especially.
In addition, when containing (methyl) acrylic acid modified polypropylene at least as (a), on mechanical characteristics, thermotolerance, oil-proofness, wearability, pressure contact, effect is obvious, when containing (methyl) acrylic acid modified polypropylene and unsaturated carboxylic acid-modified styrene copolymer, remarkable especially as (a).
Formed article of the present invention satisfies above-mentioned all characteristics, and because the fusion again of formed article and can utilizing again, even bending can albefaction yet, in addition, easy damaged does not particularly have both flame retardant resistance, wearability, oil-proofness.
Therefore, flame retardant resin composition of the present invention is the flame retardant resin composition that is suitable for the formed articles such as wiring material of wiring material, optical fibre core, optical fiber cable, sheet, pipe or pressure contact excellence.
Above-mentioned and other purposes of the present invention, feature and advantage can be clearer and more definite from following record.
Embodiment
Below explain the present invention.
At first, explain each composition of flame retardant resin composition of the present invention.
(a-1) by unsaturated carboxylic acid-modified polyolefine
The present invention is said to be by adopting unsaturated carboxylic acid with polyolefin modified by unsaturated carboxylic acid-modified polyolefine, the resin of unsaturated carboxylic acid graft on polyolefine.
As the unsaturated carboxylic acid among the present invention, can enumerate unsaturated carboxylic acid and acid anhydrides thereof, for example, can enumerate vinylformic acid, methacrylic acid, toxilic acid, methylene-succinic acid, fumaric acid, maleic anhydride, itaconic anhydride, fumaric acid anhydride etc.
As the polyolefine among the present invention, can enumerate the multipolymer of polyethylene (straight chain shaped polyethylene, ultra-low density polyethylene, high density polyethylene(HDPE)), polypropylene (multipolymer of homo-polypropylene, propylene-ethylene random copolymers, propylene-ethylene block copolymer or propylene and other a small amount of alpha-olefins (for example, 1-butylene, 1-hexene, 4-methyl-1-pentene etc.)), ethene and alpha-olefin etc.
Polyolefinic modification can by for example in the presence of organo-peroxide with the heating of polyolefine and unsaturated carboxylic acid, mixing carrying out.The modification amount that is caused by unsaturated carboxylic acid is generally 0.5～15 quality %.
As passing through unsaturated carboxylic acid-modified polyolefine, particularly, can enumerate, for example, (trade(brand)names such as Port リ ボ Application De P-1002, P-1009, Network ロ Application プ ト Application (strain) manufacturing), ア De テ Star Network ス L-6100M, L-6101 etc. (trade(brand)name, Japanese polyethylene (strain) is made), ア De マ one XE070, NE070 etc. (trade(brand)name, Mitsui Chemicals (strain) is made) etc.
(a-2) by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer
Said among the present invention by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer, be meant by adopting unsaturated carboxylic acid the resin of unsaturated carboxylic acid graft on ethylene-vinyl acetate copolymer with the ethylene-vinyl acetate copolymer modification.
As unsaturated carboxylic acid, can use with (a-1) in the same material that uses.
Said ethylene-vinyl acetate copolymer is to make ethene and vinyl acetate copolymerized and material that obtain.
The modification of ethylene-vinyl acetate copolymer is with (a-1) same, for example, in the presence of organo-peroxide ethylene-vinyl acetate copolymer and unsaturated carboxylic acid heated, mixing carrying out.The modification amount that is caused by unsaturated carboxylic acid is generally 0.5～15 quality %.
As by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer, can enumerate, for example, ア De マ one VF600, VF500 (be trade(brand)name, Mitsui Chemicals (strain) is made).
(a-3) by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer
In the present invention, saidly be meant by adopting unsaturated carboxylic acid the resin of unsaturated carboxylic acid graft on ethene-(methyl) acrylate copolymer by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer with ethene-(methyl) acrylate copolymer modification.
As unsaturated carboxylic acid, can use with (a-1) in the same material that uses.
Said ethene-(methyl) acrylate copolymer can be enumerated, for example, and ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl methacrylate ethyl ester multipolymer etc.
The modification of ethene-(methyl) acrylate copolymer is with (a-1) same, for example, in the presence of organo-peroxide ethene-(methyl) acrylate copolymer and unsaturated carboxylic acid heated, mixing carrying out.The modification amount that is caused by unsaturated carboxylic acid is generally 0.5～15 quality %.
As by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer, can enumerate, for example, モ デ イ パ one A-5200, A-8200 (be trade(brand)name, Japanese grease (strain) is made).
(a-4) by unsaturated carboxylic acid-modified styrene copolymer
In the present invention, said by unsaturated carboxylic acid-modified styrene copolymer, be meant by adopting unsaturated carboxylic acid the resin of unsaturated carboxylic acid graft on styrene copolymer with the styrene copolymer modification.
As unsaturated carboxylic acid, can use with (a-1) in the same material that uses.
Said styrene copolymer is meant based on the block of conjugated diene compound and aromatic ethenyl compound and the multipolymer and the hydrogenation thing thereof of random structure.As aromatic ethenyl compound, can enumerate, for example, vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, 1,1-diphenyl benzene ethene, N, the N-diethyl is to aminoethyl vinylbenzene, Vinyl toluene, to t-butyl styrene etc.In addition,, can enumerate as conjugated diene compound, for example, divinyl, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene etc.
The modification of styrene copolymer is with (a-1) same, for example, in the presence of organo-peroxide styrene copolymer and unsaturated carboxylic acid heated, mixing carrying out.The modification amount that is caused by unsaturated carboxylic acid is generally 0.5～15 quality %.
As by unsaturated carboxylic acid-modified styrene copolymer, can enumerate, for example, Network レ イ ト Application 1901FG (JSR Network レ イ ト Application (strain) manufacturing).
(a-5) ethene-(methyl) acrylic copolymer, (a-6) ethene-(methyl) acrylate-(methyl) acrylic copolymer
In the present invention, ethene-(methyl) acrylic copolymer, ethene-(methyl) acrylate-(methyl) acrylic copolymer can be used with the resin of above-mentioned (a-1)～(a-4), or be replaced the resin of (a-1)～(a-4).
As ethene-(methyl) acrylic copolymer, can enumerate, for example, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer etc., as ethene-(methyl) acrylate-(methyl) acrylic copolymer, can enumerate, for example, ethylene-methyl acrylate-acrylic copolymer, ethylene-propylene acetoacetic ester-acrylic copolymer, ethylene-methyl methacrylate methyl esters-acrylic copolymer, ethylene-methyl methacrylate ethyl ester-acrylic copolymer, ethylene-methyl acrylate-Sipacril 2739OF, ethylene-propylene acetoacetic ester-Sipacril 2739OF, ethylene-methyl methacrylate methyl esters-Sipacril 2739OF, ethylene-methyl methacrylate ethyl ester-Sipacril 2739OF etc.
Particularly, can enumerate, for example, ニ ユ Network レ Le, ベ イ マ Star Network (be trade(brand)name, Mitsui デ ユ Port Application Port リ ケ ミ カ Le (strain) is made) etc.
