WO2004014995A1 - Composition de resine pour recouvrir des fils metalliques et des cables - Google Patents

Composition de resine pour recouvrir des fils metalliques et des cables Download PDF

Info

Publication number
WO2004014995A1
WO2004014995A1 PCT/US2003/024909 US0324909W WO2004014995A1 WO 2004014995 A1 WO2004014995 A1 WO 2004014995A1 US 0324909 W US0324909 W US 0324909W WO 2004014995 A1 WO2004014995 A1 WO 2004014995A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
resin
weight
styrene
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2003/024909
Other languages
English (en)
Inventor
Sho Sato
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2002230310A external-priority patent/JP4007877B2/ja
Application filed by General Electric Co filed Critical General Electric Co
Priority to AU2003269953A priority Critical patent/AU2003269953A1/en
Publication of WO2004014995A1 publication Critical patent/WO2004014995A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/427—Polyethers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides

Definitions

  • the invention relates to the resin compositions for wire and cable covering materials containing polyphenylene ether resin (abbreviated as PPE). More specifically, the invention relates to resin compositions for wire and cable covering materials that excel in non-halogen, fire retardancy and chemical resistance.
  • PPE polyphenylene ether resin
  • amorphous resins excel in dimensional precision after injection molding because of their amorphous structural characteristics. Taking advantage of this characteristic, they are widely used in the industrial applications involving large size molding objects where precision assembly is required. However, a consequence of the amorphous structure is organic chemical permeability resulting in weak chemical resistance and easy attacked by oil, organic solvent etc.
  • crystalline resins have outstanding chemical resistance because of their crystalline characteristic, and are used in applications involve exposure to oil, or organic solvent etc.
  • crystalline resins are not suitable for large size molded objects because of their low dimensional precision due to the molding shrinkage phenomenon.
  • the inorganic fillers, such as glass fibers are added to improve dimensional stability, this results in high density, low ductility impact strength, and different shrinkages in the injection molding flow direction and perpendicular flow, and results in defects like warpage or deformation.
  • Polyphenylene ether resin is a non-crystalline thermoplastic resin with well-balanced mechanical properties, outstanding electrical properties and low water-absorbing property and excellent dimensional resistance. Moreover, polyphenylene ether resin is compatible with polystyrene resin which is also a non-crystalline thermoplastic resin, and can be modified easily.
  • the resin composition (herein after, abbreviated to PPE/PS resin composition) containing PPE resin and styrene resin has outstanding molding processing characteristics and impact resistance (US Patent No. 3,383,435), and is widely used for automobile parts, electrical and electronic components.
  • PPE/PS resin composition is amorphous resin, and chemical resistance, specially resistance against aromatic hydrocarbon solvent is poor, e.g.
  • polyphenylene ether resin is distributed finely in the matrix of nylon, and the distribution is controlled by the compatibilizer and is called as non-compatible alloy.
  • the chemical permeability to polyphenylene ether resin is suppressed, and the chemical resistance is improved.
  • the low dimensional stability resulted from shrinkage during molding of nylon is improved by distributing polyphenylene ether resin in nylon.
  • the improvement in the dimensional precision is inadequate. It is clear that new technology to improve the chemical resistance of compositions containing polyphenylene ether resin is still needed.
  • syndiotactic styrene polymer having syndiotactic structure
  • syndiotactic polymer or syndiotactic polystyrene polymer in three-dimensional structure
  • experimentation involving blending syndiotactic styrene polymer -with various resins has been carried out.
