CN1954029A - Thermoplastic polymer composition - Google Patents
Thermoplastic polymer composition Download PDFInfo
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- CN1954029A CN1954029A CNA2005800156589A CN200580015658A CN1954029A CN 1954029 A CN1954029 A CN 1954029A CN A2005800156589 A CNA2005800156589 A CN A2005800156589A CN 200580015658 A CN200580015658 A CN 200580015658A CN 1954029 A CN1954029 A CN 1954029A
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- rubber
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- ethylene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
Disclosed is a thermoplastic polymer composition which has both excellent heat resistance and excellent chemical resistance while having flexibility and excellent formability. The thermoplastic polymer composition is composed of a fluororesin (A) and a non-fluorine crosslinked rubber (B). The fluororesin (A) is composed of a fluorine-containing ethylenic polymer (a), and the a non-fluorine crosslinked rubber (B) is composed of at least one kind of rubber (b) which is at least partially crosslinked.
Description
Technical field
The present invention relates to contain the composition of the thermoplastic polymer of specific fluorine resin and specific cross-linked rubber, also relate to moulding product, sheet material, film, lamination structure body and the wire outer skin made by this thermoplastic polymer composition simultaneously.
Background technology
Cross-linked rubber is widely used in fields such as trolley part, household electrical appliances parts, wire outer skin and medical article because having excellent thermotolerance, chemical resistant properties and flexibility.But when using cross-linked rubber to make the moulding product, generally all to pass through complicated step, such as: (1) uncrosslinked rubber carries out crosslinked operation etc. with operation, (2) of linking agent, acid neutralizing agent and the mixing processing of filling agent with operation, (3) applying pressure machine or the baking oven that forcing machine or injection moulding machine carry out moulding, thereby makes that will obtain the moulding product needed through the long time.Cross-linked rubber be because can not carry out fusion after crosslinked in addition, also have can not fuse etc. following process in addition can not recycling etc. shortcoming.
In order to solve the above problems, developed so-called dynamic crosslinking technology, wherein, with linking agent melting mixing in forcing machine, and carry out crosslinked simultaneously thermoplastic resins such as polypropylene-based resin, uncrosslinked bridging property rubber.
As dynamic crosslinking rubber (TPV), for example the rubber of following structure is being studied widely, in this structure, in polypropylene-based resin, be dispersed with crosslinked ethylene-propylene-elastoprene (EPDM) (reference example as: the spy opens flat 06-287368 communique, Te Kaiping 06-256571 communique and spy open flat 11-228750 communique), and wherein a part is practical.
But the above-mentioned TPV that is formed by polypropylene-based resin and crosslinked EPDM is a polypropylene-based resin owing to its matrix, and therefore in fact it does not have thermotolerance more than the fusing point of polypropylene-based resin, and its chemical resistant properties is also relatively poor in addition.
In order to develop all good TPV of thermotolerance and chemical resistant properties, and for example use polyester resin or 4-methyl-1-pentene resinoid as matrix, and in structure decentralized crosslinking rubber, the rubber that obtains so known (reference example as: the spy opens flat 10-212392 communique and the spy opens flat 11-269330 communique), but, with compare with the TPV that crosslinked EPDM forms by polypropylene-based resin, though the thermotolerance of these TPV and chemical resistant properties have had some improvement, but not enough, but also there are problems such as flexibility and mechanical characteristic difference.
In addition, for using fluorine resin in the structure as matrix, disperse crosslinked viton carrying out research (reference example as: the spy opens clear 61-57641 communique, and the spy opens flat 05-140401 communique and the spy opens flat 06-228397 communique) as the TPV of cross-linked rubber.This TPV has excellent thermotolerance and chemical resistant properties because of the matrix fluorine resin, but it lacks winter hardiness, and physical propertiess such as flexibility and compression set rate are poor, and its forming process is also insufficient.
Summary of the invention
The objective of the invention is, provide to have excellent thermotolerance and chemical resistant thermoplastic polymer composition, its softness, and forming process excellence concurrently.
Promptly the present invention relates to the composition of following thermoplastic polymer, described composition is the composition that contains the thermoplastic polymer of fluorine resin (A) and floride-free cross-linked rubber (B), and fluorine resin (A) contains fluorine-containing vinyl-type polymer (a), in the floride-free cross-linked rubber (B), crosslinked at least a portion at least a rubber (b).
The molten point of preferred fluorine-containing vinyl-type polymer (a) is 120 ℃～310 ℃.
Preferred rubber (b) is that rubber, silicon are that rubber, polyurethane series rubber and Epicholorohydrin are at least a rubber in the rubber for being selected from by ethylene series rubber, acrylic rubber, nitrile.
Preferred cross-linked rubber (B) is in the presence of fluorine resin (A) and linking agent (C), and rubber (b) has been carried out the rubber that dynamic crosslinking is handled.
Fluorine resin in the preferred structure (A) forms external phase, and cross-linked rubber (B) forms disperse phase.
Preferred fluorine resin (A) is the multipolymer of tetrafluoroethylene and ethene.
Preferred fluorine resin (A) is the multipolymer of the perfluoro-ethylene type unsaturated compound of tetrafluoroethylene and following general formula (1) expression;
CF
2＝CF-R
f 1 (1)
In the formula, R
f 1Expression-CF
3And/or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
The fusing point of the multipolymer of the perfluoro-ethylene type compound that preferred tetrafluoroethylene and above-mentioned general formula (1) are represented is 120 ℃～245 ℃.
