CN101798408B - Polymer composition used as covering of electrical conduit and insulated electrical conduit - Google Patents
Polymer composition used as covering of electrical conduit and insulated electrical conduit Download PDFInfo
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- CN101798408B CN101798408B CN2009101346186A CN200910134618A CN101798408B CN 101798408 B CN101798408 B CN 101798408B CN 2009101346186 A CN2009101346186 A CN 2009101346186A CN 200910134618 A CN200910134618 A CN 200910134618A CN 101798408 B CN101798408 B CN 101798408B
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Abstract
The invention aims to provide a polymer composition which is used as a covering of an electrical conduit and only occupies a very small space. The composition has a lower melting point and improves the flame-retardant performance obviously. The polymer composition used as the covering of the electrical conduit contains 100 parts by weight of polyolefine polymer used as a basic polymer, 2 to 45 parts by weight of polyamide and 60 to 90 parts by weight of metal hydroxide. The polyamide is the copolymer of polyamide 6 and polyamide 66.
Description
Technical field
The present invention relates to as the conductivity cell coverture, especially be suitable for the obducent polymer compsn of conductivity cell of vehicle.
Background technology
Recently, the vehicle part utmost point needs miniaturized.The insulated electro conduit that is used for vehicle also needs miniaturized.
Yet, think always and give vehicle insulated electro conduit excellent flame-retardant, and to keep the miniaturized of this insulated electro conduit be unusual difficulty.That is to say that conventional mini-cable can not reach gratifying flame retardant properties.Equally, when to as heavy addition particulate inorganic flame retardance element in the obducent polymer compsn of conductivity cell for example during Marinco H, its flame retardant properties can improve.Yet in this case, its mechanical property is tended to remarkable reduction.
In order to overcome foregoing problems, the someone proposes with polymeric amide instead of part Marinco H.Through such settling mode, resulting insulated electro conduit can show the flame retardant properties of improving when keeping its original mechanical property.
In addition, japanese patent application publication No. 2002-146118 (A) discloses a kind of polymer compsn, and said composition comprises olefin polymer and has dystectic relatively polymeric amide more than 200 ℃.In this case, owing to added polyamide component, the thermotolerance that said composition can be improved.Yet because the adding of polyamide component, this polymer compsn has the fusing point that is higher than conventional alkylene compsn.Correspondingly, in its forming process subsequently, will adopt higher temperature.The employing of higher temperature not only can cause the thermal destruction of compsn self, also can cause the thermal destruction of each polymeric constituent of forming polymer compsn.And the resulting product for example strength of materials and the wearability of insulated electro conduit also can receive negative impact.
Summary of the invention
Provide the present invention to hope the problem that solves for a long time in order to overcome those skilled in the art.The invention is intended to provide a kind of and only take very little spatial polymer compsn as the conductivity cell coverture.This polymer compsn has lower fusing point, and therefore can show excellent flame-retardant.Polymer compsn according to the present invention is compared with cable cover aggregation compositions of the prior art has lower fusing point, and therefore it can not cause the TR internal shaping of its thermal destruction.
On the one hand, a kind of obducent polymer compsn of conductivity cell that can be used as is provided, it comprises:
100 weight parts contain the base polymer of polyolefin polymer;
The 2-45 weight parts of polyamide, based on the base polymer of 100 weight parts, this polymeric amide is the multipolymer of polyamide 6 and polyamide 66; With
The 60-90 parts by weight of metal hydroxide is based on the base polymer of 100 weight parts.
Preferably, this polyolefin polymer contains at least a Vestolen PP 7052.
On the other hand, a kind of insulated electro conduit with the electroconductive that has covered above-mentioned polymer compsn also is provided.
Embodiment
As base polymer, can comprise the polyamide component of 55-98 weight part polyolefin polymer and surplus according to polymer compsn of the present invention, based on the base polymer of 100 weight parts.
As polyolefin polymer, can include but not limited to Vilaterm, Vestolen PP 7052, polybutylenes, vinyl-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene rubber(EPR), ethylene-butene copolymer or the like according to polymer compsn of the present invention.Preferably, use ethylene-propylene rubber(EPR).This is because ethylene-propylene rubber(EPR) can be prepared and have needed enhanced thermotolerance of conductivity cell coverture and flexible polymer compsn.
In this case, can use at least two kinds of aforementioned polyolefin polymers together.For example, when polypropylene copolymer and ethylene-propylene rubber(EPR) when being equal to or less than 4: 1 mixed, can guarantee that gained insulation conductance pipe has the strength of materials character of improvement.