  • Syndiotactic styrene polymer is crystalline and from the styrene molecular structure is highly compatible with polyphenylene ether resin, like conventional atactic styrene polymer, and blend compositions of polyphenylene ether resin and syndiotactic styrene polymer are well-known.
  • Such blend compositions have been described in various patents, such as Kokai no. 01-182344, Kokai no. 01-82350, Kokai no. 02-64140, Kokai no. 02-92948, Kokai no. 02-218724, Kokai no. 03-126743, Kokai no. 05-86296, Kokai no. 05-209098, Kokai no.
  • polyphenylene ether resin is widely used as the resin composition for wires and cables covering material.
  • PVC resin has low heat resistant temperature of 60°C, and contains halogen as fire retardant, which produces dioxin during combustion and pollutes the environment, and the regulations restricting its use are being tightened.
  • tetrafluoroethylene can be used as the resin composition for wires and cables covering material.
  • tetrafluoroethylene is fire retardant but possesses a disadvantage of drip inhibition, and is also processed with difficulty when blended with other resin composition.
  • thermal shrinkage it fails the 5V test of UL94, and there is always a fear of short circuit by destruction of wires and cables covering material in case of a fire.
  • tetrafluoroethylene contains fluoride, it is inherent in the problem of environmental pollution like the above-mentioned PVC resin.
  • the present invention solves the above mentioned issues with conventional technology, and offers a resin composition for wires and cables covering material, which is excellent in fire retardancy with non-halogen, excels in the chemical resistance, specifically in the distorted area and produces neither glaze nor a crack, and further has excellent compatibility, processabihty, heat resistance, impact resistance and flexibility.
  • resin composition I a resin composition where polyphenylene ether resin is blended with syndiotactic styrene polymer, styrene resin and non-halogen fire retardant in fixed ratio
  • resin composition II a resin composition obtained by blending polyphenylene ether resin with syndiotactic styrene polymer, styrene resin, non-halogen fire retardant and thermoplastic elastomer in fixed ratio
  • resin composition II a resin composition obtained by blending polyphenylene ether resin with syndiotactic styrene polymer, styrene resin, non-halogen fire retardant and thermoplastic elastomer in fixed ratio
  • E thermoplastic elastomer
  • component (A) is poly(2,6-dimethyl-l,4-phenylene)ether having intrinsic viscosity in the range of 0.08 to 0.60dl/g when measured in chloroform at 30°C in the first two embodiments.
  • non-halogen fire retardant (D) is aromatic phosphoric ester in the first and third embodiments.
  • thermoplastic elastomer (E) is the block copolymer of styrene and butadiene or styrene and isoprene in the second embodiment.
  • thermoplastic elastomer (E) is the block copolymer of styrene and butadiene or styrene and isoprene in the second embodiment.
  • PPE resin is the common name of the polymer having structure unit represented by general formula (I): [Formula I]
  • R ! , R 2 , R 3 and R independently represents hydrogen atom, halogen atom, hydrocarbon group, substituted hydrocarbon group, alkoxy group, cyano group, phenoxy group or nitro group respectively
  • n is the value representing polymerization degree
  • the polymer represented by general formula (I) can be used independently or can be used as copolymer formed by combining at least two kinds.
  • R , R 2 , R 3 and R 4 are chlorine, bromine, iodine, methyl, ethyl, propyl, aryl, phenyl, benzyl, methylbenzyl, chloromethyl, bromomethyl, cyanoethyl, cyano, methoxy, ethoxy, phenoxy, nitro groups etc.
  • the preferred PPE resm is the polymer havingR and R as alkyl group, specifically alkyl group having 1 to 4 carbon atoms, and R " t R 4 as hydrogen atom or alkyl group having 1 to 4 carbon atoms, n is preferred to be at least 50.
  • polyphenylene ether resin examples include poly(2,6-dimethyl-l,4-phenylene)ether, poly(2,6-di ethyl- l,4-phenylene)ether, poly(2-methyl-6-ethyl-l,4-phenylene)ether, poly(2-methyl-6-propyl-l,4-phenylene) ether, poly(2,6-dipropyl- 1 ,4-phenylene)ether, poly(2-ethyl-6-propyl- 1 ,4-phenylene)ether, poly(2,6-dimethoxy- 1 ,4-phenylene)ether, poly(2,6-dichloromethyl- 1 ,4-phenylene)ether, poly(2,6-dibromomethyl-l ,4-phenylene)ether, poly(2,6-diphenyl-l ,4-phenylene)ether, poly(2,6-ditolyl-l,4-phenylene)ether, poly(2,6-d