Preferred fluorine resin (A) is the perfluoro-ethylene type unsaturated compound unit that contains 19mol%～90mol% tetrafluoroethylene units, 9mol%～80mol% ethylene unit and the following general formula of 1mol%～72mol% (1) expression;
CF
2＝CF-R
f 1 (1)
In the formula, R
f 1Expression-CF
3And/or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
Preferred fluorine resin (A) is a poly(vinylidene fluoride).
Preferred rubber (b) is for being selected from least a rubber in the group of being made up of ethylene-propylene-elastoprene, ethylene-propylene rubber, isoprene-isobutylene rubber, halogenated butyl rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-divinyl rubber, dimethyl silicone rubber, vinyl methyl silicone rubber and vinylbenzene-diene-styrene block copolymer.
Preferred linking agent (C) is for being selected from least a compound in the group of being made up of organo-peroxide, aminocompound, oxy-compound, phenol resins based compound, sulfocompound, bismaleimide amine compound and quinonoid compound.
Preferred rubber (b) is the above compounds of 2 functionalities, and its intramolecularly has a bridging property functional group at least, and linking agent (C) can with above-mentioned functional group reactions.
The composition of preferred described thermoplastic polymer further contains fire retardant.
In addition, the present invention relates to moulding product, sheet material, film, wire outer skin of making by the composition of above-mentioned thermoplastic polymer and the LAN cable that possesses this wire outer skin.
In addition, the present invention relates to have the lamination structure body of the layer that forms by described thermoplastic polymer composition.
Embodiment
The present invention relates to the composition of thermoplastic polymer, described composition is the composition that contains the thermoplastic polymer of fluorine resin (A) and floride-free cross-linked rubber (B), and fluorine resin (A) contains fluorine-containing vinyl-type polymer (a), in the floride-free cross-linked rubber (B), crosslinked at least a portion at least a rubber (b).
The fusing point of preferred fluorine resin (A) is 120 ℃～310 ℃, more preferably 150 ℃～290 ℃, and more preferably 170 ℃～250 ℃.If the fusing point of fluorine resin (A) is lower than 120 ℃, the tendency that the composition of the thermoplastic polymer that then obtains has thermotolerance to reduce; Under the situation of with melting condition rubber (b) being carried out dynamic crosslinking in the presence of fluorine resin (A) and the linking agent (C), need melt temperature is arranged on more than the fusing point of fluorine resin (A), if and the fusing point of fluorine resin (A) has surpassed 310 ℃, carry out when crosslinked above-mentioned, rubber (b) has the trend of thermal ageing.
Fluorine resin (A) is limited especially, and it is so long as contain the polymkeric substance of at least a fluorine-containing vinyl-type polymer (a) and get final product.The ethylene type unsaturated compound that constitutes fluorine-containing vinyl-type polymer (a) can exemplify as follows: tetrafluoroethylene, perfluoroolefine, chloro trifluoro-ethylene, trifluoro-ethylene, hexafluoro-isobutene, vinylidene fluoride, vinyl fluoride, trifluorochloroethylenes such as perfluoro-ethylene type unsaturated compound shown in general formula (1), and as following general formula fluoroolefin such as (2) etc.
CF
2＝CF-R
f 1 (1)
(in the formula (1), R
f 1Expression-CF
3And/or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl);
CH
2＝CX
1(CF
2)
nX
2 (2)
(in the formula (2), X
1Expression hydrogen atom or fluorine atom, X
2Expression hydrogen atom, fluorine atom or chlorine atom, n is 1～10 integer).
In addition, as the ethylene type unsaturated compound that constitutes fluorine-containing vinyl-type polymer (a), except above-mentioned fluoroolefin and perfluoroolefine, can also enumerate no fluoride type unsaturated compound.As no fluoride type unsaturated compound, can enumerate ethene, propylene, alkyl vinyl ether class etc.Herein, alkyl vinyl ether is meant and has the alkyl vinyl ether that carbonatoms is 1～5 alkyl.
Excellent and be easy to the viewpoint of forming process from the thermotolerance of the composition of resulting thermoplastic polymer and oil-proofness, in the middle of these examples, the preferred fluorine-containing vinyl-type polymer (a) that is formed by tetrafluoroethylene and ethene that uses more preferably uses the fluorine-containing vinyl-type polymer (a) that contains 20mol%～80mol% tetrafluoroethylene units, 80mol%～20mol% ethylene unit.In addition, the fluorine-containing vinyl-type polymer (a) that is formed by tetrafluoroethylene and ethene can contain the third composition, as the third composition, can enumerate 2,3,3,4,4,5,5-seven fluoro-1-amylene (CH
2=CFCF
2CF
2CF
2H) etc.
The content of preferred the third composition is 0.1mol%～3mol% of fluorine-containing vinyl-type polymer (a).
In addition, thermotolerance, oil-proofness and excellent in flame retardance from the composition of resulting thermoplastic polymer, and the viewpoint that is easy to forming process is set out, and preferred fluorine-containing vinyl-type polymer (a) is to be formed by the perfluoro-ethylene type unsaturated compound that tetrafluoroethylene and following general formula (1) are represented;
CF
2＝CF-R
f 1 (1)
In the formula, R
f 1Expression-CF
3And/or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
Specifically can enumerate following combination: tetrafluoroethylene/hexafluoropropylene, tetrafluoroethylene/CF
2=CF-OR
f 2, tetrafluoeopropene/R 1216/CF
2=CF-OR
f 2Deng.As CF
2=CF-OR
f 2, can enumerate perfluor (ethylene methacrylic ether), perfluor (ethyl vinyl ether), perfluor perfluors (alkyl vinyl ether) such as (propyl vinyl ether).
The third composition that in the fluorine-containing vinyl-type polymer (a) that forms by tetrafluoroethylene and the represented perfluoro-ethylene type unsaturated compound of general formula (1), can contain in addition, other.
