CN100374502C - Poly(butylene terephthalate) resin composite and multilayered insulating wire containing the same - Google Patents
Poly(butylene terephthalate) resin composite and multilayered insulating wire containing the same Download PDFInfo
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- CN100374502C CN100374502C CNB2005100714074A CN200510071407A CN100374502C CN 100374502 C CN100374502 C CN 100374502C CN B2005100714074 A CNB2005100714074 A CN B2005100714074A CN 200510071407 A CN200510071407 A CN 200510071407A CN 100374502 C CN100374502 C CN 100374502C
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- polybutylene terephthalate
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- 229920001707 polybutylene terephthalate Polymers 0.000 title claims abstract description 73
- -1 Poly(butylene terephthalate) Polymers 0.000 title claims abstract description 38
- 239000000805 composite resin Substances 0.000 title 1
- 238000000576 coating method Methods 0.000 claims abstract description 48
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000728 polyester Polymers 0.000 claims abstract description 26
- 229920001971 elastomer Polymers 0.000 claims abstract description 23
- 239000000806 elastomer Substances 0.000 claims abstract description 23
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 239000011342 resin composition Substances 0.000 claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 150000001408 amides Chemical class 0.000 claims description 14
- 239000003381 stabilizer Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 4
- 150000007970 thio esters Chemical class 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- 238000012661 block copolymerization Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims 1
- 238000001125 extrusion Methods 0.000 abstract description 18
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000004952 Polyamide Substances 0.000 abstract description 3
- 229920002647 polyamide Polymers 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 14
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 238000007765 extrusion coating Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- IEBJZLRZRKTGFN-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C1=CC=CC=C1 Chemical compound N=NC=NN.N=NC=NN.C1=CC=CC=C1 IEBJZLRZRKTGFN-UHFFFAOYSA-N 0.000 description 2
- 239000006085 branching agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000012438 extruded product Nutrition 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
- B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
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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
-
- 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
-
- 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
-
- 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
- H01B3/421—Polyesters
- H01B3/422—Linear saturated polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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- Polymers & Plastics (AREA)
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a modified polybutylene terephthalate resin composition and a multi-layer insulative electric wire, the modified polybutylene terephthalate resin composition consists of polybutylene terephthalate 50-95wt%, styrene-ethylene-butadiene-styrene copolymer 1-20wt%, polyester elastomer 1-30wt%, and titanium dioxide 0.5-10wt%; the insulative electric wire includes includes a wire, a first coating of one or more layers of polybutylene terephthalate resin, and a second coating formed of polyamide. The modified polybutylene terephthalate resin composition of the invention has good flowability and extrusion performance, is capable of being used for manufacturing the multi-layer insulative electric wire with improved wire appearance, heat resistance, abradability solderability and insulating property, with high efficiency.
Description
Technical field
The present invention relates to a kind of polybutylene terephthalate resin composition and the multi-layer insulated electrical wire that comprises the insulating coating that above-mentioned composition makes of modification.More particularly, the present invention relates to the polybutylene terephthalate resin composition of the good modification of a kind of flowability and extrusion performance, and the multi-layer insulated electrical wire that comprises the insulating coating that above-mentioned composition makes, its outward appearance homogeneity, thermotolerance, wear resistance and insulating property are good.
Technical background
Polyester (crystalline resins) is commonly used for insulation compound.But because it is mobile and extrusion performance is poor, there are some problems in polyester.Specifically be that because it extrudes the fluctuation in the output, the electric wire that is got by polyester has uneven insulating coating.Therefore, insulating property and thermotolerance reduce, and easily because of temperature change changes, thereby make the processibility variation.
Simultaneously, along with the development of the trend toward miniaturization of selectron (ultraelectronic) product of recent use high frequency and electric/electronic, used insulated line requires to have the electric stability and the insulation layer of reinforcement in the small sized product.