  • poly(2,6-dimethyl-l,4-phenylene)ether is generally prefened.
  • PPE resin when PPE resin is copolymer, tri-substituted alkyl phenol in the above mentioned repetitive polyphenylene ether unit e.g. copolymer having a part of group derived from 2,3,6-trimethylphenol, can be included. Further, in the PPE resin, copolymer having grafted styrene compound etc., can be used appropriately. As styrene compound grafted PPE, such as styrene, -methylstyrene, vinyl toluene, chlorostyrene etc., copolymer obtained by graft polymerization are included. Moreover, a modifier that has polar group can modify PPE resin.
  • polar group such as acidic hydride, carbonyl group, acid anhydride, acid amide, carboxylate ester, azide, sulfon group, nitrile group, cyano group, isocyanate ester, amino group, imide group, hydroxyl group, epoxy group, oxazoline group, thiol group etc.
  • polar group such as acidic hydride, carbonyl group, acid anhydride, acid amide, carboxylate ester, azide, sulfon group, nitrile group, cyano group, isocyanate ester, amino group, imide group, hydroxyl group, epoxy group, oxazoline group, thiol group etc.
  • the most preferred PPE resin is poly(2,6-dimethyl-l,4-phenylene)ether having intrinsic viscosity 0.12 to 0.51 dl/g (measured at 30°C using chloroform as a solvent).
  • component (A) polyphenylene ether resin is blended by 10 to 70 parts by weight, preferably 20 to 60 parts by weight with 100 parts by weight of resin composition I. If the blend ratio of component (A) is less than 10 parts by weight, the fire retardancy will be inadequate, on the other hand if it exceeds 70 parts by weight, chemical resistance will be weak and hence, neither is prefened.
  • component (BT) syndiotactic styrene polymer
  • Syndiotactic styrene polymer (B) used in the invention is styrene polymer having high degree syndiotactic structure.
  • syndiotactic structure where phenyl group or substituted phenyl group is positioned alternatively on the opposite side of side chain corresponding to the primary chain that is fomied by carbon-carbon bond, and the tacticity is dete ⁇ nined by Nuclear Magnetic Resonance method( 13 C — N M R method).
  • Nuclear Magnetic Resonance method( ' C — NMRmethod) determines the existing ratio of constitutional block of successive units, such as diode in case of 2 units, triode when 3 units and pentad for 5 units.
  • styrene polymer having syndiotacticity at least 75%, preferably at least 85% in diode or at least 30%, preferably at least 50% in case of racemic pentad.
  • styrene polymer are polystyrene, poly (alkyl styrene), poly (halogenated styrene) , poly(alkoxystyrene), poly(vinylbenzoate ester) and their mixtures, or copolymer comprising mainly of these components.
  • poly(alkylstyrene) such as poly(methylstyrene), poly(ethylstyrene), poly(isopropylstyrene), poly(t-butylstyrene) etc.
  • poly(halogenated styrene) such as poly(chlorostyrene), poly(bromostyrene), poly(fluorostyrene) etc.
  • poly(alkoxystyrene) such as poly(methoxystyrene), poly(ethoxystyrene) etc. are listed.
  • polystyrene polymer polystyrene, poly(p-methylstyrene), poly(m-methylstyrene), poly(p-tertiary-butyl styrene) are prefened, and further copolymer of styrene and p-methylstyrene can also be listed.
  • the preferred molecular weight of syndiotactic styrene polymer although it is not restricted but generally weight-average molecular weight (Mw) is atleast 10,000, and above all, the most appropriate is at least 50,000. If the weight-average molecular weight is less than 10,000, it has the tendency of weak chemical resistance. Furthermore, there are no restrictions about molecular weight distribution, and is appropriate for various things.
  • the melting point of syndiotactic styrene polymer is in the range of 200 to 310°C , and has outstanding chemical resistance as compared to conventional styrene polymer having atactic structure.