Become from the forming process of the composition of the thermoplastic polymer that obtains and to be easy to the aspect and to consider, under the situation of this multipolymer that forms by tetrafluoroethylene and the represented perfluoro-ethylene type unsaturated compound of above-mentioned general formula (1), preferred especially fusing point is 120 ℃～245 ℃, and this fusing point can be set by the copolymerization ratio of regulating the represented perfluoro-ethylene type compound of tetrafluoroethylene and above-mentioned general formula (1).
In addition, excellent and be easy to the viewpoint of forming process from thermotolerance, the oil-proofness of the composition of resulting thermoplastic polymer, preferred fluorine-containing vinyl-type polymer (a) is that the perfluoro-ethylene type unsaturated compound by tetrafluoroethylene, ethene and following general formula (1) expression forms;
CF
2＝CF-R
f 1 (1)
(in the formula, R
f 1Expression-CF
3And/or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.)
More preferably fluorine-containing vinyl-type polymer (a) contains the tetrafluoroethylene units of 19mol%～90mol%, the ethylene unit of 9mol%～80mol%, and the perfluoro-ethylene type unsaturated compound unit of 1mol%～72mol% general formula (1) expression; Further preferred fluorine-containing vinyl-type polymer (a) contains the tetrafluoroethylene units of 20mol%～70mol%, the ethylene unit of 20mol%～60mol%, and the perfluoro-ethylene type unsaturated compound unit of 1mol%～60mol% general formula (1) expression.
In addition, can contain in the fluorine-containing vinyl-type polymer (a) that the perfluoro-ethylene type unsaturated compound of being represented by tetrafluoroethylene, ethene and general formula (1) forms and append composition, as appending composition, can enumerate 2,3,3,4,4,5,5-seven fluoro-1-amylene (CH
2=CFCF
2CF
2CF
2H) etc.
The content that preferably appends composition is 0.1mol%～3mol% of fluorine-containing vinyl-type polymer (a).
Further, excellent and be easy to the viewpoint of machine-shaping from thermotolerance, the oil-proofness of the composition of resulting thermoplastic polymer, fluorine-containing vinyl-type polymer (a) is preferably poly(vinylidene fluoride).
In the floride-free cross-linked rubber (B), at least a portion at least a rubber (b) has taken place crosslinked, and contain fluorine atoms not in the cross-linked rubber.In addition, be preferably floride-free non-silicon rubber.Herein, in the floride-free non-silicon cross-linked rubber, at least a portion at least a rubber (b) has taken place crosslinked, and contain fluorine atoms not in the cross-linked rubber, and does not contain the silicone skeleton that is formed by silicon and Sauerstoffatom.
Rubber (b) is not limited especially, for example for being selected from the situation of at least a rubber in the group of forming by olefines rubber, acrylic rubber, nitrile rubber, silicon class rubber, polyurethanes rubber and Epicholorohydrin class rubber, be preferred from the thermotolerance and the oil-proofness excellence aspect of the composition that can make the thermoplastic polymer that obtains.
As olefines rubber, can enumerate polydiene, butyl-like rubber, vinyl rubber etc.
As polydiene, can enumerate vinylbenzene-polydienes such as natural rubber, synthetic polyisoprene, divinyl rubber, chloroprene rubber, styrene butadiene rubbers, vinylbenzene-diene-styrene block copolymer etc.Herein, vinylbenzene-polydiene also comprises its hydride or sour modifier etc.
As butyl-like rubber, can enumerate halogenated butyl rubber such as isoprene-isobutylene rubber, chloro isoprene-isobutylene rubber or bromo isoprene-isobutylene rubber etc.
As vinyl rubber, can enumerate ethylene-propylene rubber (EPM), ethylene-propylene-elastoprene (EPDM), polyvinyl chloride, chlorosulfonated polyethylene rubber etc.
Acrylic rubber can be enumerated acrylic rubber, ethylene acrylic rubber etc.As nitrile rubber, can enumerate acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-divinyl rubber etc.As silicon class rubber, can enumerate diformazan silicon rubber, vinyl methyl silicone rubber, phenyl-methyl silicone rubber, phenyl vinyl methyl silicone robber, trifluoropropyl siloxane etc.As polyurethanes rubber, can enumerate polyester-polyurethane rubber and polyether-polyurethane rubber etc.
From the more excellent viewpoint of thermotolerance, oil-proofness of the composition of resulting thermoplastic polymer, in these rubber, preferably from the group that following rubber is formed, select at least a: ethylene-propylene-elastoprene, ethylene-propylene rubber, isoprene-isobutylene rubber, halogenated butyl rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-divinyl rubber, diformazan silicon rubber, vinyl methyl silicone rubber and styrene-butadiene-styrene block copolymer.
In the cross-linked rubber (B) at least its part to have formed crosslinked be necessary.
About the addition of rubber (b), be 100 weight parts with respect to fluorine resin (A), preferred rubber (b) is 10～1000 weight parts, more preferably 50～900 weight parts, more preferably 100～800 weight parts.
If rubber (b) less than 10 weight parts, the flexibility of the composition of the thermoplastic polymer that then obtains has the tendency of reduction.If rubber (b) surpasses 1000 parts, the forming process of the composition of the thermoplastic polymer that then obtains has low tendency.
The composition of thermoplastic polymer of the present invention can obtain by following manufacture method: carry out the compound manufacture method by passing through crosslinked floride-free cross-linked rubber (B) melting mixing in advance to the gimmick in the fluorine resin (A), perhaps in the presence of fluorine resin (A) and linking agent (C), under melting condition, rubber (b) is carried out dynamic crosslinking and handle, thereby carry out the compound manufacture method.