Recently the trend of the battery of the AC power source adapter of electronic product such as Personal Computer, mobile telephone and indicating meter and VTR camera also is towards miniaturization and high-performance development.At this on the one hand, more and more need its thermotolerance, insulating property and the better multi-layer insulated electrical wire of outward appearance homogeneity.
Therefore, the inventor finds to comprise that the insulated line of the insulating coating that is made by modification polybutylene terephthalate resin composition has obviously improved the required physicals of insulated line, has finished the present invention thus; Above-mentioned resin combination comprises polybutylene terephthalate, polyester elastomer, SIS/SEBS and the titanium dioxide of proper ratio.
Summary of the invention
The purpose of this invention is to provide the good polybutylene terephthalate resin composition of a kind of flowability and extrusion performance.
Another purpose of the present invention provides a kind of outward appearance homogeneity, thermotolerance, wear resistance and the good multi-layer insulated electrical wire of insulating property.
Another purpose of the present invention provides a kind of coating resin composition that is used for the coating multiple insulated line, and it comprises the polybutylene terephthalate main ingredient.
Another purpose of the present invention provides a kind of extruded product that is made by the polybutylene terephthalate resin composition of modification.
Description of drawings
Fig. 1 is the sectional view of multi-layer insulated electrical wire, and described electric wire comprises lead, two-layer coating and the polyamide coating layer that is made by polybutylene terephthalate resin composition of the present invention.
Fig. 2 is the schematic flow sheet that shows multi-layer insulated electrical wire manufacture method of the present invention.
Embodiment
The invention provides a kind of polybutylene terephthalate resin composition and the multi-layer insulated electrical wire that comprises the insulating coating that above-mentioned composition makes of modification.
One aspect of the present invention provides a kind of polybutylene terephthalate resin composition, and it comprises 50-95 weight % polybutylene terephthalate, 1-20 weight % SIS/SEBS, 1-30 weight % polyester elastomer and 0.5-10 weight % titanium dioxide.
Described polybutylene terephthalate resin composition is used in the extruded product, comprises pipe, film, line etc., is used on coating insulated line of the present invention.
The present invention provides a kind of multi-layer insulated electrical wire on the other hand, and it comprises lead, one or more layers polybutylene terephthalate resin first coating, and second coating that is formed by polymeric amide; Above-mentioned polybutylene terephthalate resin carries out polymerization afterwards and makes by mixing 50-95 weight % polybutylene terephthalate, 1-20 weight % SIS/SEBS, 1-30 weight % polyester elastomer and 0.5-10 weight % titanium dioxide.
The present invention hereinafter is described in further detail.
The invention provides a kind of polybutylene terephthalate (hereinafter referred is " PBT ") resin combination, it comprises 50-95 weight % polybutylene terephthalate, 1-30 weight % polyester elastomer, 1-20 weight % SIS/SEBS and 0.5-10 weight % titanium dioxide.
When using twin screw extruder under 240-280 ℃, to mix and extruding described PBT, SIS/SEBS, polyester elastomer and during titanium dioxide, form the PBT resin of modification.Those skilled in the art are used to form the mixing and the expressing technique of resin easily.
The modified PBT of Xing Chenging has improved the required physicals of insulated line thus, comprises flowability, extrusion performance, outward appearance homogeneity, thermotolerance, wear resistance and insulating property, has improved workability thus.In this article, term " flowable " is meant the flowability that is suitable for making electric wire, is meant that in detail flowability guarantees that the melting behaviour of the solution tension force of polymkeric substance in forcing machine, polymkeric substance and the external diameter of electric wire can not be affected.
The melt temperature that is used as the PBT of main ingredient in the resin combination of the present invention is 220-240 ℃, and limiting viscosity (I.V.) is 0.7-1.3dl/g, better is 0.75-1.2dl/g.If the I.V. of PBT extrudes difficult processing to carry out less than 0.7dl/g.On the other hand, if surpass 1.3dl/g, then, can cause occurring being separated or the physical properties variation owing to extrude the processing temperature difference between PBT and other component (being SIS/SEBS and polyester elastomer).