In the present invention, as (a) composition, use at least a resin that is selected from (a-1)～(a-6).
Above-mentioned (a) composition is brought into play high mechanical characteristics by carry out ionic bond with magnesium hydroxide described later on nanometer～micron level.Think that the hard that magnesium hydroxide had originally, intensity, enhancing and resinous principle are integrated owing to magnesium hydroxide and the powerful combination of resinous principle, the flame retardant resin composition that obtains has high mechanical characteristics.Consequently, think that the amount of the magnesium hydroxide that flame retardant resin composition contains is many more, just can improve wearability significantly more.In addition, because the mortise of resinous principle and magnesium hydroxide even with the bending of formed article surface, also albinism can not take place, can obtain the very high formed article of intensity.In addition, by magnesium hydroxide, the resin in the resinous principle has the combination of very firm microcosmic, therefore, can swelling in oil component, can have high oil-proofness.
Particularly, by using by (methyl) acrylic acid modified polypropylene, more preferred the use by (methyl) acrylic acid modified polypropylene with by 2 kinds of compositions conducts of unsaturated carboxylic acid-modified styrene copolymer (a), oil-proofness, wearability are become significantly to improve, even heavy addition magnesium hydroxide, flowability is also very good, can obtain excellent formability.In addition, in electric wire, can have excellent especially pressure contact.
As by (methyl) acrylic acid modified polypropylene, for example, can enumerate the acrylic acid modified polypropylene of in above-mentioned (a-1), enumerating such as Port リ ボ Application De P-1002.
In addition, as by unsaturated carboxylic acid-modified styrene copolymer, for example, can enumerate the toxilic acid modified phenylethylene analog copolymers of enumerating in above-mentioned (a-4) such as Network レ イ ト Application 1901FG.
In addition,, confirmed when burning, to promote thermo-negative reaction, in addition, prevented that by forming shell burning from spreading, and demonstrates high flame retardant because resin and magnesium hydroxide have powerful combination in the resinous principle.Use is by (methyl) acrylic acid modified polyolefine and/or ethene-(methyl) acrylic copolymer during as (a) composition, big with these flame retardant resistances, intensity, effect that wearability is corresponding, therefore, the preferred use by (methyl) acrylic acid modified polyolefine and/or ethene-(methyl) acrylic copolymer at least a portion as (a) composition.
In addition, because (a) composition has ionic the combination with magnesium hydroxide, therefore, even polypropylene is a small amount of, also can satisfy the heating deformation characteristic, thus, it is good that flame retardant resistance, process at ends, insulation characterisitic, thermotolerance become.Think this be because, magnesium hydroxide becomes catalyzer, (a) part of composition takes place crosslinked.
In order to make this flame retardant resistance, process at ends, insulation characterisitic better,, preferably use by (methyl) acrylic acid modified polyolefine, particularly by (methyl) acrylic acid modified polypropylene as (a) composition.
Preferred implementation of the present invention is following flame retardant resin composition, and said composition contains (B) magnesium hydroxide of 100 mass parts～300 mass parts with respect to (A) described later resinous principle of 100 mass parts.In this embodiment, (A) in the resinous principle, (a) content of composition is 22～85 quality %, preferred 25～85 quality %, more preferably 45～80 quality %, further preferred 45～75 quality %.When content is very few, can not obtain excellent wearability, oil-proofness, in addition, when making electric wire, the pressure contact significantly reduces sometimes.In addition, when content was too much, elongation significantly reduced, and perhaps, when using as electric wire, added to produce man-hour in the pressure contact sometimes and ruptured.
In addition, another embodiment of the invention is following flame retardant resin composition, and said composition is with respect to (A) described later resinous principle of 100 mass parts, and it is above and be lower than (B) magnesium hydroxides of 100 mass parts to contain 75 mass parts.In this embodiment, (A) in the resinous principle, (a) content of composition is 35～100 quality %, and preferred 35～85 quality % are more preferably 40～70 quality %.Magnesium hydroxide after a little while, even heavy addition (a) composition, elongation can not reduce yet, and can keep rerum natura, and can keep the pressure contact.In this embodiment, in order to keep wearability, oil-proofness, flame retardant resistance, (a) content of composition in (A) resinous principle is at least 35 quality %.
(b) polypropylene
Polypropylene as use that can be in the present invention, can enumerate, the multipolymer of homo-polypropylene, propylene-ethylene random copolymer, propylene-ethylene block copolymer or propylene and other a small amount of alpha-olefins (for example, 1-butylene, 1-hexene, 4-methyl-1-pentene etc.).Particularly, can enumerate, for example, イ デ ミ Star PP (trade(brand)name, bright dipping petroleum chemistry (strain) is made) or サ Application ア ロ マ one (trade(brand)name, サ Application ア ロ マ one (strain) made) etc.
Wherein, the ethylene/propylene olefinic random copolymer is meant that the ethene component content is about 1～5 quality %, and the ethylene/propylene alkene block copolymer is meant that the ethene component content is about 5～15 quality %.
Contained polyacrylic MFR (ASTM-D-1238, L condition, 230 ℃) preferred 0.1～60g/10 minute, more preferably 0.1～25g/10 minute, further preferred 0.3～15g/10 minute.
In containing in the flame retardant resin composition of (B) magnesium hydroxide that above-mentioned (A) resinous principle with respect to 100 mass parts is 100 mass parts～300 mass parts as preferred implementation of the present invention, in (A) resinous principle, (b) polyacrylic content is 10～75 quality %, preferred 15～70 quality %, more preferably 15～65 quality %.When content was very few, formability, thermotolerance significantly reduced, and in the time of too much, wearability or pressure contact might reduce.
In addition, as of the present invention another preferred embodiment to contain above-mentioned (A) resinous principle with respect to 100 mass parts be more than 75 mass parts and be lower than in the flame retardant resin composition of (B) magnesium hydroxide of 100 mass parts, in (A) resinous principle, (b) polyacrylic content is 0～60 quality %.
(c) ethene-alpha-olefin copolymer
As the ethylene/alpha-olefin copolymer that uses in the present invention, for example, can enumerate ethene and carbonatoms and be the multipolymer of 4～12 alpha-olefin, object lesson as alpha-olefin, can enumerate 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene etc.
As ethylene/alpha-olefin copolymer, particularly, can enumerate, LLDPE (straight chain shape new LDPE (film grade)), LDPE (new LDPE (film grade)), VLDPE (ultra-low density polyethylene), EBR (ethene/1-butylene rubber) and synthetic ethylene/alpha-olefin copolymer etc. in the presence of metalloscene catalyst, wherein, preferred synthetic ethylene/alpha-olefin copolymer in the presence of metalloscene catalyst.
The preferred 940kg/m of the density of ethylene/alpha-olefin copolymer
3Below, be more preferably 930kg/m
3Below, preferred especially 928kg/m
3Below.The lower limit of this density has no particular limits, usually preferred 875kg/m
3More than.
In addition, as ethylene/alpha-olefin copolymer, its melt flow rate (MFR) (hereinafter referred to as MFR) (ASTMD-1238) preferred 0.5～50g/10 minute.