Here the dynamic crosslinking of indication is handled and is meant, uses Banbury mixer (Banbury mixer), pressure kneader, forcing machine etc., makes rubber (b) carry out dynamic crosslinking in melting mixing.In these machines, because forcing machines such as biaxial extruder can apply these characteristics of high shear strength, so forcing machines such as biaxial extruder are preferred.Handle by dynamic crosslinking, can control the phase structure of fluorine resin (A) and cross-linked rubber (B) and the dispersion of rubber (b).
As linking agent (C), be preferably at least a compound that is selected from the group of forming by organo-peroxide, aminocompound, oxy-compound, phenol resins compounds, sulfocompound, bismaleimide aminated compounds and quinonoid compound.
As organo-peroxide, can enumerate 2,5-dimethyl-2,5-is two-(tert-butyl hydroperoxide) hexin-3,2,5-dimethyl-2,5-is two-dialkyl peroxides such as (tert-butyl hydroperoxide) hexane, peroxidation two cumenes; Hydrogen peroxide such as diisopropyl benzene hydrogen peroxide, cumene hydroperoxide.
In addition, as aminocompound, can enumerate the amino own ester (H of carboxylamine-6-
2N-CO
2(CH
2)
6NH
2), 1,4-butane diamines, 1,4-diamino-cyclohexane etc.
In addition, if necessary, can use crosslinking coagent simultaneously with linking agent (C).
Can wait according to the condition of kind that is used for crosslinked rubber (b) and melting mixing and suitably select linking agent (C).
In addition, rubber (b) preferably has at least more than one bridging property functional group at intramolecularly.In the case, preferred use can with compound more than 2 functionalities of this bridging property functional group reactions as linking agent (C).
As the bridging property functional group that rubber (b) can have, can enumerate hydroxyl, epoxy group(ing), amino, carboxyl, dehydration carboxyl, chlorine, bromine etc.
In addition, for example when the bridging property functional group that rubber (b) is had is the dehydration carboxyl, can use aminocompound as linking agent (C); When the bridging property functional group that rubber (b) is had was hydroxyl, the compound that can use isocyanate compound or contain the carboxyl that dewaters was as linking agent (C).
About the proportional quantity of linking agent (C), preferably with respect to 100 parts by weight of rubber (b), linking agent (C) is 0.1～10 weight part, more preferably 0.2～8 weight part.If linking agent (C) is less than 0.1 weight part, crosslinked carry out insufficient of rubber (b) then, the thermotolerance of the composition of the thermoplastic polymer that obtains and oil-proofness have the tendency of decline.If surpass 10 weight parts, the forming process of the composition of the thermoplastic polymer that then obtains has the tendency of decline.
So-called ' under the melting condition ' is meant under fluorine resin (A) and rubber (b) fused temperature.Carry out the fused temperature according to the difference of the glass transition temperature of fluorine resin (A) and rubber (b) and/or fusing point and difference, preferably carrying out the fused temperature is 120 ℃～330 ℃, more preferably 130 ℃～320 ℃.If discontented 120 ℃ of temperature, the then tendency that is dispersed with thickization between fluorine resin (A) and the rubber (b); If temperature has surpassed 330 ℃, there is rubber (b) that the tendency of thermal ageing takes place.
The composition of the thermoplastic polymer of gained can have following structure: fluorine resin (A) forms external phase, and cross-linked rubber (B) forms disperse phase; Perhaps fluorine resin (A) and cross-linked rubber (B) form external phase altogether, and wherein preferred fluorine resin (A) forms external phase, and cross-linked rubber (B) forms the structure of disperse phase.
Rubber (b) had formed under the situation of matrix originally disperseing, and along with the carrying out of crosslinking reaction, rubber (b) becomes cross-linked rubber (B), and melt viscosity rises, and cross-linked rubber (B) forms disperse phase, perhaps and fluorine resin (A) forms common external phase together.
If can form such structure, then the composition of thermoplastic polymer of the present invention has good forming process when showing excellent thermotolerance and oil-proofness.At this moment, the average mark shot of cross-linked rubber (B) directly is preferably 0.01 μ m～20 μ m, more preferably 0.1 μ m～10 μ m.
In addition, the ideal form of the composition of thermoplastic polymer of the present invention is that fluorine resin (A) forms external phase, and cross-linked rubber (B) forms the structure of disperse phase, for the composition of thermoplastic polymer of the present invention, the common continuous structure that contains fluorine resin (A) and cross-linked rubber (B) in the part of this structure also is fine.
In addition, in the composition of thermoplastic polymer of the present invention, further contain fire retardant in, demonstrate excellent flame-retardant performance.In this case, fire retardant is not limited especially, can use normally used fire retardant arbitrarily.For example can enumerate metal hydroxidess such as magnesium oxide, aluminium hydroxide; The phosphoric acid flame retardant; Halogen-containing flame retardant such as brominated flame-retardant, chlorine-containing flame retardant etc., preferably metal hydroxides and phosphoric acid flame retardant.In addition, also can together use flame retardants such as ANTIMONY TRIOXIDE SB 203 99.8 PCT, zinc borate or molybdenum oxide etc. to be fuming and prevent agent etc.
About the proportional quantity of above-mentioned fire retardant, with respect to the fluorine resin (A) and the floride-free cross-linked rubber (B) that amount to 100 weight parts, preferred above-mentioned fire retardant is 1～100 weight part.If above-mentioned fire retardant is less than 1 weight part, then add flame retardant effect that fire retardant brings and not obvious; If above-mentioned fire retardant has surpassed 100 weight parts, then in the tendency that variation is arranged aspect formability and the flexibility.