As polypropylene copolymer, can include but not limited to alfon, ethylene-propylene rubber(EPR) of alfon, toxilic acid modification or the like according to polymer compsn of the present invention.Preferably, in order to improve the intensive property of resultant polymer composition, the alfon of alfon and toxilic acid modification is used together.In this case, when the alfon of alfon and toxilic acid modification with 5: 1-3: during 2 mixed, this polymer compsn can obtain good plasticity.Term used herein " alfon " is meant the Vestolen PP 7052 that only is made up of propylene.Alfon can be from Prime Polymer Co., Ltd, acquisitions such as Mitsubishi Engineering-Plastics Corporation.Term used herein " alfon of toxilic acid modification " refers to the alfon of Maleic Acid, Anhydrous modification.The alfon of toxilic acid modification can be from Chemtura Corporation, acquisitions such as Mitsui Chemicals Inc..
As polyamide component, the preferred use has low-melting polymeric amide in polymer compsn according to the present invention.As the polymeric amide with the fusing point that is equal to or less than 190 ℃, the multipolymer of polyamide 6 and polyamide 66 is known.For example, above-mentioned multipolymer can be from Toray Industries, Inc., acquisitions such as Mitsubishi Engineering-Plastics Corporation.When in polymer compsn according to the present invention, using the multipolymer of polyamide 6 and polyamide 66, this polymer compsn can be shaped under the situation that does not cause its thermal destruction.Therefore, this polymer compsn has the processability of improvement.
According to polymer compsn of the present invention, the amount that can exist as the multipolymer of the polyamide 6 of polyamide component and polyamide 66 is the 2-45 weight part, based on the base polymer of 100 used weight parts.If the amount that polyamide component exists is less than 2 weight parts, just can not obtain enough flame retardant resistances.On the contrary, if the amount that polyamide component exists just can not obtain enough physical strengths greater than 45 weight parts.
An embodiment according to polymer compsn of the present invention can contain metal hydroxide component, and it joins in the used base polymer.As metal hydroxide component, the oxyhydroxide that can include but not limited to divalence or trivalent metal ion according to polymer compsn of the present invention is Marinco H, white lake, calcium hydroxide etc. for example.Preferably, in polymer compsn according to the present invention, use Marinco H.The metal hydroxides that use has 0.1 μ m-20 μ m median size is an ideal.In order to strengthen affinity or the miscibility with other component, improve the wearability of corresponding polymer compsn simultaneously, can carry out surface treatment to metal hydroxides with coupling agent.
The amount that polymer compsn according to the present invention contains metal hydroxide component is the 60-90 weight part, based on the base polymer of 100 used weight parts.Based on the base polymer of 100 used weight parts,, then can not give resultant polymer composition enough flame-retardant natures if the amount that metal hydroxide component exists is less than 60 weight parts.On the contrary, based on the base polymer of 100 used weight parts, if the amount that metal hydroxide component exists greater than 90 weight parts, then can not be given for example wearability of the required usually mechanical property of conductivity cell coverture to resultant polymer composition.Say that in further detail routine is added the amount of the metal hydroxide component in the polymer compsn to for being equal to or less than 200 weight parts, based on the base polymer of 100 used weight parts.In other words, contain a large amount of metal hydroxide component in the prior art polymers compsn.In this case, the mechanical property of resultant polymer composition can not be suitable for vehicle forever.On the other hand, the amount that polymer compsn according to the present invention contains metal hydroxide component is equal to or less than 90 weight parts, based on the base polymer of 100 used weight parts.Preferably, can contain the metal hydroxide component of 70-80 weight part according to polymer compsn of the present invention, based on the base polymer of 100 used weight parts.
Can further contain inhibitor according to of the present invention as the obducent polymer compsn of conductivity cell; Metal passivator is copper(greening)inhibitor for example; Processing aid is lubricant or wax for example, tinting material, pigment; Fire retardant is zinc borate and silica-based fire retardant or the like for example, and all these can often be used in the olefin-based polymer compsn.Said components can be added with appropriate amount well known to those skilled in the art.