Ethylene/alpha-olefin copolymer among the present invention can be enumerated synthetic material in the presence of metalloscene catalyst, or common straight chain type new LDPE (film grade) or ultra-low density polyethylene etc., wherein, and preferred synthetic material in the presence of metalloscene catalyst.As such material, for example, " カ one ネ Le " (trade(brand)name) made by Japanese Port リ ケ system (strain), " エ ボ リ ユ one " (trade(brand)name) made by Sumitomo Mitsui polyolefine (strain) are gone on the market.
In the present invention, the content of ethene-alpha-olefin copolymer in (A) described later resinous principle is 0～65 quality %, preferred 0～50 quality %, more preferably 0～40 quality %.When content was too much, wearability or pressure contact, intensity significantly reduced sometimes.
(d-1) ethylene-vinyl acetate copolymer, (d-2) ethene-(methyl) acrylate copolymer
Said ethylene-vinyl acetate copolymer is ethene and the vinyl acetate copolymerized resin that obtains among the present invention, said ethene-(methyl) acrylate copolymer, can enumerate, for example, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate methyl terpolymer, ethylene-methyl methacrylate ethyl ester multipolymer.Particularly, as ethylene-vinyl acetate copolymer, can enumerate, for example, エ バ Off レ Star Network ス (trade(brand)name, Mitsui デ ユ Port Application Port リ ケ ミ カ Le (strain) is made) etc., as ethene-(methyl) acrylate copolymer, can enumerate, for example, エ バ Le ロ イ (trade(brand)name, Mitsui デ ユ Port Application Port リ ケ ミ カ Le (strain) is made) etc.These can use a kind separately, also can be mixed with two or more.
(d-1) among the present invention and/or (d-2) content of composition in (A) described later resinous principle be 0～40 quality %, preferred 0～25 quality % is more preferably 0～20 quality %, preferred especially 0～15 quality %.When content was too much, wearability, intensity may reduce.
(e) styrene copolymer (styrenic elastomerics)
Styrene copolymer of the present invention is based on the multipolymer of the block of conjugated diene compound and aromatic ethenyl compound and random structure or its hydrogenation thing.
As aromatic ethenyl compound, for example, vinylbenzene, t-butyl styrene, alpha-methyl styrene, p-methylstyrene, Vinylstyrene, 1 are arranged, 1-diphenyl benzene ethene, N, the N-diethyl is to aminoethyl vinylbenzene, Vinyl toluene, to t-butyl styrene etc., can select more than a kind or 2 kinds, wherein, optimization styrene.
In addition, as conjugated diene compound, for example, divinyl, isoprene, 1,3-pentadiene, 2 are arranged, 3-dimethyl-1,3-butadiene etc. can be selected more than a kind or 2 kinds, wherein, and preferred divinyl.
As above-mentioned styrene copolymer, particularly, can enumerate, for example, セ プ ト Application 4077, セ プ ト Application 4055, セ プ ト Application 8105 (trade(brand)name, (strain) Network ラ レ makes), ダ イ Na ロ Application 1320P (trade(brand)name, JSR (strain) makes) etc.
In the present invention, the content of styrene copolymer in (A) described later resinous principle is 0～40 quality %, and preferred 5～35 quality % are more preferably 5～20 quality %.When content was too much, wearability, intensity, oil-proofness might reduce.
(f) softener of rubber
As the softener of rubber among the present invention, can use the liquid or low-molecular-weight synthetic tenderizer of mineral oil of non-aromatic class.
The mineral oil softener that uses as rubber is the mixture that has made up aromatic ring, naphthenic hydrocarbon ring and alkane hydrocarbon chain three, what respectively the carbonatoms of alkane hydrocarbon chain is accounted for total carbon atom number is called paraffinic more than 50%, it with naphthenic hydrocarbon ring carbon atom number 30～40% the cycloalkane that is called, with the aromatic series carbonatoms is the fragrant same clan that is called more than 30%, and distinguishes.
Paraffinic and cycloalkane in the preferred above-mentioned difference of the mineral oils softener of rubber that uses among the present invention.
As above-mentioned softener of rubber, particularly, ダ イ ア Na プ ロ セ ス オ イ Le PW90, PW380 (trade(brand)name, シ エ Le company makes) etc. are arranged.
The content of softener of rubber of the present invention in (A) described later resinous principle is 0～20 quality %, preferred 0～10 quality %.When content was too much, wearability, intensity, oil-proofness reduced sometimes.
Flame retardant resin composition of the present invention and formed body contain at least a in (a-1)～(a-6) of being selected from of (A) resinous principle that the conduct of specified quantitative must composition respectively, (b) composition as essential composition or any composition, (c) as required, (d-1) and/or (d-2), (e) and (f) composition, by containing (B) magnesium hydroxide of mentioned component and specified quantitative, even do not carry out special crosslinking reaction, also have thermotolerance and high flame retardant, and mechanical characteristics, wearability, oil-proofness are very excellent.
When adding metal hydrate such as magnesium hydroxide in common resin, wearability significantly reduces.In the present invention, even heavy addition is as the magnesium hydroxide of metal hydrate in resin of the present invention, wearability can not reduce yet, and wearability can improve on the contrary.Therefore, can have both flame retardant resistance and wearability.In addition, when containing magnesium hydroxide in a large number usually, oil-proofness can reduce significantly, even but material of the present invention contains magnesium hydroxide in a large number, and oil-proofness can not reduce yet, and can keep the good excellent rerum natura of balance.
In addition, when using, have the very excellent rerum natura of pressure contact, can not produce the protuberance phenomenons such as (contain り and go up Ga り) of strain relief (strain relief), demonstrate excellent pressure contact as electric wire.
For in the present invention in specific resinous principle, add a large amount of magnesium hydroxides the time, wearability does not reduce the technology that improves on the contrary, also there is not clear and definite explanation, but infer be because, magnesium hydroxide and (a) composition have strong ionic combination, the all fine and combinations securely under the nanometer state of magnesium hydroxide and polymkeric substance, thus, the original hard that has of magnesium hydroxide, intensity, enhancing and resinous principle are integrated, so, the wearability of resin combination significantly improves.Because such effect even the bending forming surface does not produce albinism yet, can obtain the very high formed body of intensity.In addition, owing to have very firm microcosmic combination,, can keep rerum natura even also can swelling in oil component by magnesium hydroxide.
In the present invention, (A) in the resinous principle, the preferred 1.3 quality % of the content of unsaturated carboxylic acid composition (a)～6.0 quality % are more preferably 2.0 quality %～5.5 quality %.So-called unsaturated carboxylic acid composition is meant the unsaturated carboxylic acid composition that for example adopts (a-1) composition～use when (a-4) unsaturated carboxylic acid of composition carries out modification, is the acrylic or methacrylic acid as the copolymer composition of (a-5), (a-6) composition.In addition, in (a-1)～(a-4), " content of unsaturated carboxylic acid composition " and " unsaturated carboxylic acid-modified amount " same meaning.Content by making the unsaturated carboxylic acid composition can keep the pressure contact performance of excellent especially intensity, wearability, oil-proofness, electric wire in specific scope, can have excellent elongation, flame retardant resistance simultaneously.