In resin combination of the present invention, the consumption of described PBT is preferably 50-95 weight %.If the content of PBT then because of its deficiency can cause forming disperse phase, loses the proper property of PBT thus less than 50 weight % in the resin combination.On the other hand, if surpass 95 weight %, then excessive meeting causes causing degraded appearance in that to extrude in the processing flowability at a high speed extremely low.
Be preferably, in resin combination, the consumption of described SIS/SEBS is 1-20 weight %.If the content of SIS/SEBS surpasses 20 weight %, then extrude processing and excess shrinkage can occur afterwards, make the in uneven thickness of insulated line like this.On the other hand, if less than 1 weight %,, can cause occurring being separated because the consistency of it and PBT and polyester elastomer is poor, so just unfavorable to the electrical property of insulated line.
Be preferably, the Xiao A hardness of described SIS/SEBS is 70-80, and the flowability under 10Kg load and 230 ℃ is 10-15g/ minute.
Described polyester elastomer is by the hard section of block copolymerization and soft section thermoplastic polymer that makes.Usually, aromatic dicarboxylic acid is as hard section, and lower glycol or polyalkylene oxide are as soft section.
The example of aromatic dicarboxylic acid comprises that terephthalic acid (PTA), a benzene diformazan (IPA), a benzene diformazan dimethyl ester or dimethyl terephthalate (DMT) (DMT) (are to replace 1,5-two naphthalene dicarboxylic acids (1,5-NDCA), 2,6-two naphthalene dicarboxylic acids (2,6-NDCA) or diacid and dimethylated aromatic dicarboxylic acid ester) or their mixture.Wherein, preferred DMT.
Described lower glycol can be ethylene glycol, propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol or 1,4 cyclohexane dimethanol.Preferably 1, the 4-butyleneglycol.
Described polyalkylene oxide can be polyoxyethylene glycol, polypropylene glycol or polytetramethylene glycol (PTMEG).Better be PTMEG.
And, can use branching agent to improve the melt tension of polyester elastomer, improve the stability of the extrusion that is used for making insulated line thus, improve insulating property thus.The example of described branching agent comprises glycerine, tetramethylolmethane or neopentyl glycol, wherein, better is glycerine.
In described resin combination, the consumption of described polyester elastomer is preferably 1-30 weight %.If the content of polyester elastomer surpasses 30 weight %, then can occur and being separated of PBT, be unfavorable for the extrusion performance and the flowability of insulated line like this.On the other hand, if less than 1 weight %, then the elasticity of resin combination can reduce, and causes the output fluctuation of extruding of insulated line thus.As a result, the insulation layer of insulated line can be inhomogeneous.
With regard to the electrical property of insulated line, in resin combination, the present invention better uses the titanium dioxide of 0.5-10 weight %.If the content of titanium dioxide is less than 0.5 weight %, the heat that insulated line produces can cause variable color.On the other hand, if surpass 10 weight %, then serious breaking can appear in the outside surface at insulated line, makes the electrical property variation of insulated line.
Resin combination of the present invention can also comprise arylamine, phenol, thioesters or phosphorous acid ester group thermo-stabilizer.Be preferably, in resin combination, the consumption of described thermo-stabilizer is 0.1-5 weight %.The content of described thermo-stabilizer is the usual amounts in field under the present invention.
The proof voltage of the modified PBT resin that the present invention forms, thermotolerance, flexible, weldability, flowability, extrusion performance and outward appearance homogeneity are good, therefore are suitable for forming the insulation layer that constitutes multi-layer insulated electrical wire.At this on the one hand, the present invention also provides the insulated line that comprises above-mentioned PBT resin.
Insulated line of the present invention comprises lead, one or more layers first coating that is formed by PBT, and second coating that forms by polymeric amide, wherein, described PBT resin carries out polymerization afterwards and makes by mixing 50-95 weight %PBT, 1-20 weight % SIS/SEBS, 1-30 weight % polyester elastomer and 0.5-10 weight % titanium dioxide.