  • Such kind of syndiotactic styrene polymer can be manufactured by carrying out the polymerization of the styrene monomer (monomer conesponding to the above-mentioned styrene polymer) in the absence of an inactive hydrocarbon solvent or solvent, using condensation product of titanium compound and trialkyl aluminium with water as catalyst (e.g., Kokai no. 62-104818, Kokai no. 63-268709). Moreover, commercial product can also be used.
  • the above mentioned syndiotactic styrene polymer can be modified by modifier which has polar group.
  • polar group such as acidic hydride, carbonyl group, acid anhydride, acid amide, carboxylate ester, azide, sulfon group, nitrile group, cyano group, isocyanate ester, amino group, imide group, hydroxyl group, epoxy group, oxazoline group, thiol group etc.
  • acid anhydride and epoxy groups are preferred as polar groups and amongst the acid anhydride, maleic anhydride is preferred.
  • component (B) syndiotactic styrene polymer blends with 15 to 75 parts by weight, preferably 25 to 65 parts by weight to 100 parts by weight of resin composition I. If the blending ratio of component (B) is less than 15 parts by weight, the chemical resistance would be weak, on the other hand if more than 75 parts by weight, fire retardancy would be low, and therefore neither is prefened.
  • Styrene resin (C) used in the invention is the styrene resin not having syndiotactic structure other than above mentioned syndiotactic styrene polymer (B).
  • styrene resin not having syndiotactic structure homopolymer of styrene compound prepared by radical polymerization or styrene compound and the compound containing monomer that can be copolymerized, are mentioned.
  • styrene compound examples include styrene; alkyl substituted styrene, such as -methylstyrene, -ethylstyrene, -methyl-p-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene; halogenated styrene, such as o-chlorostyrene, m-chlorostyrene, p- chlorostyrene, p-bromostyrene, dichlorostyrene, dibromostyrene, trichlorostyrene, tribromostyrene etc. are listed, but styrene and -methylstyrene are preferred most amongst the all.
  • styrene compound and monomer that can be copolymerized are vinyl cyanide, such as acrylonitrile, methacrylonitrile, fumaronitrile, maleonitrile or methyl methacrylate, methyl acrylate, methacrylic acid, acrylic acid, maleic anhydride, are listed, but acrylonitrile is prefened most amongst the all.
  • component (C) styrene resin is blended by 0 to 50 parts by weight, preferably 10 to 40 parts by weight to 100 parts by weight of resin composition I. If the blend ratio of component (C) exceeds 50 parts by weight to 100 parts by weight of resin composition I, the chemical resistance would be weak and fire retardancy would also be low, and hence is not prefened.
  • phosphate ester fire retardants are prefened.
  • phosphate ester fire retardant such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate etc. or their substituted compound are listed.
  • the condensed phosphate ester that can be used in the invention is represented by the following general formula: [Formula 2]
  • R is the group selected from Al to A4; wherein, n varies from 1 to 1 0, Ax to AR are phenyl group, tolyl group or xylyl group respectively. Further, when n is at least 2, multiple AR4 may be same or differ). From the viewpoint of fire retardancy and heat-resistant, it is desirable that R is the structure of (A4). These can be used independently or atleast two types can also be used together.
  • the preferred phosphate ester fire retardant is aromatic phosphate ester having aromatic group. It is desirable that non-halogen fire retardant (D) is blended by 5 to 40 parts by weight, preferably 10 to 30 parts by weight corresponding to 100 parts by weight of resin composition I. If the blend ratio of component (D) is less than 5 parts by weight to
  • the resin composition II comprises thermoplastic elastomer (E) in addition to the other above described component (A), component (B), component (C) and component
  • thermoplastic elastomer (E) being used in the invention are styrene thermoplastic elastomer, polyolefin thermoplastic elastomer, polyester thermoplastic elastomer etc.
  • hydrogenated block copolymer of styrene and butadiene or styrene and isoprene of styrene thermoplastic elastomer are prefened.