(B) magnesium hydroxide
In the present invention, can use commercially available magnesium hydroxide usually.In the present invention, magnesium hydroxide can be untreated, also can implement surface treatment.As surface treatment, can enumerate, for example, fatty acid treatment, phosphoric acid are handled, titanic acid ester is handled, adopt the processing of silane coupling agent etc.From with the aspect of the binding characteristic of (A) resinous principle, in the present invention, preferably use untreated, or the magnesium hydroxide that uses silane coupling agent to handle.
Silane coupling agent among the present invention preferably has the silane coupling agent of vinyl, methacryloxy, glycidyl, amino endways.Particularly, can enumerate, for example, vinyltrimethoxy silane, vinyltriethoxysilane, glycidoxy-propyltrimethoxy silane, the epoxypropoxy triethoxyl silane, the epoxypropoxy methyl dimethoxysilane, methyl allyl acyloxypropyl trimethoxysilane, the methacryloxypropyl triethoxyl silane, the methacryloxypropyl methyl dimethoxysilane, mercaptopropyl trimethoxysilane, mercaptopropyltriethoxysilane, aminopropyl triethoxysilane, aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl tripropyl methyl dimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl tripropyl Trimethoxy silane etc.Wherein, preferred vinyl Trimethoxy silane, vinyltriethoxysilane, methacryloxypropyl triethoxyl silane, methacryloxypropyl methyl dimethoxysilane etc.As the surface treatment method that adopts silane coupling agent, can adopt normally used method to handle, for example, can mix not surface treated magnesium hydroxide by doing in advance, perhaps carry out wet processed, perhaps the blending silane coupling agent waits and obtains when mixing.The content of the silane coupling agent that uses can suitably add and carry out the needed sufficient amount of surface treatment, particularly, with respect to magnesium hydroxide, preferred 0.1～2.5 weight %, more preferred 0.2～1.8 weight %, further preferred 0.3～1.0 weight %.
In addition, also can obtain the magnesium hydroxide that has carried out silane coupling agent.As having carried out the surface-treated magnesium hydroxide with silane coupling agent, particularly, can enumerate, キ ス マ 5L, キ ス マ 5N, キ ス マ 5P (are trade(brand)name, consonance chemistry (strain) is made) or Off ア イ Application マ グ MO-E (trade(brand)name, (strain) TMG makes) etc.
In addition,, can enumerate as untreated magnesium hydroxide, for example, キ ス マ 5 (trade(brand)name, consonance chemistry (strain) is made), マ グ ニ Off イ Application H5 (trade(brand)name, ア Le ベ マ one Le (strain) is made) etc.
In the present invention, when handling magnesium hydroxide, can only use any one silane coupling agent, also can use more than 2 kinds simultaneously with silane coupling agent.
In the present invention, can use separately respectively and not carry out the surface-treated magnesium hydroxide, or carry out the surface-treated magnesium hydroxide, also can use simultaneously.Can also use simultaneously and carry out different surface-treated magnesium hydroxides.
In flame retardant resin composition preferred embodiment of the present invention, (B) content of magnesium hydroxide is 100～300 mass parts with respect to 100 mass parts (A) resinous principle, and preferred 120～250 mass parts are more preferably 120～230 mass parts.When content is very few, on flame retardant resistance, have problems, in the time of too much, exist mechanical characteristics significantly to reduce, perhaps the problem of lower temperature resistance reduction.As mentioned above, in this embodiment, (A) contain (a) composition of 22～85 quality % in the resinous principle.
In addition, in another flame retardant resin composition preferred embodiment of the present invention, (B) content of magnesium hydroxide is that 75 mass parts are above and be lower than 100 mass parts with respect to 100 mass parts (A) resinous principle, and preferred 80 mass parts are above and be lower than 100 mass parts.As mentioned above, in this embodiment, (A) contain (a) composition of 35～100 quality % in the resinous principle.
In addition, for improving flame retardant resistance, can also in flame retardant resin composition of the present invention, add trimeric cyanamide tricyanic acid ester cpds.The thin person of trimeric cyanamide cyanurate preferable particle size.The median size of the trimeric cyanamide tricyanic acid ester cpds that uses among the present invention is preferably below the 10 μ m, is more preferably below the 7 μ m, further below the preferred 5 μ m.The lower limit of this median size has no particular limits, usually being lower limit about 3 μ m.In addition, from dispersed aspect, the preferred use carried out surface-treated trimeric cyanamide tricyanic acid ester cpds.As the trimeric cyanamide tricyanic acid ester cpds that can use in the present invention, for example, MCA-0, MCA-1 (be trade(brand)name, Mitsubishi Chemical's (strain) make) are arranged, or by the trimeric cyanamide tricyanic acid ester cpds of Chemie Linz Gmbh list marketing.In addition, as carrying out surface-treated trimeric cyanamide tricyanic acid ester cpds with lipid acid, having carried out silane surface-treated trimeric cyanamide tricyanic acid ester cpds, MC640, MC860 (be trade(brand)name, daily output chemistry (strain) is made) etc. are arranged.
As the trimeric cyanamide tricyanic acid ester cpds that can use in the present invention, for example, the trimeric cyanamide cyanurate of following structure is arranged.
In flame retardant resin composition of the present invention, as required, can also contain at least a kind that is selected from zinc, zinc hydroxyl stannate and the zinc borate, in addition, can further improve flame retardant resistance.By using these compounds, the speed that forms shell during burning increases, and the shell of formation is more firm.Therefore, can by the trimeric cyanamide tricyanic acid ester cpds that inside produces gas flame retardant resistance be improved tremendously with when burning.
Below the preferred 5 μ m of the median size of the zinc borate of Shi Yonging, zinc hydroxyl stannate, zinc, be more preferably below the 3 μ m in the present invention.
As the lead borate that uses among the present invention, particularly, can enumerate, for example, ア Le カ ネ Star Network ス FRC-500 (2ZnO/3B
2O
33.5H
2O), FRC-600 (be trade(brand)name, marshy land chemistry (strain) make) etc.In addition, as zinc (ZnSnO
3), zinc hydroxyl stannate (ZnSn (OH)
6), ア Le カ ネ Star Network ス ZS, ア Le カ ネ Star Network ス ZHS (be trade(brand)name, marshy land chemistry (strain) is made) etc. are arranged.
In formed article, can also in the scope of not damaging purpose of the present invention, in flame retardant resin composition of the present invention, suitably contain normally used various additive, for example oxidation inhibitor, metal passivator, fire-retardant (helping) agent, weighting agent, lubricant etc.
As oxidation inhibitor, can enumerate, 4,4 '-dioctyl diphenylamine, N, N '-diphenyl-para-phenylene diamine, 2,2,4-trimethylammonium-1, the amine antioxidants such as polymkeric substance of 2-dihydroxyl quinoline, tetramethylolmethane four (3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester), octadecyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester, 1,3,5-trimethylammonium-2,4, phenolic antioxidants such as 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, two (2-methyl-4-(the positive alkylthio propionyloxy of 3-)-5-tert-butyl-phenyl) thioether, 2-mercaptobenzimidazole and zinc salt thereof, tetramethylolmethane four sulfur type antioxidants such as (3-lauryl thiopropionates) etc.