The lead that is used for insulated line can be a kind of lead that is used for common wiring, for example copper.
The polymeric amide that is used for insulated line can be common commercially available polymeric amide.But preferred I.V. is 1-2, better is the polymeric amide of 1.1-1.3.
Second coating that is formed by polymeric amide can be multilayer form.From stretchiness and flexible, better form second coating that is form of single sheet.
In insulated line of the present invention, described PBT resin and polymeric amide form the multilayer that covers described lead.Described PBT resin can be a single or multiple lift.But preferably make the PBT resin formation for double-deck.
When lead covers with individual layer PBT resin coating, when satisfying the requiring of insulated line desired physical properties (as proof voltage, thermotolerance, flexible, weldability, flowability, extrusion performance and outward appearance homogeneity), described resin coating requires to form thicker thickness.
But the coating of thicker resin is difficult to make little insulated line, and satisfies physicals, as weldability and workability.
At this on the one hand, require coating thin as far as possible, fully satisfy the required physical properties of insulated line simultaneously.
For this reason, in preferred implementation of the present invention, lead covers successively with the two-layer insulating coating and the good polyamide coating layer of frictional coefficient of modified PBT resin formation.
Fig. 1 has illustrated the sectional view of multi-layer insulated electrical wire, and described electric wire comprises the coating that is made by the above-mentioned PBT resin combination of the present invention.
In Fig. 1, three coatings of lead 1 usefulness (that is, and by first and second coatings 2 of modified PBT resin formation of the present invention and 3 and the 3rd coating 4 that forms by polymeric amide) cover successively, form multi-layer insulated electrical wire 5 thus, its resistance, thermotolerance and high abrasion resistance.
For insulated line of the present invention, coating is formed on the lead by independent order extrusion coating method.This is can form the single coating that the mixture by modified PBT and polymeric amide forms because be coated with modified PBT and polymeric amide simultaneously, causes the physicals of insulated line can not be satisfactory.Good insulating property are guaranteed in this order insulation of the present invention coating.
And when extruding, the total thickness of coating is the 60-160 micron, compares conventional coiling technology, and the physical properties of insulated line can improve.
Insulated line of the present invention can be by common extrusion coating method manufacturing.Coat-thickness by extrusion coated formation there is not special restriction.For example, when diameter of wire is about 0.4mm, form very thin multi-layer insulated electrical wire, promptly the total thickness of coating is about 100 microns (each coating is about 33 microns).
Those skilled in the art in the invention know the extrusion coating method of electric wire.Fig. 2 is the schematic flow sheet that shows multi-layer insulated electrical wire coating process of the present invention.Use automation system to carry out under the linear speed of extrusion coated 160-280 more fortunately ℃ bowl temperature, the screw rod speed of rotation of 10-30RPM and 100-500MPM, make it can not produce degree of eccentricity.After each expressing technique, in each cooling zone, coating is cooled to 100 ℃ or following, each layer separated.
Multi-layer insulated electrical wire of the present invention can be used for the high-performance variable depressor, and its weight ratio conventional transformer is lighter, and volume is littler.And multi-layer insulated electrical wire of the present invention can efficiently be used for microelectronic product, as battery charger, printer, digital camera or the mobile telephone of VTR, printing press, facsimile recorder, computer, umformer, recreational machine etc.
Hereinafter the present invention is described in further detail by embodiment.But following examples only are used for explanation, are used to limit the present invention anything but.
Embodiment
By mixing component described in the following table 1, carry out each modified PBT resin that polymerization prepares embodiment 1 and Comparative Examples 1-4 afterwards.
Simultaneously, the annealed copper bare wire (solid wire) of use diameter 0.4mm or single strand wire are as lead.Described lead covers the modified PBT resin of embodiment 1 and Comparative Examples 1-4, forms first and second insulating coatings, then, covers polymeric amide, forms the 3rd coating, and the total thickness that makes coating is 0.65mm.
These insulating coatings of described lead use common equipment shown in Figure 2 to form.
Described lead offers extrusion coated streamline and preheating from discharging drum etc.As shown in Figure 2, lead is through pinblock and extrusion die, and afterwards through first forcing machine 6, second forcing machine 7 and the 3rd forcing machine 8, order covers first, second and the 3rd coating.Through after each forcing machine 6,7 and 8, described lead respectively in first cooling zone 9, second cooling zone 10 and 11 coolings of the 3rd cooling zone, as shown in Figure 2.The pin hole existence of evaluation gained coating structure, external diameter, degree of eccentricity etc.Afterwards, the gained coating structure use to determine that the capstan winch 12 of linear speed pulls out with constant speed, use then winding machine 13 with them on drum.
At this moment, carry out under the linear speed of the screw rod speed of rotation of described extrusion coated cylinder temperature, 30RPM at 260 ℃ and 300MPM.Below be the physical properties of estimating the multi-layer insulated electrical wire that makes thus under the condition of room temperature (25 ℃) and 45% relative humidity, the results are shown in Table 1 for it.
＜electric wire outward appearance 〉
By observing the outward appearance that crack on each insulated line on the bobbin or flaw are with the naked eye estimated insulated line.Satisfying the following electric wire outward appearance that requires is chosen as good: there are not crack, smooth surface, evenly gloss and surface color, and sticking and wear and tear hardly when scraping with nail.
＜workability 〉
The workability of estimating described multi-layer insulated electrical wire by the flowability and the extrusion performance of material.According to following standard, on 100g/ minute basis, estimate flowability by the output of extruding in the certain hour in the forcing machine extrusion process:
± 2g or following: excellent
± 5g or following: good
± 10g or following: in
(unit: ampere, stability A) is estimated extrusion performance to motor load by forcing machine.Estimate the stable as follows of motor load on the basis of 30RPM and 20A: even the amperage fluctuation range is
± 2A or following: excellent
± 5A or following: good
± 10A or following: in
＜thermotolerance 〉
The thermotolerance of following evaluation multi-layer insulated electrical wire: at 118MPa (12Kg/mm
2) heavy burden under be on the axle of 6mm around diameter with 10 circle multi-layer insulated electrical wires, afterwards 225 ℃ of down heating 30 minutes.Then, will be around the multi-layer insulated electrical wire uncoiling on the axle, the crack that visual inspection exists.When not observing the crack, add the voltage 1 minute of 3000V.When not having circuit defect, estimate the electric wire of being tested and pass through class requirement.After carrying out 10 tests, according to following standard evaluation thermotolerance:
Test by 10 times: excellent
Test by 9 times: good
Test by 8 times: normal
By 7 times the test or below: poor
＜weldability 〉
According to KS (Korean Industrial Standard) C 3006.16, take off 34 samples (length is about 15cm separately) from identical bobbin.The front end that then length is about each sample of 40mm immerses according to KS D 6704 and is set in middle scheduled time of 50Sn (solder flux) preset temperature under.From 50Sn, taking out afterwards immediately with suitable fragment wiping specimen gently.Whether evenly be formed on by the visual inspection solder flux on the immersion part of specimen and estimate weldability, except each immerses the end (about 10mm) of part.
＜insulating property 〉
For diameter is 0.05mm or above insulated line, according to the legal measurement breakdown voltage of multiple twin.In described multiple twin is legal, take off 3 specimen (length is about 50cm) from identical bobbin.Each specimen doubling, and with the long part of the about 12cm of predetermined number stranded each specimen under predetermined tension.After removing tension force, cut the part of each doubling, and apply the sine-shaped voltage of alternating current of about 60Hz 1 minute.According to following standard, estimate insulating property according to the proof voltage of each specimen:
Anti-8Ky or above voltage: excellent
Anti-7Kv or above voltage: good
Anti-6Ky or above voltage: in
＜wear resistance 〉
Inject the insulated line sample, form the plate-like that thickness is about 2mm, use wearability test machine (Taberabrasion test) to measure the wear resistance of injecting sample then.After repeating 1000 times under the load of 500g, measure, and use H-18 as grinding stone.Evaluation of result is a wear intensity (mg/1000 time).