  • the prefened hydrogenated styrene block copolymer is obtained by the hydrogenation of block polymer comprising polymer block A of mainly at least 2 vinyl aromatic compound and polymer block B of mainly at least 1 conjugate diene compound, e.g., hydrogenated product of vinyl aromatic compound-conjugate diene compound block copolymer containing structure A-B-A, B-A-B-A, (A-B) 4 -Si,
  • the hydrogenated block copolymer contains vinyl aromatic compound by 5 to 60% by weight, preferably 10 to 50% by weight, and further about the block structure, polymer block A mainly of vinyl aromatic compound is vinyl aromatic compound polymer block. Furtheraiore, if vinyl aromatic compounds exceeds 50% by weight, preferably vinyl aromatic compound of at least 70% by weight, it contains copolymer block structure of hydrogenated conjugate diene compound.Furthermore, block B of mainly hydrogenated conjugate diene compound is hydrogenated conjugate diene polymer block. If hydrogenated conjugate diene compound exceeds 50% by weight, preferably conjugate diene compound of at least 70% by weight, it contains copolymer block structure of vinyl aromatic compound.
  • polymer block A mainly of vinyl aromatic compound and polymer block B mainly of hydrogenated conjugate diene compound has random or tapered(the monomer components are increased or decreased as per molecular chain) distribution of molecular chain of vinyl aromatic compound or hydrogenated conjugate diene compound, or can be partial block or their arbitrary combination is also possible.
  • polymer block mainly of vinyl aromatic compound and polymer block mainly of hydrogenated conjugate diene compound are at least 2 blocks respectively, then each polymer block can either have the same structure or different structure.
  • Vinyl aromatic compound that forms the hydrogenated block copolymer are selected from below mentioned examples: styrene, — methylstyrene, vinyltoluene, p-tertiary- butylstyrene, but styrene is prefened most.
  • conjugate diene compound before hydrogenation which forms hydrogenated conjugate diene compound are selected from butadiene, isoprene, 1,3-pentadiene, 2,3- dimethyl-l,3-butadiene etc. but the preferred one are butadiene, isoprene and their combination. Therefore polymer block of mainly conjugate diene compound before hydrogenation is the micro structure in the block that can be chosen arbitrarily, e.g. in polybutadiene block, the micro structure is 20 to 50%, preferably 25 to 45%.
  • average molecular weight of hydrogenated styrene block copolymer comprising above mentioned structure is in the range of 5,000 to 1000,000, preferably 10,000 to 800,000, and further preferred range is 30,000 to 500,000 and molecular weight distribution (Mw/Mn) (ratio of average molecular weight (Mw) and number average molecular weight (Mn)) is below 10.
  • Mw/Mn molecular weight distribution
  • the molecular structure of hydrogenated block copolymer can be a straight chain, branched, radiation type or various combinations.
  • the block copolymer comprising above mentioned structure can be prepared by any of the method. According to preparation method mentioned in Kokai no. 40-23798, vinyl aromatic compound- conjugate diene compound block copolymer is synthesized in inactive solvent using lithium catalyst, and further can also be obtained by preparation method for hydrogenated vinyl aromatic compound- conjugate diene compound block copolymer mentioned in kokai no. 42-8704 and kokai no. 43-6636. Specifically, the hydrogenated block copolymer using titanium hydrogenated catalyst with outstanding weather resistance, heat-resistant degradation nature is prefened e.g., hydrogenated block copolymer can be synthesized by the method mentioned in Kokai no. 59-133203 and Kokai no.
  • thermoplastic elastomer (E) is blended by 10 to 200 parts by weight, preferably 20 to 150 parts by weight with respect to 100 parts by weight of resin composition I. If the blend ratio of component (E) is less than 10 parts by weight, the tensile elongation at break is inadequate, on the other hand if exceeds 200 parts by weight, the chemical resistance and fire retardancy would be low, and hence neither is prefened.