As metal passivator, can enumerate N; N '-(3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl) hydrazine, 3-(N-o-hydroxy formyl) amino-1,2; 4-triazole, 2,2 '-oxalyl amido two (ethyl-3-(3,5 di-tert-butyl-hydroxy phenyl) propionic ester) etc.
As fire-retardant (helping) agent, weighting agent, can enumerate graphite, clay, zinc oxide, stannic oxide, titanium oxide, magnesium oxide, molybdenum oxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT, polysiloxane compound, quartz, talcum, lime carbonate, magnesiumcarbonate, white carbon black etc.
As lubricant, can enumerate, hydro carbons, fatty acid, fatty acyl amide, ester class, alcohols, metallic soap class, polysiloxane-based etc., wherein, preferred hydro carbons or polysiloxane-based.
Flame retardant resin composition of the present invention can obtain above-mentioned each composition melting mixing by normally used kneading devices such as twin shaft mixing extruder, banbury mixers, kneader, rollers.
Below formed articles such as insulated line of the present invention, cable, optical fiber cable are described.
As formed article of the present invention, for example, have in the outside of conductor or optical fiber wire rod, optical fibre core or flame retardant resin composition that the periphery of other formed bodys has the invention described above as the insulated line of coating layer or cable etc.Above-mentioned insulated line or cable can be coated on making of conductor, optical fiber, set insulated line or other formed bodys on every side by using common extrusion shaping machine that flame retardant resin composition of the present invention is extruded.In addition, for pipe, also can adopt in the same way and make.
Size or shape for formed body of the present invention have no particular limits, and can suitably determine according to purposes.For example, in the time of in being used in insulated line, the wall thickness that is formed on the coating layer of conductor insualtion resin composition on every side also has no particular limits, but preferred 0.15～2mm.In addition, insulation layer can be a multilayered structure, also can also have middle layer etc. except the coating layer that is formed by flame retardant resin composition of the present invention.
Below, based on embodiment the present invention is described in more detail, but the present invention is not limited to these.
Embodiment
At first, at room temperature do and mix each composition shown in table 1～3, carry out melting mixing, make the flame retardant resin composition of embodiment 1～19 and comparative example 1～7 with banbury mixers.
Then, use is used to make the coating unit of extruding of electric wire, (conductor directly is the zinc-plated soft copper strand of 0.48mm φ, constitutes: 7/0.16mm φ) go up and coat each flame retardant resin composition of melting mixing in advance by extrusion molding, make each insulated line at conductor.External diameter is 0.98mm (wall thickness of insulation layer is 0.25mm).
The insulated line that obtains is carried out following evaluation test.
Tension test
Make tubular piece by electric wire, carry out tension test.At distance between bench marks 25mm, draw speed 50mm/ tests under dividing.Elongation is more than 100%, and tensile strength is to be necessary more than the 18MPa.
Oil resistant test
Test method is, based on JIS C 3005 standards, adopts the JIS2 test oil, after carrying out 24 hours dippings under 85 ℃, carries out tension test.
The tensile strength residual rate is more than 80%, and the elongation residual rate is qualified more than 80%.
Abrasion test
Use the R=0.225 grinding wheel, test by the reciprocal method of emery wheel according to JASO D 608 standards.Increase the weight of to be 7N.Number of times is qualified more than 700 times, is more preferably more than 900 times, and is further preferred more than 1000 times.
The pressure contact of electric wire
Use hand press, adopt モ レ Star Network ス Mi-II terminal stud (コ ネ Network ) to carry out the pressure contact, observe then.Have place fracture and surpass plate afterbody (vowing the buttocks part) person in the part of pressure contact edge and be considered as defective (*) at the protuberance of strain relief separated wire coating portion, non-cracking, swelling within the limits prescribed, the person is qualified (zero).
Flame retardant resistance
Carry out horizontal burning test according to the UL1581 standard.Burning continues that the person is defective more than 60 seconds.
Anti-traumatic
Employing is used the R=0.125mm grinding wheel according to the test method of the reciprocal method of grinding wheel of the wear-resistant test of JASO D 608 standards, carries out 4 back and forth wearing and tearing under heavy burden 5N.Observe sample thereafter.
" zero " (very): no wound or do not have albefaction
" * " (bad): have wound or albefaction remarkable
Outward appearance
For outward appearance, the external diameter by the visual inspection insulated line has the state on no change or surface, and these are represented for good usefulness zero, and the external diameter change, is oozed dew (Block リ one De) person's usefulness * expression at unstable person, the coarse person of surface appearance.
Use following substances as each material.
(a-1) by unsaturated carboxylic acid-modified polypropylene
Acrylic acid modified polypropylene
Trade(brand)name: Port リ ボ Application De P-1002 manufacturers: Network ロ Application プ ト Application (strain)
Acrylic acid modified amount: 6 quality %
Acrylic acid modified polyethylene
Trade(brand)name: Port リ ボ Application De P-1009 manufacturers: Network ロ Application プ ト Application (strain)
Acrylic acid modified amount: 6 quality %
The toxilic acid modified poly ethylene
Trade(brand)name: ア De マ one XE070 manufacturers: Mitsui Chemicals (strain)
Toxilic acid modification amount: 1 quality %
The toxilic acid modified poly ethylene
Trade(brand)name: ア De テ Star Network ス L-6100M manufacturers: Japanese polyethylene (strain)
Toxilic acid modification amount: 1 quality %
(a-4) by unsaturated carboxylic acid-modified styrene copolymer
Toxilic acid modified phenylethylene analog copolymer
Trade(brand)name: Network レ イ ト Application 1901FG manufacturers: JSR Network レ イ ト Application (strain)
Toxilic acid modification amount: 1.7 quality %
(a-5) ethene-(methyl) acrylic copolymer
Ethylene-methacrylic acid copolymer
Trade(brand)name: ニ ユ Network レ Le N1207C manufacturers: Mitsui デ ユ Port Application Port リ ケ ミ カ Le (strain)
Methacrylic acid content: 12 quality %
(b) polyethylene
Block polypropylene (B-PP)
Trade(brand)name: 150GK manufacturers: bright dipping petroleum chemistry (strain)
Atactic Polypropelene (R-PP)
Trade(brand)name: BC6DR manufacturers: Japan polypropylene (strain)
(c) ethene-alpha-olefin copolymer
Metalloscene catalyst polyethylene (density: 898kg/m
3)
Trade(brand)name: カ one ネ Le KF-360 manufacturers: Japanese Port リ ケ system (strain)
(d-1) ethylene-vinyl acetate copolymer
Trade(brand)name: エ バ Off レ Star Network ス V-527-4 manufacturers: Mitsui デ ユ Port Application Port リ ケ ミ カ Le (strain)
Vinyl acetate content: 17 quality %
(e) styrene copolymer
SEPS (styrene-ethylene-propylene-styrene multipolymer)
Trade(brand)name: セ プ ト Application 4077 manufacturerss: (strain) Network ラ レ
Trade(brand)name: セ プ ト Application 2104 manufacturerss: (strain) Network ラ レ
HSBR (the hydrogenation thing of styrene butadiene random copolymer)
Trade(brand)name: ダ イ Na ロ Application 1320P manufacturers: JSR (strain)
(f) softener of rubber
Trade(brand)name: ダ イ ア Na プ ロ セ ス オ イ Le PW90 manufacturers: シ エ Le company
(B) magnesium hydroxide
The magnesium hydroxide of silane treatment
Trade(brand)name: キ ス マ 5L manufacturers: consonance science (strain)
Untreated magnesium hydroxide
Trade(brand)name: キ ス マ 5 manufacturerss: consonance science (strain)
The magnesium hydroxide of fatty acid treatment
Trade(brand)name: キ ス マ 5 AL manufacturerss: consonance science (strain)
Lubricant
Polyethylene wax
Trade(brand)name: AC Port リ エ チ レ Application NO.6 manufacturers: ヘ キ ス ト company
In addition, among all embodiment and comparative example, all be the protective agent イ Le ガ ノ Star Network ス 1010 (チ バ ス ペ シ ヤ リ テ イ ケ ミ カ Le ズ makes for trade(brand)name, Hinered phenols protective agent) that adds 1 mass parts with respect to the resinous principle (A) of 100 mass parts.