About the proportional quantity of above-mentioned flame retardant, with respect to the fluorine resin (A) and the floride-free cross-linked rubber (B) that amount to 100 weight parts, preferred above-mentioned flame retardant is 1～70 weight part, more preferably 5～50 weight parts.If above-mentioned flame retardant is less than 1 weight part, it is not obvious then to add the flame retardant effect that flame retardant brings; If above-mentioned flame retardant has surpassed 70 weight parts, then in the tendency that variation is arranged aspect the flexibility of formability and the formed body that obtains.
In addition, in the scope that does not influence effect of the present invention, can add following material in the thermoplastic polymer's of the present invention composition: other polymkeric substance such as polyethylene, polypropylene, polymeric amide, polyester, urethane; Inorganic filling materials such as lime carbonate, talcum, clay, titanium oxide, carbon black, barium sulfate; Dyestuff, lubricant, photostabilizer, weather-proof stablizer, static inhibitor, UV light absorber, antioxidant, parting agent, whipping agent, spices, oil, gentle tenderizer etc.
The composition of thermoplastic polymer of the present invention can carry out forming process by general method for processing forming and contour machining equipment etc.As method for processing forming, can adopt for example injection moulding, extrusion moulding, compressed moulding, blow molding, roll molded and arbitrary method such as vacuum forming.According to application target, the processed moulding of the composition of thermoplastic polymer of the present invention is the formed body of arbitrary shape.
Further, the present invention also comprises formed bodys such as sheet material that the composition that uses thermoplastic polymer of the present invention obtains, film, wire outer skin; Also comprise the lamination structure body in addition, described lamination structure body have layer that the composition by thermoplastic polymer of the present invention forms and by other materials forms layer.
Above-mentioned wire outer skin generally is to be used to the material that flame retardant resistance is provided, prevents mechanical injuries in line/cable that electronic equipments such as computer are used, thus be used for holding copper cash with and the tubular body arranged inside of covering material.Its method of forming limits especially, can enumerate known method, for example carries out the method etc. of extrusion moulding with pinblock and single shaft forcing machine.
Wire outer skin is because have above-mentioned formation, so its formability, flexibility are good, demonstrates excellent especially thermotolerance, also is well-adapted for requiring that always the crust of the LCC (LimitedComb ustible Cable) than high flame retardant is arranged therefore.According to purposes etc., wire outer skin of the present invention can be set different thickness, is generally the thickness in 0.2mm～1.0mm scope.Wire outer skin of the present invention has the thickness of above-mentioned scope, so flexibility is outstanding especially.
Wire outer skin of the present invention is to use the formed body of the composition molding of thermoplastic polymer of the present invention, excellences such as its flame retardant resistance, flexibility.
Wire outer skin of the present invention is limited especially, its can be used for the electronic equipments distribution with electric wire, electrical equipment with communications such as 600 volts of insulated wires, LAN cables with cable etc.Above-mentioned LAN cable etc. is all the LAN cable.
LAN also belongs to one of the present invention with cable, and described LAN is characterised in that with cable this cable has wire outer skin of the present invention.As the LAN cable, can enumerate top ceiling interlayer cable (plenum cable), above-mentioned in addition LCC is suitable for this cable very much.
Though LAN of the present invention can set suitable thickness with cable, be generally the thick forming composition of 0.2mm～1.0mm, LAN of the present invention with cable because have wire outer skin of the present invention, so flame retardant resistance, flexibility etc. are outstanding.
The composition of thermoplastic polymer of the present invention and the moulding product that formed by said composition, sheet material, film can be used in the following article: trolley part, mechanical part, electrical and electronic parts, office appliance, daily necessities, building materials, groceries etc.Lamination structure body of the present invention can be used as food product containers, fuel container, socket, flexible pipe etc.
Embodiment
Then, enumerate embodiment the present invention is described.But the present invention is not limited only to related embodiment.
＜hardness 〉
The particle of the composition of the thermoplastic polymer that use embodiment and comparative example are made, with this particle by thermocompressor 250 ℃, the condition lower compression moulding of 10MPa, make the sheet test film of thickness 2mm, use these test films, measure A hardness according to JIS-K6301.
＜tensile break strength and tension fracture elongation rate 〉
The particle of the composition of the thermoplastic polymer that use embodiment and comparative example are made, with this particle by thermocompressor 250 ℃, the condition lower compression moulding of 10MPa, making thickness is the sheet test film of 2mm, therefrom the dumbbell shaped test film of stamping-out thickness 2mm, wide 5mm.The dumbbell shaped test film that use obtains, use autoplotter (manufacturing of (strain) Shimadzu Seisakusho Ltd.), according to JIS-K6301, under 50mm/ minute condition, tensile break strength and tension fracture extensibility under measuring 23 ℃, and the tensile break strength under 140 ℃.
＜compression set rate 〉
The particle of the composition of the thermoplastic polymer that use embodiment and comparative example are made, use injection moulding machine, be under 250 ℃ the condition at roller temperature, making diameter is that 29.0mm, thickness are the right cylindrical moulding product of 12.7mm, according to JIS-K6301, after placing 22 hours under the condition of 120 ℃ of temperature, compress variation 25%, measure the compression set rate.
＜chemical resistant properties 〉
The particle of the composition of the thermoplastic polymer that use embodiment and comparative example are made, with this particle by thermocompressor 250 ℃, the condition lower compression moulding of 10MPa, making thickness is the sheet test film of 2mm, and therefrom stamping-out thickness is 2mm, widely is the dumbbell shaped test film of 5mm.The dumbbell shaped test film that obtains is dipped in the JIS3 oil, placed 70 hours at 100 ℃.Then, take out the dumbbell shaped test film, use autoplotter (manufacturing of (strain) Shimadzu Seisakusho Ltd.), according to JIS-K6301, under 50mm/ minute condition, the tensile break strength under testing 23 ℃ calculates the variation ratio with respect to the tensile break strength before soaking.