  • components (A) to (D), or components (A) to (E) commonly used additive agents such as pigments, dyes, fire retardancy supporter, stiffener (e.g. glass fibre, carbon fibre, whisker etc.), filler (e.g.
  • plasticizer oil, low molecular weight polyethylene, epoxidized soybean oil, polyethyleneglycol, fatty acid ester, etc.
  • fluidity improving agent antistatic agent
  • compatibilizer dicarboxylic acid and anhydrate, such as maleic anhydride, citric acid
  • antibacterial agent etc. can be added during blending or molding of the resin
  • the light stabilizer or ultraviolet absorbent such as hindered amine compound, benzoate compound, benzotriazole compound, benzophenone or formamidine etc. are effective in granting and improving the weather resistance.
  • nucleating agents such as inorganic talc, metallic salts of aromatic carboxylic acid, organic nucleating agents, such as sorbitol or metallic salts of aromatic phosphoric acid are effective in granting and improving the rigidity and brittleness.
  • Preparation method for the resin composition and molded object There is no restriction for the preparation method of resin compositions I and II used in the invention, the usual method can be used satisfactorily, and the common melt-mixing method is suitably adopted. Although use of small amount of solvent is also possible, generally it is unnecessary.
  • twin-screw extruder As melt and kneading apparatus, single screw extruder, twin-screw extruder, banbury mixer, roller mixer, kneader, brabender plastograph etc., are listed, but twin-screw extruder is preferred for melting and kneading methods. Since there are no restrictions for melting and kneading temperatures, but the common range is 150 to 350°C.
  • GPPS styrene resin
  • HIPS High Impact Styrene resin
  • Component (D): non-halogen fire retardant: compound represented by the following formula (i), but mixed compound having r 1 to 10 (brand name: CR733S, obtained from Daihachi Chemicals Co. ltd.) [Formula 3]
  • Stabilizer 2 Phenol stabilizer (brand name: Mark A050, obtained from Asahi Denka Kogyo Co. Ltd.),
  • the pellets were manufactured by melting and kneading the components in the ratio as shown in table 1 by using 30mm twin-screw extruder at melting temperature 280°C and revolution speed 280 ipm. Further, test piece was prepared using the pellets at temperature 280°C and tool temperature 60°C by injection molding.
  • the electric wire of outer diameter 0.94mm was made using the obtained pellet at temperature 280°C and linear velocity 130 to 260m/hour.
  • the following characteristic evaluations were performed for the obtained test piece and electric wire. The results are shown in Table 1.
  • the measuring method used for characteristic evaluation is as follows:
  • the resin composition for wires and cables covering material is excellent in fire retardancy with non-halogen, chemical resistance and melting properties, and since it also excels in workability, heat resistance, impact resistance and flexibility, the industrial utility value as a resin composition for wire cable covering material is extremely high.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine destinée à un utilisateur en tant que matière de recouvrement pour fils métalliques et câbles, qui est très ignifuge, sans être halogénée, et présente une grande résistance chimique et d'excellentes propriétés de fusion, ainsi qu'une grande aptitude à être travaillée, une grande résistance à la chaleur une grande résistance aux impacts et une grande souplesse. La composition de résine constituant un matériau de recouvrement pour fils métalliques et câbles est obtenue par mélange d'une résine d'éther de polyphénylène avec un polystyrène syndiotactique, une résine de polystyrène atactique et un ignifugeant non halogéné, ou bien par mélange d'une résine d'éther de polyphénylène avec un polystyrène syndiotactique, une résine de polystyrène atactique, un ignifugeant non halogéné et un élastomère thermoplastique selon des rapports fixés.
PCT/US2003/024909 2002-08-07 2003-08-07 Composition de resine pour recouvrir des fils metalliques et des cables Ceased WO2004014995A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003269953A AU2003269953A1 (en) 2002-08-07 2003-08-07 Resin composition for wire and cable coverings