The quality % of the content of each material, (a) composition and (a) amount (quality %), the test-results of the acid in the composition are shown in table 1～3.In the table, the content of composition (a)～(f) is respectively to become component (quality %) in resinous principle (A) total amount, and the content of magnesium hydroxide and polyethylene wax is the content separately (mass parts) with respect to 100 mass parts resinous principles (A).
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | |
| Acrylic acid modified polypropylene | ポリボンドP1002 | 40 | 40 | 40 | 20 | 30 | 60 | 40 | 40 | 15 | 25 |
| Acrylic acid modified polyethylene | ポリポンドP1009 | 20 | |||||||||
| The toxilic acid modified poly ethylene | アドマ-XE070 | 5 | 5 | ||||||||
| Toxilic acid modified styrenics elastomerics | クレイトン1901FG | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 10 | 5 |
| The toxilic acid modified poly ethylene | L-6100M | ||||||||||
| Ethylene-methacrylic acid copolymer | ニユクレルN1207C | 10 | |||||||||
| Vinyl-vinyl acetate copolymer | V-527-4 | ||||||||||
| B-PP | B-PP | 20 | 30 | 20 | 20 | 20 | 15 | 20 | 20 | 70 | 15 |
| R-PP | R-PP | ||||||||||
| ME-PE 0.898 | カ-ネルKF-360 | 30 | 20 | 30 | 25 | 30 | 30 | 5 | 55 | ||
| SEPS | SEPS4077 | 15 | |||||||||
| SEPS2104 | |||||||||||
| HSBR | ダイナロン1320P | 10 | 10 | ||||||||
| OIL | ダイアナプロセスオイルPW-90 | 5 | |||||||||
| The magnesium hydroxide of silane treatment | キスマ5L | 150 | 150 | 150 | 120 | 175 | 200 | 120 | 225 | ||
| Untreated magnesium hydroxide | キスマ5 | 150 | 150 | ||||||||
| The magnesium hydroxide of fatty acid treatment | キスマ5AL | ||||||||||
| Polyethylene wax | ACポリエチレンNO.6 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| (a) the quality % of composition | 50 | 50 | 50 | 50 | 55 | 75 | 50 | 50 | 25 | 30 | |
| The amount of acid | 2.57 | 2.57 | 2.57 | 2.57 | 3.22 | 3.82 | 2.57 | 2.57 | 1.07 | 1.585 | |
| Tensile strength (MPa) | 26.5 | 28.4 | 26.1 | 26.8 | 28.9 | 23.5 | 27.6 | 29.8 | 21.5 | 24.2 | |
| Elongation (%) | 180 | 200 | 190 | 160 | 120 | 220 | 150 | 120 | 250 | 130 | |
| Wearability | 1800 | 1200 | 1650 | 1700 | 1900 | 1400 | 2000 | 2000 | 900 | 1300 | |
| Level is fire-retardant | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | |
| Anti-traumatic | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Outward appearance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Oil-proofness | |||||||||||
| Tensile strength residual rate (%) | 94 | 88 | 91 | 90 | 92 | 92 | 92 | 93 | 87 | 87 | |
| Elongation residual rate (%) | 105 | 114 | 109 | 108 | 106 | 108 | 105 | 107 | 113 | 116 | |
| The pressure contact | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
Table 2
| Embodiment | 11 | 12 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | |
| Acrylic acid modified polypropylene | ポリボンドP1002 | 40 | 40 | 40 | 30 | 40 | 40 | 90 | 30 | |
| Acrylic acid modified polyethylene | ポリボンドP1009 | 40 | ||||||||
| The toxilic acid modified poly ethylene | アドマ-XE070 | |||||||||
| Toxilic acid modified styrenics elastomerics | クレイトン1901FG | 10 | 10 | 10 | 10 | 10 | 10 | 10 | ||
| The toxilic acid modified poly ethylene | L-6100M | 10 | 10 | |||||||
| Ethylene-methacrylic acid copolymer | ニユクレルN1207C | 20 | ||||||||
| Vinyl-vinyl acetate copolymer | V-527-4 | 15 | ||||||||
| B-PP | B-PP | 20 | 15 | 20 | 20 | 20 | 20 | 20 | 40 | |
| R-PP | R-PP | 30 | 10 | |||||||
| ME-PE 0.898 | カ-ネルKF-360 | 15 | 30 | 15 | 30 | 30 | 10 | |||
| SEPS | SEPS4077 | |||||||||
| SEPS2104 | 30 | |||||||||
| HSBR | ダイナロン1320P | |||||||||
| OIL | ダイアナプロセスオイルPW-90 | |||||||||
| The magnesium hydroxide of silane treatment | キスマ5L | 150 | 120 | 150 | 150 | 150 | 150 | 80 | 90 | |
| Untreated magnesium hydroxide | キスマ5 | |||||||||
| The magnesium hydroxide of fatty acid treatment | キスマ5AL | 150 | ||||||||
| Polyethylene wax | ACポリエチレンNO.6 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| (a) the quality % of composition | 50 | 70 | 50 | 40 | 50 | 50 | 50 | 100 | 44 | |
| The amount of acid | 2.57 | 4.97 | 2.57 | 1.97 | 2.57 | 2.50 | 2.50 | 5.57 | 1.97 | |
| Tensile strength (MPa) | 29.7 | 25.6 | 20.3 | 232 | 25.3 | 22.3 | 21.4 | 28.3 | 25.5 | |
| Elongation (%) | 150 | 170 | 210 | 130 | 130 | 160 | 150 | 200 | 230 | |
| Wearability | 2200 | 1500 | 700 | 1100 | 1100 | 1400 | 1200 | 1100 | 800 | |
| Level is fire-retardant | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | Qualified | |
| Anti-traumatic | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Outward appearance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Oil-proofness | ||||||||||
| Tensile strength residual rate (%) | 94 | 93 | 84 | 86 | 88 | 92 | 89 | 92 | 89 | |
| Elongation residual rate (%) | 105 | 106 | 126 | 123 | 112 | 106 | 111 | 109 | 114 | |
| The pressure contact | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
Table 3
| Comparative example | 1 | 2 | 3 | 4 | 5 | 6 | 7 | |
| Acrylic acid modified polypropylene | ポリボンドP1002 | 40 | 70 | 40 | 70 | 10 | ||
| Toxilic acid modified styrenics elastomerics | クレイトン1901FG | 10 | 10 | 10 | ||||
| Ethylene-methacrylic acid copolymer | ニユクレルN1207C | 20 | 20 | |||||
| B-PP | B-PP | 60 | 60 | 20 | 20 | 10 | 90 | |
| ME-PE 0.898 | カ-ネルKF-360 | 40 | 30 | 30 | 10 | 30 | ||
| The magnesium hydroxide of silane treatment | キスマ5L | 150 | 150 | 70 | 150 | 350 | 150 | 150 |
| Polyethylene wax | ACポリエチレンNO.6 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
| (a) the quality % of composition | 0 | 10 | 50 | 90 | 50 | 90 | 10 | |
| The amount of acid | 0 | 0.17 | 2.57 | 6.60 | 2.57 | 6.60 | 0.6 | |
| Tensile strength (MPa) | 22.4 | 23.2 | 26.8 | 30.3 | 32.5 | 31.2 | 23.2 | |
| Elongation (%) | 260 | 200 | 160 | 40 | 10 | 20 | 70 | |
| Wearability | 400 | 550 | 900 | 1200 | 1000 | 800 | 600 | |
| Level is fire-retardant | Qualified | Qualified | Defective | Qualified | Qualified | Qualified | Qualified | |
| Anti-traumatic | × | ○ | ○ | ○ | ○ | ○ | ○ | |
| Outward appearance | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| Oil-proofness | ||||||||
| Tensile strength residual rate (%) | 78 | 83 | 90 | - | - | - | - | |
| Elongation residual rate (%) | 125 | 121 | 112 | - | - | - | - | |
| The pressure contact | × | × | ○ | × | × | × | × | |
Can be clear and definite from table 1～3, embodiment 1～19 has obtained good result in all assessment items.
In contrast, do not containing under the situation that (a) composition (comparative example 1) or content departs from the scope of the present invention (comparative example 2,6), on oil-proofness or pressure contact processibility, elongation, having problems.In addition, when not adding (a) composition, anti-traumatic also significantly reduction.In addition, do not contain (b) composition or surpass scope of the present invention when a lot (comparative example 4,7), do not satisfy oil-proofness, pressure contact processibility.When magnesium hydroxide content is lower than scope of the present invention (comparative example 3), flame retardant resistance is defective, on the contrary, in the time of too much (comparative example 5), obtains the result of mechanical characteristics, oil-proofness, pressure contact poor in processability.
To sum up, the flame retardant resistance of flame retardant resin composition of the present invention, thermotolerance, mechanical characteristics, oil-proofness, wearability, pressure contact excellence, and when landfill, burning etc. are discarded, can not dissolve and separate out heavy metal compound or produce a large amount of cigarettes, obnoxious flavour, can solve present environmental problem.Above-mentioned effect is at the magnesium hydroxide that uses untreated magnesium hydroxide and/or silane treatment during as magnesium hydroxide, and is effective especially.
In addition, effective especially when the content of (a) in the resinous principle is 45～80 quality %, in addition, when the content of the unsaturated carboxylic acid in the resinous principle was 1.3 quality %～6.0 quality %, effect was obvious, and is when being 2.0 quality %～5.5 quality %, remarkable especially.
In addition, when containing (methyl) acrylic acid modified polypropylene as (a) at least, effect is obvious, and is when containing (methyl) acrylic acid modified polypropylene and unsaturated carboxylic acid-modified styrene copolymer as (a), remarkable especially.
In addition, formed article of the present invention satisfies above-mentioned all characteristics, and because the fusion again of formed article and can utilizing again, even bending can albefaction yet, in addition, easy damaged does not particularly have both flame retardant resistance, wearability, oil-proofness.
Therefore, flame retardant resin composition of the present invention is the flame retardant resin composition that is suitable for the formed articles such as wiring material of wiring material, optical fibre core, light 7 lines, sheet, pipe or pressure contact excellence.
Industrial applicibility
The invention provides a kind of flame retardant resin composition and the formed article that uses it, the flame retardant resistance of described flame retardant resin composition, thermotolerance, mechanical characteristics, oil-proofness, wearability, pressure contact excellence, and when landfill, burning etc. are discarded, can not dissolve and separate out heavy metal compound or produce a large amount of cigarettes, obnoxious flavour, can solve present environmental problem.In addition, the present invention also provides a kind of these characteristics that satisfies, and can utilize again owing to the fusion again of formed article, even bending can albefaction yet, in addition, easy damaged not particularly has both the formed article such as resin combination, wiring material, optical fibre core, optical fiber cable, sheet, pipe of flame retardant resistance or wearability, oil-proofness, the wiring material of pressure contact excellence.
With embodiments of the present invention the present invention has been described, but as long as we do not specify, then be not any details that our invention will be defined in explanation, be construed as the explanation of in the spirit and scope of not violating the invention shown in claims of enclosing, making wide region.
Claims (11)
1. a flame retardant resin composition wherein, with respect to (A) resinous principle of 100 mass parts, contains (B) magnesium hydroxide of 100 mass parts～300 mass parts, and described (A) resinous principle comprises:
The resin (a) of 22 quality %～85 quality %, this resin (a) be selected from (a-1) by unsaturated carboxylic acid-modified polyolefine, (a-2) by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer, (a-3) by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer, (a-4) by unsaturated carboxylic acid-modified styrene copolymer, (a-5) ethene-(methyl) acrylic copolymer and (a-6) at least a in ethene-(methyl) acrylate-(methyl) acrylic copolymer;
(b) polypropylene of 10 quality %～75 quality %;
(c) ethene-alpha-olefin copolymer of 0 quality %～65 quality %;
(d-1) ethylene-vinyl acetate copolymer of 0 quality %～20 quality % and/or (d-2) ethene-(methyl) acrylate copolymer;
(e) styrenic elastomerics of 0 quality %～40 quality %; And
(f) softener of rubber of 0 quality %～20 quality %.
2. a flame retardant resin composition wherein, with respect to (A) resinous principle of 100 mass parts, contains (B) magnesium hydroxide of 100 mass parts～300 mass parts, and described (A) resinous principle comprises:
The resin (a) of 25 quality %～85 quality %, this resin (a) be selected from (a-1) by unsaturated carboxylic acid-modified polyolefine, (a-2) by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer, (a-3) by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer, (a-4) by unsaturated carboxylic acid-modified styrene copolymer, (a-5) ethene-(methyl) acrylic copolymer and (a-6) at least a in ethene-(methyl) acrylate-(methyl) acrylic copolymer;
(b) polypropylene of 10 quality %～75 quality %;
(c) ethene-alpha-olefin copolymer of 0 quality %～65 quality %;
(d-1) ethylene-vinyl acetate copolymer of 0 quality %～20 quality % and/or (d-2) ethene-(methyl) acrylate copolymer;
(e) styrenic elastomerics of 0 quality %～40 quality %; And
(f) softener of rubber of 0 quality %～20 quality %.
3. flame retardant resin composition, wherein, with respect to (A) resinous principle of 100 mass parts, it is above and be lower than (B) magnesium hydroxides of 100 mass parts to contain 75 mass parts, and described (A) resinous principle comprises:
The resin (a) of 35 quality %～100 quality %, this resin (a) be selected from (a-1) by unsaturated carboxylic acid-modified polyolefine, (a-2) by unsaturated carboxylic acid-modified ethylene-vinyl acetate copolymer, (a-3) by unsaturated carboxylic acid-modified ethene-(methyl) acrylate copolymer, (a-4) by unsaturated carboxylic acid-modified styrene copolymer, (a-5) ethene-(methyl) acrylic copolymer and (a-6) at least a in ethene-(methyl) acrylate-(methyl) acrylic copolymer;
(b) polypropylene of 0 quality %～60 quality %;
(c) ethene-alpha-olefin copolymer of 0 quality %～65 quality %;
(d-1) ethylene-vinyl acetate copolymer of 0 quality %～20 quality % and/or (d-2) ethene-(methyl) acrylate copolymer;
(e) styrenic elastomerics of 0 quality %～40 quality %; And
(f) softener of rubber of 0 quality %～20 quality %.
4. each described flame retardant resin composition in the claim 1～3, wherein, above-mentioned (B) magnesium hydroxide is (B-1) the untreated magnesium hydroxide and/or (B-2) magnesium hydroxide of silane treatment.
5. each described flame retardant resin composition in the claim 1～4, wherein, in above-mentioned (A) resinous principle, content (a) is 45 quality %～80 quality %.
6. each described flame retardant resin composition in the claim 1～5, wherein, in above-mentioned (A) resinous principle, the content of unsaturated carboxylic acid composition (a) is 1.3 quality %～6.0 quality %.
7. each described flame retardant resin composition in the claim 1～6, wherein, in above-mentioned (A) resinous principle, the content of unsaturated carboxylic acid composition (a) is 2.0 quality %～5.5 quality %.
8. each described flame retardant resin composition in the claim 1～7 wherein, as (a), contains by (methyl) acrylic acid modified polypropylene at least.
9. any described flame retardant resin composition in the claim 1～8 wherein, as (a), contains by (methyl) acrylic acid modified polypropylene with by unsaturated carboxylic acid-modified styrene copolymer at least.
10. formed article wherein, has in the claim 1～9 each described flame retardant resin composition as coating layer in the outside of conductor or optical fiber wire rod and/or optical fibre core.
11. a formed article, it obtains by each described flame retardant resin composition in the moulding claim 1～9.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004370366 | 2004-12-22 | ||
| JP370366/2004 | 2004-12-22 | ||
| JP265265/2005 | 2005-09-13 | ||
| JP2005265265A JP5144007B2 (en) | 2004-12-22 | 2005-09-13 | Flame retardant resin composition and molded article using the same |
| PCT/JP2005/024157 WO2006068304A1 (en) | 2004-12-22 | 2005-12-22 | Flame-retardant resin composition and formed article using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101080456A true CN101080456A (en) | 2007-11-28 |
| CN101080456B CN101080456B (en) | 2011-02-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800434349A Active CN101080456B (en) | 2004-12-22 | 2005-12-22 | Flame-retardant resin composition and formed article using the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5144007B2 (en) |
| CN (1) | CN101080456B (en) |
| DE (1) | DE112005003235T5 (en) |
| HK (1) | HK1110884A1 (en) |
| WO (1) | WO2006068304A1 (en) |
Cited By (5)
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| CN102010536A (en) * | 2010-12-16 | 2011-04-13 | 上海交通大学 | Low-smoke halogen-free flame retardant polyolefin composite material and preparation method thereof |
| CN102140192A (en) * | 2011-04-07 | 2011-08-03 | 上海交通大学 | Low-smoke halogen-free polyolefine composite material and preparation method thereof |
| CN103459487A (en) * | 2011-05-02 | 2013-12-18 | 古河电气工业株式会社 | Flame-retardant resin composition and molded article |
| CN103502350A (en) * | 2011-06-27 | 2014-01-08 | 古河电气工业株式会社 | Flame retardant resin composition and molded article |
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| JP5144013B2 (en) * | 2004-12-22 | 2013-02-13 | 古河電気工業株式会社 | Flame retardant resin composition and molded body using the same |
| JP5260868B2 (en) * | 2006-12-19 | 2013-08-14 | 古河電気工業株式会社 | Insulating resin composition and insulated wire |
| JP5202849B2 (en) * | 2007-01-16 | 2013-06-05 | 古河電気工業株式会社 | Flame retardant resin composition and molded article using the same |
| JP4897959B2 (en) * | 2007-01-22 | 2012-03-14 | 古河電気工業株式会社 | Flame retardant optical fiber cord or cable |
| JP2008180827A (en) * | 2007-01-24 | 2008-08-07 | Furukawa Electric Co Ltd:The | Optical fiber cable |
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| JP2002170441A (en) * | 2000-12-01 | 2002-06-14 | Sumitomo Wiring Syst Ltd | Insulated wire |
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| JP2004043546A (en) * | 2002-07-09 | 2004-02-12 | Sumitomo Wiring Syst Ltd | Olefin resin composition and covered electric wire |
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-
2005
- 2005-09-13 JP JP2005265265A patent/JP5144007B2/en active Active
- 2005-12-22 WO PCT/JP2005/024157 patent/WO2006068304A1/en active Application Filing
- 2005-12-22 DE DE112005003235T patent/DE112005003235T5/en not_active Ceased
- 2005-12-22 CN CN2005800434349A patent/CN101080456B/en active Active
-
2008
- 2008-05-21 HK HK08105603.0A patent/HK1110884A1/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102010536A (en) * | 2010-12-16 | 2011-04-13 | 上海交通大学 | Low-smoke halogen-free flame retardant polyolefin composite material and preparation method thereof |
| CN102140192A (en) * | 2011-04-07 | 2011-08-03 | 上海交通大学 | Low-smoke halogen-free polyolefine composite material and preparation method thereof |
| CN103459487A (en) * | 2011-05-02 | 2013-12-18 | 古河电气工业株式会社 | Flame-retardant resin composition and molded article |
| CN103502350A (en) * | 2011-06-27 | 2014-01-08 | 古河电气工业株式会社 | Flame retardant resin composition and molded article |
| CN104078140A (en) * | 2013-03-29 | 2014-10-01 | 日立金属株式会社 | Halogen- and phosphorus-free flame-retardant insulated wire and halogen- and phosphorus-free flame-retardant insulated cable |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101080456B (en) | 2011-02-23 |
| DE112005003235T5 (en) | 2007-10-31 |
| HK1110884A1 (en) | 2008-07-25 |
| WO2006068304A1 (en) | 2006-06-29 |
| JP2006199923A (en) | 2006-08-03 |
| JP5144007B2 (en) | 2013-02-13 |
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