＜flame retardant resistance 〉
The particle of the composition of the thermoplastic polymer that use embodiment and comparative example are made, with this particle by thermocompressor 250 ℃, the condition lower compression moulding of 10MPa, make the sheet test film of thickness 2mm, therefrom stamping-out thickness is the sheet test film of 2mm, long 50mm, wide 50mm.With the sheet test film that obtains, use taper calorimeter (Cone Calorimeter, the smart mechanism of (strain) Japan is done manufacturing) to carry out combustion test, obtain heat generation rate and the rate of being fuming.
Use following fluorine-containing vinyl-type polymer (a-1), fluorine-containing vinyl-type polymer (a-2), rubber (b-1), rubber (b-2), rubber (b-3), rubber (b-4), linking agent (C-1), linking agent (C-2), fire retardant (D) and flame retardant (E) in embodiment and the comparative example.
＜fluorine-containing vinyl-type polymer (a-1) 〉
Tetrafluoroethylene-ethylene copolymer (220 ℃ of fusing points, Daikin Industries (strain) system, NEOFLONETEE EP-620)
＜fluorine-containing vinyl-type polymer (a-2) 〉
Tetrafluoraoethylene-hexafluoropropylene copolymer (the weight ratio of tetrafluoroethylene and R 1216=75/25; 192 ℃ of fusing points)
＜rubber (b-1) 〉
Maleic anhydride modified thing (Asahi Chemical Industry's (strain) system, Toughtec M1943) through the hydrogenant styrene-butadiene-styrene block copolymer
＜rubber (b-2) 〉
Ethylene-propylene rubber (JSR (strain) system, EP57P)
＜rubber (b-3) 〉
The cross-linked silicone rubber powder (Dow Corning Toray Co.Ltd., E-600)
＜rubber (b-4) 〉
Not sulphurated siliastic (Dow Corning Toray Co.Ltd., SH851U)
＜linking agent (C-1) 〉
The amino own ester of carboxylamine 6-(Daikin Industries (strain) system, V-1)
＜linking agent (C-2) 〉
2,5-dimethyl-2,5-pair-(tert-butyl hydroperoxide) hexin-3 (NOF Corp's system, Perhexyne 25B)
＜fire retardant (D) 〉
Brominated flame-retardant (Supreme Being people changes into (strain) system, FIRE GUARD 7500)
＜flame retardant (E) 〉
ANTIMONY TRIOXIDE SB 203 99.8 PCT (Japanese concentrate (strain) system, PATOX-M)
Embodiment 1～3
With above-mentioned fluorine-containing vinyl-type polymer (a-1), rubber (b-1) and linking agent (C-1) in the ratio pre-mixing shown in the table 1 after, drop into biaxial extruder, under the condition of 260 ℃ of roller temperatures and screw speed 100rpm, carry out melting mixing, produce the particle of the composition of thermoplastic polymer respectively.
Embodiment 4～6
With above-mentioned fluorine-containing vinyl-type polymer (a-1), rubber (b-2) and linking agent (C-2) in the ratio pre-mixing shown in the table 1 after, drop into biaxial extruder, under the condition of 260 ℃ of roller temperatures and screw speed 100rpm, carry out melting mixing, produce the particle of the composition of thermoplastic polymer respectively.
Carry out morphological examination by scanning electron microscope (NEC (strain)), according to its result as can be known, the composition of the thermoplastic polymer by embodiment 1～6 gained has fluorine resin (A) and forms the structure that external phase and cross-linked rubber (B) form disperse phase.
The particle of the composition of the thermoplastic polymer that use obtains is measured hardness, tensile break strength, tension fracture extensibility and compression set rate by above-mentioned method, and chemical resistant properties is estimated, and its result is as shown in table 1.
Comparative example 1
Except not adding linking agent (C-1), make the particle of the composition of thermoplastic polymer similarly to Example 3.
Comparative example 2
Except not adding linking agent (C-2), make the particle of the composition of thermoplastic polymer similarly to Example 6.
Carry out morphological examination by scanning electron microscope (NEC (strain)), according to its result as can be known, the composition of the thermoplastic polymer by comparative example 1 and comparative example 2 gained has rubber (b) and forms external phase, and fluorine resin (A) forms the structure of disperse phase.
The particle of the composition of the thermoplastic polymer that use obtains is measured hardness, tensile break strength, tension fracture extensibility and compression set rate by above-mentioned method, simultaneously chemical resistant properties is estimated, and its result is as shown in table 1.
Comparative example 3
With 30 weight part polypropylene (Grand Polymer Co.Ltd., J106W), 70 parts by weight of ethylene-propylene-elastoprene (JSR (strain), EPDM EP21), 0.5 weight part linking agent (Japanese grease (strain), Parkmil D) after the pre-mixing, use the Plastmil kneading device, under 230 ℃, the condition of 50rpm, carry out 10 minutes melting mixings, the synthetic dynamic crosslinking rubber (TPV-1) that forms by polypropylene and crosslinked EPDM.
Carry out morphological examination by scanning electron microscope (NEC (strain)), according to its result as can be known, the composition of the thermoplastic polymer of gained has polypropylene and forms external phase, and crosslinked ethylene-propylene-elastoprene forms the structure of disperse phase.
Use is entirely the particle of resulting dynamic crosslinking rubber (TPV-1), measures hardness, tensile break strength, tension fracture extensibility and compression set rate by above-mentioned method, simultaneously chemical resistant properties is estimated, and its result is as shown in table 1.