The obducent polymer compsn of conductivity cell that can be used as according to the present invention can further contain at least a annexing ingredient; For example lubricant, tinting material, pigment or the like of nitrogen based flameproofing such as melamine cyanurate, flame retardant such as zinc borate and silica-based fire retardant, toughener such as clay, lime carbonate and talcum, inhibitor, metal passivator, processing aid for example, all these can add in the polyamide-based polymers mixture usually.Above-mentioned interpolation component can be added with appropriate amount well known to those skilled in the art.
Can in being generally used for preparing any device of insulativity cover aggregation compositions, prepare as the obducent polymer compsn of conductivity cell according to of the present invention through mixing and mediating aforementioned component.Such device can comprise Bunbury ' s mixing machine, roller mill, compacting kneader etc.Usually, at first prepare base polymer, in base polymer, adding at least a then is not the component of base polymer.But, the preparation method that can be used as the obducent polymer compsn of conductivity cell according to the present invention is not limited.In other words, base polymer can join in the mixture of other component or other component and go.
Kneading can be carried out under the minimum temperature of mediating can realizing.Specifically, select temperature on the fusing point of the multipolymer of used polyamide 6 and polyamide 66 10-20 ℃.In this case, through the thermal history and the thermal destruction of minimize polymer compsn self, the conductivity cell coverture of gained can obtain excellent mechanical property.
The obducent polymer compsn of conductivity cell that can be used as according to the present invention can directly be applied in the preparation of insulated electro conduit.Yet resulting composition also can be before supplying to the preparation process of insulated electro conduit, and advanced row is further handled for example granulation.
Preparing in the process of insulated electro conduit by polymer compsn according to the present invention, can use the method that is applied in usually in the insulation conductance control fully.For example, the preparation of insulated electro conduit comprises the extruding polymerization compositions.In the process, particularly insulated coverings forming process of preparation insulated electro conduit, select lower temperature to come the melt polymer component.As a result, gained insulated electro conduit can have the insulated coverings that has very good mechanical properties.Especially, select temperature on the fusing point of the multipolymer of used polyamide 6 and polyamide 66 40 ℃-50 ℃.
Provide following embodiment scope of the present invention is described.Yet embodiment provides just to the purpose of setting forth, and the present invention is not limited to this.
Preparation as the obducent polymer compsn of conductivity cell
Embodiment 1-8 and Comparative Example A An-K can be used as the obducent polymer compsn of conductivity cell about preparation.The polymer compsn of these embodiment 1-8 and Comparative Example A An-K gathers and is provided among the following table 1-3.In table 2 and 3, all concentration or contents level unit are all with " weight part " unit description.Related polymer compositions is mediated under the minimum temperature of mediating can realizing.
Table 1
| Abbreviation | ||
| ?HPP | Alfon | Prime?Polymer?Co.，Ltd. |
| ?MMHPP | The alfon of toxilic acid modification | Chemtura?Corporation |
| ?EPR | Ethylene-propylene rubber(EPR) | Prime?Polymer?Co.，Ltd. |
| ?PA6 | Polyamide 6 | Toray?Industries，Inc. |
| ?PA66 | Polyamide 66 | Mitsubishi Engineering-Plastics Corporation |
| ?PA-CP | The multipolymer of polyamide 6 and polyamide 66 | Toray?Industries，Inc. |
| ?Mg(OH) 2 | Marinco H | Kyowa?Chemical?Industry?Co.，Ltd. |
| ?AA | Anti-aging reagent | ADEKA?Corporation |
Table 2
Table 3
The evaluation of polymer compsn
It is 0.14 or 0.22mm that the compsn of embodiment 1-8 and Comparative Example A An-K is applied to xsect respectively
2Conductor on.Aforementioned various polymer compsns are extruded the sample of preparation insulated electro conduit.The external diameter that each insulated electro conduit sample has is 0.85mm or 0.95mm.Temperature in the extrusion is set at 230 ℃.
According to the present invention, owing to polymer compsn can be extruded under relatively low temperature, so polymer compsn is avoided the danger of thermal destruction basically.
Insulated electro conduit sample is tested to confirm their various character, comprised tensile elongation (speed), burnout time (being flame-retardant nature), wearability, residual anti-aging reagent (amount), and thermotolerance.
Tensile elongation (speed)
The test tensile elongation is to confirm whether they have the needed mechanical properties of polymkeric substance cable coverture.Measure tensile elongation through JIS C3005-4.16 method.In more detail, remove conductor respectively from each insulated electro conduit sample.Each coverture has the mark of a pair of interval 50mm.Each obducent two terminal portions is snapped on the chuck of tester for elongation, and stretches from the speed of 200mm/min.Measure on each coverture this then to the distance between the mark.Concerning data, the elongation of specimen must just be passed through more than or equal to 500%.Elongation is not passed through this test less than 500% specimen.
Burnout time (flame-retardant nature)
The test burnout time is to confirm whether they have the needed flame-retardant nature of polymkeric substance cable coverture.Measure the burnout time through JIS C3005-6.19 (with reference to its Figure 11) method.The insulated electro conduit that will have 600mm length tilts to place with about miter angle.Will with insulated electro conduit upper end at a distance of 500mm and be a part of that part of of insulated electro conduit with reductibility flame treating 15 seconds.For the flame-retardant nature of evaluation test sample, measure the flame-out time.For following data, the burnout time of specimen must just pass through in 70 seconds.Burnout time is not passed through this test greater than 70 seconds specimen.
Wearability
Through YPES-11-01-204,6.99 (with reference to its Fig. 7) method test wearability.At length, as shown in Figure 7 the protecting of insulated electro conduit sample that each length is about 750mm.Spring wire with thickness 0.45mm ± 0.01mm is contacted with each insulated electro conduit.On this position, make each insulated electro conduit load 7N ± 0.05N.Write down the reciprocal time of each sample.For following data, this reciprocal time must be equal to or greater than 300 and just pass through.Reciprocal time is not tested through wearability less than 300 specimen.
Thermotolerance
Each insulated electro conduit is crooked around turning axle, be allowed to condition at the atmospheric condition held then 10,000 hours.Respectively write down the temperature of in sample not finding slight crack thereafter.When under specimen is being equal to or higher than 120 ℃ temperature, all not having slight crack, this specimen be considered to " through ".In other words, be equal to or higher than when sample under 120 ℃ the temperature and showing splitting resistance, then think this specimen " through ".On the contrary, when under specimen only is being lower than 120 ℃ temperature, showing splitting resistance, then think this specimen " not through ".
Residual anti-aging reagent (amount)
For residual anti-aging reagent (being inhibitor), based on the amount of the anti-aging reagent that is added, residual anti-aging reagent must be equal to, or greater than 90 weight % just to be passed through.Amount with residual anti-aging reagent is not passed through this test less than the specimen of 90 weight % (based on the amount of the anti-aging reagent that is added).
The value of each residual anti-aging reagent is measured as follows:
The electric coverture of the aforementioned insulated electro conduit of 2g is partly taken out, freezing, grind then.Afterwards, the specimen that obtains thus being carried out Suo Shi with chloroform solvent extracted 10 hours.The extract that obtains is thus further concentrated.In spissated extract, add methyl alcohol, reach 40ml up to the TV of methyl alcohol and concentrated extract mixture.(the HSS-2000 system can obtain from JASCO company to let mixture carry out the performance liquid chromatography test; Post: Mightysil RP-18GP (150mm/4.6mm) can obtain from Kanto Kagaku; Column temperature: 40 ℃; Detector: UV (275nm); Thinner: methyl alcohol; Flow velocity: 1.0ml/min; Import (amount) with sample: 10 μ l).
The result of above-mentioned 5 kinds of tests is summarised in the above-mentioned table 2 and 3.In table 2 and 3, " P " expression " through ", " F " expression " is not passed through ".Top table 2 and 3 shows that all are as the tensile elongation that all demonstrates improvement according to the polymer compsn of insulated electro conduit of the present invention, burnout time, the anti-damage property of wasting, residual anti-aging reagent and thermotolerance.Simultaneously, can in the TR that can not cause its thermal destruction, extrude or be shaped according to polymer compsn of the present invention.In addition, not only demonstrate the flame retardant properties of improvement, and can prepare and only take very little spatial insulated electro conduit according to polymer compsn of the present invention.
According to an aspect of the present invention; Because can be used as the obducent polymer compsn of conductivity cell comprises the base polymer that 100 weight parts contain polyolefin polymer; The 2-45 weight parts of polyamide; 60-90 parts by weight of metal hydroxide, this polymeric amide are the multipolymers of polyamide 6 and polyamide 66, have lower fusing point so it is compared with cable cover aggregation compositions of the prior art.Therefore, this polymer compsn can not cause the TR internal shaping of its thermal destruction.Simultaneously, this polymer compsn has obtained excellent flame-retardant.In addition, this polymer compsn is very suitable for preparation and only takies very little spatial insulated electro conduit.Therefore, the conductivity cell of gained is suitable for vehicle.
Especially, when polyolefin compositions contained at least a polyacrylic polymer, the gained conductivity cell can obtain excellent thermotolerance.
According to a further aspect in the invention, because the insulation conductance pipe has the electroconductive that is coated with above-mentioned polymer compsn, this coverture can for example be shaped under the situation of the strength of materials and wearability not damaging other required characteristic of polymkeric substance cable coverture.In addition, the insulated electro conduit has not only obtained excellent flame-retardant performance matter, but also only takies very little space.
Top embodiment and embodiment provide with spirit in order to set forth explanation scope of the present invention.These embodiments and embodiment let those skilled in the art know better.Other embodiment and embodiment are within expectation of the present invention.Therefore, the present invention should only be subject to incidental claim.
Claims (4)
1. one kind is used as the obducent polymer compsn of conductivity cell, and it comprises:
100 weight parts contain the base polymer of polyolefin polymer, and wherein this polyolefin polymer comprises Vestolen PP 7052 and the ethylene-propylene rubber(EPR) that ratio was equal to or less than 4: 1;
The 2-45 weight parts of polyamide, based on the base polymer of 100 weight parts, wherein this polymeric amide is the multipolymer of polyamide 6 and polyamide 66, and has the fusing point that is equal to or less than 190 ℃; With
60-90 weight part Marinco H is based on the base polymer of 100 weight parts.
2. one kind is used as the obducent polymer compsn of conductivity cell, and it comprises:
100 weight parts contain the base polymer of polyolefin polymer, and wherein this polyolefin polymer comprises Vestolen PP 7052 and the ethylene-propylene rubber(EPR) that ratio was equal to or less than 4: 1;
The 2-45 weight parts of polyamide, based on the base polymer of 100 weight parts, wherein this polymeric amide is the multipolymer of polyamide 6 and polyamide 66, and has the fusing point that is equal to or less than 190 ℃; With
The 60-90 parts by weight of metal hydroxide is based on the base polymer of 100 weight parts.
3. one kind is used as the obducent polymer compsn of conductivity cell, and it comprises:
100 weight parts contain the base polymer of polyolefin polymer, and wherein this polyolefin polymer comprises Vestolen PP 7052 and the ethylene-propylene rubber(EPR) that ratio was equal to or less than 4: 1, and this Vestolen PP 7052 comprises the alfon of alfon and toxilic acid modification;
The 2-45 weight parts of polyamide, based on the base polymer of 100 weight parts, wherein this polymeric amide is the multipolymer of polyamide 6 and polyamide 66, and has the fusing point that is equal to or less than 190 ℃; With
The 60-90 parts by weight of metal hydroxide is based on the base polymer of 100 weight parts.
4. insulated electro conduit, it has the electrical conductor that has covered each polymer compsn in the claim 1,2 and 3.
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| CN2009101346186A CN101798408B (en) | 2009-02-09 | 2009-02-09 | Polymer composition used as covering of electrical conduit and insulated electrical conduit |
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| CN2009101346186A CN101798408B (en) | 2009-02-09 | 2009-02-09 | Polymer composition used as covering of electrical conduit and insulated electrical conduit |
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| CN101798408B true CN101798408B (en) | 2012-11-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256719A (en) * | 1991-09-12 | 1993-10-26 | Dsm N.V. | Flame retardant plastics composition based on a polyamide, a polyolefin, and magnesium hydroxide |
| CN1132224A (en) * | 1994-09-28 | 1996-10-02 | 埃尔夫阿托化学有限公司 | Polymide-based flame-retardant thermoplastic compositions and their application to covering of electrical cables |
| CN1468906A (en) * | 2002-06-24 | 2004-01-21 | ���з��ɹ�˾ | Polyamide and polyolefine refractory composition |
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2009
- 2009-02-09 CN CN2009101346186A patent/CN101798408B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256719A (en) * | 1991-09-12 | 1993-10-26 | Dsm N.V. | Flame retardant plastics composition based on a polyamide, a polyolefin, and magnesium hydroxide |
| CN1132224A (en) * | 1994-09-28 | 1996-10-02 | 埃尔夫阿托化学有限公司 | Polymide-based flame-retardant thermoplastic compositions and their application to covering of electrical cables |
| CN1468906A (en) * | 2002-06-24 | 2004-01-21 | ���з��ɹ�˾ | Polyamide and polyolefine refractory composition |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2002-146118A 2002.05.22 |
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