Table 1
| Form (weight %) | | Embodiment | ||||
| 1 | 2 | 3 | 4 | 1 | ||
| PBT(A) | 100 | 90 | 80 | 70 | 65 | |
| Polyester elastomer (B) | - | 10 | 10 | 10 | 20 | |
| SIS/SEBS (C) | - | - | 10 | 20 | 10 | |
| Titanium dioxide (D) | - | - | - | - | 5 | |
| Total amount | 100 | 100 | 100 | 100 | 100 | |
| Characteristic | ||||||
| Workability | X | △ | ○ | ○ | ○ | |
| The electric wire outward appearance | △ | ○ | ○ | △ | ◎ | |
| Thermotolerance | X | △ | ○ | △ | ◎ | |
| Wear resistance | △ | △ | △ | ○ | ◎ | |
| Weldability | △ | △ | ○ | ○ | ◎ | |
| Insulating property | X | X | △ | ○ | ○ | |
◎: excellent; Zero: good; △: in; X: poor
As shown in table 1, all physicalies of the insulated line of embodiment 1 (wherein using all PBT (A), polyester elastomer (B), SIS/SEBS (C) and titanium dioxide (D)) are all good.But, compare with embodiment 1 described insulated line, for the insulated line of Comparative Examples 1-4 (only use PBT or saved in the component (A)-(D) one or more), the desired physical properties of common insulated line can not be satisfactory.
Embodiment 2-4 and Comparative Examples 5
The composition and the physical properties of the multi-layer insulated electrical wire of embodiment 2-4 and Comparative Examples 5 have been listed in the following table 2.Carrying out polymerization after the component of each modified PBT resin of embodiment 2-4 and Comparative Examples 5 by mixture table 2 prepares.
Then, use first and second coatings of embodiment 2-4 and Comparative Examples 5 described each modified PBT resin formation to cover lead, and (Korea) the 3rd coating that forms cover, and makes multi-layer insulated electrical wire for KOPA KM333HS, Kolon Corporation with polymeric amide.Shown in embodiment 1, estimate the physical properties of insulated line in an identical manner.
Used material and the method that forms coating are as described in the above embodiment 1 among these embodiment.
Table 2
| Form (weight %) | Embodiment | Comparative Examples | |||
| 2 | 3 | 4 | 5 | ||
| The first layer and the second layer | PBT(A) | 54 | 74 | 84 | 95 |
| Polyester elastomer (B) | 25 | 20 | 5 | - | |
| SIS/SEBS (C) | 20 | 5 | 10 | - | |
| Titanium dioxide (D) | 1 | 1 | 0.5 | 5 | |
| Thermo-stabilizer (E) | - | - | 0.5 | - | |
| Total amount | 100 | 100 | 100 | 100 | |
| The 3rd layer | Polymeric amide | 100 | 100 | 100 | 100 |
| Characteristic | |||||
| Workability | ◎ | ◎ | ◎ | △ | |
| The electric wire outward appearance | ○ | ◎ | ◎ | ○ | |
| Thermotolerance | ◎ | ◎ | ◎ | △ | |
| Wear resistance | ◎ | ◎ | ◎ | ◎ | |
| Weldability | ◎ | ◎ | ◎ | △ | |
| Insulating property | ◎ | ◎ | △ | ○ | |
◎: excellent; Zero: good; △: in; X: poor
As shown in table 2, comprise among the embodiment 2-4 that the insulated line of the coating that is formed by PBT resin combination of the present invention presents good electric wire outward appearance, thermotolerance, wear resistance and insulating property.On the other hand, the physicals of the insulated line of Comparative Examples 5 (not using polyester elastomer (B) and SIS/SEBS (C)) is poor.
As for wear intensity, the wear intensity of the described sample of Comparative Examples 1-5 is respectively 85,91,84,81 and 52 (mg/1000 time), and the wear intensity of the described sample of embodiment 1-4 is respectively 43,67,66 and 71 (mg/1000 time).In Comparative Examples 5, other characteristic of sample is ungood, still its high abrasion resistance when adding 5% titanium dioxide.From described result as seen, when adding titanium dioxide, the high abrasion resistance of sample, and the amount of the titanium dioxide of wear resistance and adding is directly proportional.
The specification of used PBT (A), polyester elastomer (B), SIS/SEBS (C), titanium dioxide (D) and thermo-stabilizer (E) is as follows among embodiment 1-4 and the Comparative Examples 1-5:
(A)PBT：TRIBIT 1700S(Samyang Corp.，Korea)
(B) polyester elastomer: TRIEL 5400 (Samyang Corp.)
(C) SIS/SEBS: GTV55N (Kwangsung PlasticCo.korea) is characterized in that Xiao A hardness is 75, is 13g/ minute at 230 ℃ with 10Kg load current downflow
(D) titanium dioxide: R106 (DuPont)
(E) thermo-stabilizer: thioester substrate thermo-stabilizer 412S (DuPont)
Industrial applicability
Modified PBT resin of the present invention has good flowability and extrusion performance, therefore, can be efficiently for the manufacture of multi-layer insulated electrical wire, described electric wire has improved electric wire outward appearance, heat resistance, wearability, solderability and insulating properties. The insulated electric conductor that comprises the insulating barrier that is formed by modified PBT resin of the present invention satisfies the various physical properties of minitype high-performance required by electronic product.
Claims (7)
1. polybutylene terephthalate resin composition, it comprises 50-95 weight % polybutylene terephthalate, 1-20 weight % SIS/SEBS, 1-30 weight % polyester elastomer and 0.5-10 weight % titanium dioxide, polyester elastomer is made by block copolymerization aromatic dicarboxylic acid and lower glycol or polyalkylene oxide, the melt temperature of described polybutylene terephthalate is 220-240 ℃, and limiting viscosity (I.V.) is 0.7-1.3dl/g.
2. polybutylene terephthalate resin composition as claimed in claim 1 is characterized in that, it also comprises 0.1-5 weight % arylamine, phenol, thioesters or phosphorous acid ester group thermo-stabilizer.
3. polybutylene terephthalate resin composition as claimed in claim 1 is characterized in that, the Xiao A hardness of described SIS/SEBS is 70-80.
4. multi-layer insulated electrical wire, it comprises successively:
Lead;
First coating that one or more layers is formed by polybutylene terephthalate resin, described resin comprises 50-95 weight % polybutylene terephthalate, 1-20 weight % SIS/SEBS, 1-30 weight % polyester elastomer and 0.5-10 weight % titanium dioxide, polyester elastomer is made by block copolymerization aromatic dicarboxylic acid and lower glycol or polyalkylene oxide, the melt temperature of described polybutylene terephthalate is 220-240 ℃, and limiting viscosity (I.V.) is 0.7-1.3dl/g; And
Second coating that forms by polymeric amide.
5. multi-layer insulated electrical wire as claimed in claim 4 is characterized in that, described polybutylene terephthalate resin first coating also comprises 0.1-5 weight % arylamine, phenol, thioesters or phosphorous acid ester group thermo-stabilizer.
6. multi-layer insulated electrical wire as claimed in claim 4 is characterized in that, the Xiao A hardness of described styrene-ethylene-butadienestyrene copolymer is 70-80.
7. extrude product for one kind, it is by each described polybutylene terephthalate resin preparation of compositions of claim 1-3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040084467 | 2004-10-21 | ||
| KR1020040084467A KR100617706B1 (en) | 2004-10-21 | 2004-10-21 | Polybutylene Terephthalate Resin Composition and Multi-layer Insulating Electric Wire Comprising the Same |
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| Publication Number | Publication Date |
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| CN1763133A CN1763133A (en) | 2006-04-26 |
| CN100374502C true CN100374502C (en) | 2008-03-12 |
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| CNB2005100714074A Active CN100374502C (en) | 2004-10-21 | 2005-05-13 | Poly(butylene terephthalate) resin composite and multilayered insulating wire containing the same |
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| Country | Link |
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| KR (1) | KR100617706B1 (en) |
| CN (1) | CN100374502C (en) |
| HK (1) | HK1087725A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5205979B2 (en) * | 2007-01-23 | 2013-06-05 | 日立電線株式会社 | Insulated wire |
| KR100839509B1 (en) * | 2007-11-19 | 2008-06-19 | 영창실리콘 주식회사 | Fine electrical wire and the insulation |
| JP5200563B2 (en) * | 2008-02-01 | 2013-06-05 | 日立電線株式会社 | Insulated wire |
| CN102099872B (en) * | 2008-07-29 | 2012-11-14 | 古河电气工业株式会社 | Insulated wire |
| JP5468944B2 (en) * | 2010-03-12 | 2014-04-09 | 矢崎総業株式会社 | Extruded flexible flat cable |
| KR101738755B1 (en) | 2015-07-02 | 2017-05-22 | 영창실리콘 주식회사 | A method of manufacturing of environmental friendly polymer compound enhanced hydrolysis and thermal resistance and, a multilayer insulated wire and a manufacturing method therefor |
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| CN1043514A (en) * | 1988-10-07 | 1990-07-04 | 住友电装株式会社 | Improve the moulding compound of mobile polybutylene terephthalate |
| CN1445281A (en) * | 2003-04-10 | 2003-10-01 | 广州金发科技股份有限公司 | Super malleable poly butylene terephthalate (PBT) complex and its preparing method |
| KR100439695B1 (en) * | 2003-11-07 | 2004-07-12 | 영창실리콘 주식회사 | The several layer insulated wire |
| CN1513911A (en) * | 2002-12-31 | 2004-07-21 | 中国石油化工股份有限公司 | Polybutanediol terephthalate composition and its preparation method |
| CN1518579A (en) * | 2001-06-27 | 2004-08-04 | ������������ʽ���� | Flame-retardant resin composition |
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| KR100500834B1 (en) * | 2000-01-20 | 2005-07-12 | 주식회사 코오롱 | Polyester-based heat-contractible tube for coating eletrolytic condenser |
| TW495771B (en) * | 2000-01-25 | 2002-07-21 | Furukawa Electric Co Ltd | Multilayer insulated wire and transformer using the same |
| KR100537100B1 (en) * | 2000-10-24 | 2005-12-16 | 주식회사 코오롱 | Polyester-based thermal contraction tube |
-
2004
- 2004-10-21 KR KR1020040084467A patent/KR100617706B1/en active IP Right Grant
-
2005
- 2005-05-13 CN CNB2005100714074A patent/CN100374502C/en active Active
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| CN1043514A (en) * | 1988-10-07 | 1990-07-04 | 住友电装株式会社 | Improve the moulding compound of mobile polybutylene terephthalate |
| CN1518579A (en) * | 2001-06-27 | 2004-08-04 | ������������ʽ���� | Flame-retardant resin composition |
| CN1513911A (en) * | 2002-12-31 | 2004-07-21 | 中国石油化工股份有限公司 | Polybutanediol terephthalate composition and its preparation method |
| CN1445281A (en) * | 2003-04-10 | 2003-10-01 | 广州金发科技股份有限公司 | Super malleable poly butylene terephthalate (PBT) complex and its preparing method |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1763133A (en) | 2006-04-26 |
| KR20060035119A (en) | 2006-04-26 |
| HK1087725A1 (en) | 2006-10-20 |
| KR100617706B1 (en) | 2006-08-28 |
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