Table 1
| Embodiment | Comparative example | |||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 1 | 2 | 3 | ||
| Proportional quantity (weight portion) | Contain fluoroethylene polymer (a) | 50 | 40 | 30 | 50 | 40 | 30 | 30 | 30 | |
| Rubber (b-1) | 50 | 60 | 70 | 70 | ||||||
| Rubber (b-1) | 50 | 60 | 70 | 70 | ||||||
| Linking agent (C-1) | 0.12 | 0.15 | 0.20 | |||||||
| Linking agent (C-2) | 0.10 | 0.12 | 0.14 | |||||||
| Dynamic crosslinking rubber (TVP-1) | 100 | |||||||||
| Evaluation result | Hardness | 99 | 92 | 84 | 90 | 85 | 78 | 79 | 73 | 78 |
| 23 ℃ of tensile break strengths (MPa) | 19 | 15 | 12 | 20 | 14 | 12 | 7 | 9 | 10 | |
| 23 ℃ of tension fracture extensibilitys (%) | 93 | 125 | 140 | 102 | 137 | 156 | 255 | 234 | 155 | |
| 140 ℃ of tensile break strengths (MPa) | 12 | 10 | 8 | 13 | 10 | 8 | 0 | 6 | 3 | |
| Compression set rate (%) | 67 | 54 | 45 | 53 | 46 | 37 | 100 | 40 | 48 | |
| Chemical resistant properties (%) | 68 | 51 | 38 | 73 | 60 | 47 | 0 | 29 | 3 | |
Embodiment 7～10
With above-mentioned fluorine-containing vinyl-type polymer (a-2), rubber (b-3), fire retardant (D) and flame retardant (E) in the ratio pre-mixing shown in the table 2 after, drop into biaxial extruder, under the condition of 250 ℃ of roller temperatures and screw speed 100rpm, carry out melting mixing, produce the particle of the composition of thermoplastic polymer respectively.
Carry out morphological examination by scanning electron microscope (NEC (strain)), according to its result as can be known, the composition of the thermoplastic polymer by embodiment 7～9 gained has fluorine resin (A) and forms external phase, and cross-linked rubber (B) forms the structure of disperse phase.
The particle of the composition of the thermoplastic polymer that use obtains is by tensile break strength, the tension fracture extensibility and as shown in table 2 to the evaluation result of flame retardant resistance of above-mentioned method mensuration.
Comparative example 4,5
With above-mentioned fluorine-containing vinyl-type polymer (a-2), rubber (b-4), fire retardant (D) and flame retardant (E), under the situation of not adding linking agent, after the ratio pre-mixing shown in the table 2, drop into biaxial extruder, under the condition of 250 ℃ of roller temperatures and screw speed 100rpm, carry out melting mixing, produce the particle of the composition of thermoplastic polymer respectively.
Carry out morphological examination by scanning electron microscope (NEC (strain)), learn according to its result, the composition of the thermoplastic polymer by comparative example 4,5 gained has fluorine resin (A) and forms external phase, and cross-linked rubber (b-4) forms the structure of disperse phase.
The particle of the composition of the thermoplastic polymer that use obtains, the evaluation result of tensile break strength, tension fracture extensibility and the flame retardant resistance of being undertaken by above-mentioned method is as shown in table 2.
Table 2
| Embodiment | Comparative example | ||||||
| 7 | 8 | 9 | 10 | 4 | 5 | ||
| Proportional quantity (weight portion) | Fluorine-containing vinyl-type polymer (a-2) | 90 | 80 | 90 | 80 | 90 | |
| Rubber (b-3) | 10 | 20 | 10 | 20 | |||
| Rubber (b-3) | 10 | 20 | |||||
| Fire retardant (D) | 10 | 10 | 10 | 10 | |||
| Flame retardant (E) | 5 | 5 | 5 | 5 | |||
| Evaluation result | 23 ℃ of tensile break strengths (MPa) | 21 | 15 | 19 | 14 | 12 | 10 |
| 23 ℃ of tension fracture extensibilitys (%) | 312 | 256 | 286 | 238 | 112 | 101 | |
| Heat generation rate (kW/m) | 37 | 48 | 46 | 53 | |||
| The rate of being fuming (l/sec) | 3.1 | 3.8 | 3.7 | 4.2 | |||
Utilizability on the industry
The composition of thermoplastic polymer of the present invention is because be dispersed with the cross-linked rubber particle in fluorine-containing vinyl-type polymer, so be to have excellent heat resistance and chemical-resistant composition concurrently, it is soft, and the processing and forming excellence.
Claims (20)
1, the composition of thermoplastic polymer, said composition is the composition that contains the thermoplastic polymer of fluorine resin (A) and floride-free cross-linked rubber (B), wherein, fluorine resin (A) contains fluorine-containing vinyl-type polymer (a), in the floride-free cross-linked rubber (B), crosslinked at least a portion at least a rubber (b).
2, the composition of thermoplastic polymer as claimed in claim 1, wherein, the fusing point of described fluorine-containing vinyl-type polymer (a) is 120 ℃～310 ℃.
3, the composition of thermoplastic polymer as claimed in claim 1 or 2, wherein, described rubber (b) is that rubber, silicon are that rubber, polyurethane series rubber and Epicholorohydrin are at least a rubber in the group formed of rubber for being selected from by ethylene series rubber, acrylic rubber, nitrile.
4, as the composition of each described thermoplastic polymer of claim 1～3, wherein, described cross-linked rubber (B) is in the presence of fluorine resin (A) and linking agent (C), and rubber (b) has been carried out the cross-linked rubber that dynamic crosslinking is handled.
5, as the composition of each described thermoplastic polymer of claim 1～4, wherein, in its structure, described fluorine resin (A) forms external phase, and described cross-linked rubber (B) forms disperse phase.
6, as the composition of each described thermoplastic polymer of claim 1～5, wherein, described fluorine resin (A) is the multipolymer of tetrafluoroethylene and ethene.
7, as the composition of each described thermoplastic polymer of claim 1～5, wherein, described fluorine resin (A) is the multipolymer of the perfluoro-ethylene type unsaturated compound of tetrafluoroethylene and following general formula (1) expression;
CF
2＝CF-R
f 1 (1)
In the formula, R
f 1Expression-CF
3And/or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
8, the composition of thermoplastic polymer as claimed in claim 7, wherein, the fusing point of the multipolymer of the perfluoro-ethylene type unsaturated compound of tetrafluoroethylene and described general formula (1) expression is 120 ℃～245 ℃.
9, as the composition of each described thermoplastic polymer of claim 1～5, wherein, described fluorine resin (A) is following multipolymer, and described multipolymer contains the tetrafluoroethylene units of 19mol%～90mol%, the ethylene unit of 9mol%～80mol% and the perfluoro-ethylene type unsaturated compound unit of the following general formula of 1mol%～72mol% (1) expression;
CF
2＝CF-R
f 1 (1)
In the formula, R
f 1Expression-CF
3And/or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
10, as the composition of each described thermoplastic polymer of claim 1～5, wherein, described fluorine resin (A) is a poly(vinylidene fluoride).
11, as the composition of each described thermoplastic polymer of claim 1～10, wherein, described rubber (b) is for being selected from least a rubber in the group of being made up of ethylene-propylene-elastoprene, ethylene-propylene rubber, isoprene-isobutylene rubber, halogenated butyl rubber, acrylonitrile-butadiene rubber, hydrogenated acrylonitrile-divinyl rubber, dimethyl silicone rubber, vinyl methyl silicone rubber and vinylbenzene-diene-styrene block copolymer.
12, as the composition of each described thermoplastic polymer of claim 4～11, wherein, described linking agent (C) is for being selected from least a compound in the group of being made up of organo-peroxide, aminocompound, oxy-compound, phenol resins based compound, sulfocompound, bismaleimide amine compound and quinonoid compound.
13, as the composition of each described thermoplastic polymer of claim 4～12, wherein, described rubber (b) is the above compounds of 2 functionalities, and its intramolecularly has a bridging property functional group at least, and linking agent (C) can react with above-mentioned functional group.
14, as the composition of each described thermoplastic polymer of claim 1～13, said composition further contains fire retardant.
15, a kind of moulding product, these moulding product contain the composition of each described thermoplastic polymer of claim 1～14.
16, a kind of sheet material, this sheet material contains the composition of each described thermoplastic polymer of claim 1～14.
17, a kind of film, this film contains the composition of each described thermoplastic polymer of claim 1～14.
18, a kind of lamination structure body, this lamination structure body contains the composition of each described thermoplastic polymer of claim 1～14.
19, a kind of wire outer skin, this wire outer skin contains the composition of each described thermoplastic polymer of claim 1～14.
20, a kind of LAN cable is characterized in that, this LAN cable has the described wire outer skin of claim 19.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP146196/2004 | 2004-05-17 | ||
| JP2004146196 | 2004-05-17 | ||
| JP250242/2004 | 2004-08-30 |
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| Publication Number | Publication Date |
|---|---|
| CN1954029A true CN1954029A (en) | 2007-04-25 |
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ID=38059723
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005800156589A Pending CN1954029A (en) | 2004-05-17 | 2005-05-16 | Thermoplastic polymer composition |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149770B (en) * | 2008-09-09 | 2013-11-06 | 大金工业株式会社 | Method for producing fluorine rubber crosslinked molded body |
| CN104093769A (en) * | 2012-01-18 | 2014-10-08 | 旭硝子株式会社 | Method for producing acrylic rubber/fluoro-rubber composition, crosslinked composition, laminate body, and heat-resistant air rubber hose |
| CN104262736A (en) * | 2014-11-03 | 2015-01-07 | 苏州钧隆塑胶有限公司 | High-elasticity plastic |
| CN111465997A (en) * | 2017-12-26 | 2020-07-28 | 大金美国股份有限公司 | Electric wire, method for producing electric wire, and master batch |
-
2005
- 2005-05-16 CN CNA2005800156589A patent/CN1954029A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102149770B (en) * | 2008-09-09 | 2013-11-06 | 大金工业株式会社 | Method for producing fluorine rubber crosslinked molded body |
| US9416234B2 (en) | 2008-09-09 | 2016-08-16 | Daikin Industries, Ltd. | Method for producing fluorine-containing rubber molded article |
| CN104093769A (en) * | 2012-01-18 | 2014-10-08 | 旭硝子株式会社 | Method for producing acrylic rubber/fluoro-rubber composition, crosslinked composition, laminate body, and heat-resistant air rubber hose |
| CN104093769B (en) * | 2012-01-18 | 2016-01-20 | 旭硝子株式会社 | The manufacture method of acrylic rubber/fluoro-rubber composite, crosslinkable composite, duplexer and hot air rubber hose |
| CN104262736A (en) * | 2014-11-03 | 2015-01-07 | 苏州钧隆塑胶有限公司 | High-elasticity plastic |
| CN111465997A (en) * | 2017-12-26 | 2020-07-28 | 大金美国股份有限公司 | Electric wire, method for producing electric wire, and master batch |
| CN111465997B (en) * | 2017-12-26 | 2023-02-17 | 大金美国股份有限公司 | Electric wire, method for producing electric wire, and master batch |
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