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2002-230310 2002-08-07
JP2002230310A JP4007877B2 (ja) 2002-08-07 2002-08-07 ワイヤ・ケーブル被覆材用樹脂組成物
US10/632,606 US7005465B2 (en) 2002-08-07 2003-08-01 Resin composition for wire and cable coverings

Publications (1)

Publication Number Publication Date
WO2004014995A1 true WO2004014995A1 (fr) 2004-02-19

Family

ID=31719844

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/024909 Ceased WO2004014995A1 (fr) 2002-08-07 2003-08-07 Composition de resine pour recouvrir des fils metalliques et des cables

Country Status (2)

Country Link
AU (1) AU2003269953A1 (fr)
WO (1) WO2004014995A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1870908A1 (fr) 2006-06-23 2007-12-26 Delphi Technologies, Inc. Câble véhiculaire isolé sans métaux lourds non-halogénés

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356857A2 (fr) * 1988-08-31 1990-03-07 Idemitsu Kosan Company Limited Articles moulés étirés à partir des composition de polymère à base de styrène et leur procédé de fabrication
EP0422495A1 (fr) * 1989-10-13 1991-04-17 Idemitsu Kosan Company Limited Composition à base de polymère de styrène
JPH0753815A (ja) * 1993-08-17 1995-02-28 Idemitsu Kosan Co Ltd 耐衝撃性ポリスチレン系樹脂組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0356857A2 (fr) * 1988-08-31 1990-03-07 Idemitsu Kosan Company Limited Articles moulés étirés à partir des composition de polymère à base de styrène et leur procédé de fabrication
EP0422495A1 (fr) * 1989-10-13 1991-04-17 Idemitsu Kosan Company Limited Composition à base de polymère de styrène
JPH0753815A (ja) * 1993-08-17 1995-02-28 Idemitsu Kosan Co Ltd 耐衝撃性ポリスチレン系樹脂組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; OKADA, AKIHIKO ET AL: "Impact-resistant styrene polymer compositions", XP002264975, retrieved from STN Database accession no. 122:316175 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1870908A1 (fr) 2006-06-23 2007-12-26 Delphi Technologies, Inc. Câble véhiculaire isolé sans métaux lourds non-halogénés
US7408116B2 (en) 2006-06-23 2008-08-05 Delphi Technologies, Inc. Insulated non-halogenated heavy metal free vehicular cable
US7687720B2 (en) 2006-06-23 2010-03-30 Delphi Technologies, Inc. Insulated non-halogenated heavy metal free vehicular cable

Also Published As

Publication number Publication date
AU2003269953A1 (en) 2004-02-25

Similar Documents

Publication Publication Date Title
US7005465B2 (en) Resin composition for wire and cable coverings
US7524894B2 (en) Resin composition for wire and cable covering material
KR100424085B1 (ko) 난연성폴리스티렌계수지조성물및폴리스티렌계수지성형체
JPH0995610A (ja) 難燃樹脂組成物
JP2009197196A (ja) 樹脂組成物
WO1996036658A1 (fr) Procede de fabrication de polyphenylene ether modifie par acide et composition de resine de polystyrene
JP4364319B2 (ja) ポリフェニレンエーテル系樹脂組成物
JPH07224193A (ja) ポリマーの組成物
JPH07224192A (ja) ポリマー組成物
JP3797895B2 (ja) ワイヤ・ケーブル被覆材用難燃性樹脂組成物
JP5455289B2 (ja) 難燃性着色樹脂組成物の製造方法
KR100727693B1 (ko) 난염제 조성물 및 제품
WO2004014995A1 (fr) Composition de resine pour recouvrir des fils metalliques et des cables
JP2008101200A (ja) 熱可塑性樹脂組成物
JP4574150B2 (ja) 柔軟性に優れる樹脂組成物
JP4294328B2 (ja) ポリフェニレンエーテル系樹脂組成物
JP2002146037A (ja) 難燃性熱可塑性樹脂ブレンド物の製造方法
US20040152838A1 (en) Chemical-resitant polystyrene resin compositon and molded article
JP2005008762A (ja) 食品容器用樹脂組成物
JP2019104824A (ja) 樹脂組成物、樹脂組成物の製造方法、及び成形体
JP4083348B2 (ja) 熱可塑性エラストマー組成物
JP5411800B2 (ja) 柔軟性に優れる樹脂組成物を用いたワイヤ被覆材またはケーブル被覆材
JP2002155179A (ja) 難燃樹脂組成物
JP2009227886A (ja) 熱可塑性樹脂組成物
JPH0753859A (ja) 難燃性熱可塑性樹脂組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SK SL TJ TM TN TR TT TZ UA UG UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase