CN1238416C - Thermal plastic resin composition and formed articles - Google Patents
Thermal plastic resin composition and formed articles Download PDFInfo
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- CN1238416C CN1238416C CN 02153041 CN02153041A CN1238416C CN 1238416 C CN1238416 C CN 1238416C CN 02153041 CN02153041 CN 02153041 CN 02153041 A CN02153041 A CN 02153041A CN 1238416 C CN1238416 C CN 1238416C
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Abstract
The present invention provided a thermoplastic resin composition capable of readily peeling off a coated layer around electric wires by a knife, and preventing waste resin at the outlet of a dice of an extruder in coating of electric wires. This thermoplastic resin composition comprises (A) a substantially random interpolymer composed of 1-99 mol% polymer unit derived from an aromatic vinyl or vinylidene monomer and/or a hindered aliphatic or cyclic aliphatic vinyl or vinylidene monomer and 1-99 mol% polymer unit derived from at least one 2-20C [alpha]-olefin, (B) magnesium hydroxide and (C) a lubricant composed of at least one compound selected from aliphatic surfactants and fatty acid amides.
Description
Technical field
The present invention relates to a kind of thermoplastic resin and moulded products thereof, more particularly, be particularly related to a kind of thermoplastic resin composition who is suitable as cable sheathing (cover or sleeve pipe) material usefulness and electric wire coating layer formation usefulness, particularly alpha-olefin ethene or vinylidene compound copolymer compositions and moulded products thereof.
Background technology
Now, in various moulding purposes, particularly require to have purposes such as flame retardant resistance or insulativity for example in the purposes of the foreskin material of cable and a part of insulating material, the thermoplastic resin composition who has added magnesium hydroxide is well-known.In these purposes, this thermoplastic resin composition and the common moulding of metal.For example electric wire around just coating thermoplastic resin composition's layer.
But, with processing electric wires such as cutters the time,, but may not peel off easily though wish easily this thermoplastic resin composition's layer to be peeled off from electric wire.
Summary of the invention
Therefore, the present inventor has carried out research in depth in order to address the above problem, found that: will be selected from glyceryl monostearate in utilization, the two erucicamides of ethylene, at least a compound in two oleylamide of ethylene and the ethylene bis stearamide is engaged to (A) by aromatic vinyl or vinylidene monomer with specific ratio, and/or be obstructed aliphatics or annular aliphatic ethene or 1～99 mole of % of vinylidene monomer deutero-polymerized unit, with at least a carbonatoms be that 1～99 mole of % of 2～20 alpha-olefin derived polymerized unit constitutes, be essentially for example ethylene-styrene copolymer of random multipolymer, and (B) in the magnesium hydroxide and the thermoplastic resin composition who obtains forms under the situation of the coating layer around the covered electric cable, metal-stripping with the excellent electric wire processibility that just this coating layer can be peeled off from the electric wire easily with cutter etc. etc., and, forcing machine mould exit produces gum shape secretory product in the time of can also preventing that electric wire is Overmolded, so far, finished the present invention.
The objective of the invention is to, in order to solve the problem of following prior art to produce as described above, the moulded products of above-mentioned coating layer that a kind of thermoplastic resin composition is provided and forms by said composition etc., it has excellent metal-stripping, for example in the electric wire processibility that just this coating layer can be peeled off from the electric wire easily under the situation that forms the coating layer around the covered electric cable, with cutter etc., and forcing machine mould exit produces gum in the time of can also preventing that electric wire is Overmolded.
Thermoplastic resin composition's of the present invention feature is:
With 97.0～99.9: it is 20～80 weight parts that 0.1～3.0 weight ratio { [(A)+(B)]: (C) } and composition (B) are measured 100 weight parts with respect to composition (A), (B) and total (C), contains:
(A) by (1) (a) at least a aromatic vinyl or vinylidene monomer; Or
(b) at least a aliphatics or annular aliphatic ethene or the vinylidene monomer of being obstructed;
Or
(c) combination of at least a aromatic vinyl or vinylidene monomer and at least a be obstructed aliphatics or annular aliphatic ethene or vinylidene monomer;
1～99 mole of % of deutero-polymerized unit and
(2) 1～99 mole of % of the alpha-olefin derived polymerized unit of at least a carbonatoms 2～20 constitute, at least aly be essentially random multipolymer;
(B) magnesium hydroxide;
(C) be selected from the lubricant that at least a compound in aliphatic category tensio-active agent (C-1) and the fatty amide (C-2) constitutes.
As above-mentioned multipolymer (A), preferred use by at least a aromatic vinyl or 5～65 moles of % of vinylidene monomer deutero-polymerized unit, and at least a carbonatoms be 35～95 moles of % of alpha-olefin derived polymerized unit of 2～20 constitute be essentially random multipolymer.
Preferred especially use by 5～65 moles of % of vinylbenzene deutero-polymerized unit, and at least a carbonatoms be 35～95 moles of % of alpha-olefin derived polymerized unit of 2～10 constitute be essentially random multipolymer.
In addition, as above-mentioned multipolymer (A), preferred use by at least a aromatic vinyl or 5～50 moles of % of vinylidene monomer deutero-polymerized unit, and at least a carbonatoms be the pseudo-random multipolymer that 50～95 moles of % of alpha-olefin derived polymerized unit of 2～20 constitute.
Preferred especially the use by 5～50 moles of % of vinylbenzene deutero-polymerized unit, and the pseudo-random multipolymer that constitutes of 50～95 moles of % of alpha-olefin derived polymerized unit of at least a carbonatoms 2～10.
Herein, the meaning of " puppet " in the pseudo-random multipolymer is, opens as the spy and announces in the flat 7-070223 communique like that, do not have the homopolymer chain link that is made of ethene or vinylidene monomer in copolymer molecule is constructed.That is, in the random multipolymer of puppet, the head that ethene or vinylidene monomer can not take place is to the insertion to afterbody of head, head.
Above-mentioned thermoplastic resin composition of the present invention can be applicable to well that electric wire foreskin (or foreskin of cable) and electric wire coat.
The feature of moulded products of the present invention is to be made of above-mentioned thermoplastic resin composition of the present invention.
Embodiment
Below, describe thermoplastic resin composition of the present invention and moulded products thereof in detail.
Thermoplastic resin composition of the present invention is contained at least a random multipolymer (A), magnesium hydroxide (B) and the lubricant (C) of being essentially.
Multipolymer (A)
The used multipolymer (A) of the present invention is,
(A) by (1) (a) at least a aromatic vinyl or vinylidene monomer or
(b) be selected from least a in the aliphatic ethylene base monomer that is obstructed, hindered cyclic aliphatic ethylene base monomer, the aliphatics of being obstructed vinylidene monomer and the hindered cyclic aliphatics vinylidene monomer or
(c) at least a aromatic vinyl or vinylidene monomer and be selected from the inferior vinyl monomer of the aliphatic ethylene monomer that is obstructed, hindered cyclic aliphatic ethylene monomer, the aliphatics of being obstructed and the inferior vinyl monomer of hindered cyclic aliphatics at least a 1～99 mole of % of combination deutero-polymerized unit; With
(2) at least a carbonatoms is 1～99 mole of % of alpha-olefin derived polymerized unit of 2～20;
What constitute is essentially random multipolymer.
Term " multipolymer " meaning (interpolymer) used herein is: the multipolymer (copolymer) when being polymerized to multipolymer (interpolymer) by at least two kinds of monomers.
" multipolymer " meaning (copolymer) used herein is: the polymkeric substance when being polymerized to multipolymer (copolymer) by at least two kinds of monomers.
Used herein by alpha-olefin and aromatic vinyl monomer, the aromatic series vinylidene monomer, the aliphatic ethylene monomer is obstructed, hindered cyclic aliphatic ethylene monomer, the meaning that is essentially " being essentially random " in the random multipolymer that the aliphatics of being obstructed vinylidene monomer or hindered cyclic aliphatics vinylidene monomer constitute is, described like that as J.C.Randall in " the POLYMER SEQUENCE DEDERMINATION; Carbon-13NMRMethod " of the Academic press in New York distribution in 1977 71～78 pages, the monomer distribution of this multipolymer can enough " Bernoulli Jacob's statistical model " or " the markov statistical model of the 1st or the 2nd sequence " be described.
By at least a carbonatoms be 2～20 alpha-olefin and aromatic vinyl or vinylidene monomer constitute be essentially random multipolymer, the aromatic vinyl of the block that is made of 4 above unit or the consumption of vinylidene monomer are preferably aromatic vinyl or below 15% of vinylidene monomer total amount.
More preferably, this multipolymer does not have the degree of isotacticity of height or the feature of degree of syndiotacticity.This means, substantially be in the C-13NMR spectrum of random multipolymer, in expression meso binary sequence or the racemize binary sequence zone, peak that is equivalent to main chain methylene radical and methine carbon atom of any should be no more than main chain methylene radical and methine carbon atom zone, total peak 75%.
In the multipolymer that is applicable to modulation thermoplastic resin composition of the present invention, comprise the multipolymer that the alpha-olefin more than 1 and the aromatic vinyl more than 1 or vinylidene monomer and/or be obstructed aliphatics or annular aliphatic ethene or vinylidene monomer more than 1 is carried out polymerization and obtain, but be not limited only to this.
As the example of preferred alpha-olefin, can enumerate carbonatoms is 2～20, is preferably 2～12, more preferably 2～8 alpha-olefin.Wherein, be preferably ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene, and 1-octene especially.These alpha-olefins do not contain aryl.
As the aromatic vinyl that is applicable to the manufacturing multipolymer used among the present invention or the example of vinylidene monomer, can enumerate the monomer that is expressed from the next.
[Chemical formula 1]
In the formula, R
1Be that to be selected from hydrogen atom and carbonatoms be atom or group in 1～4 the alkyl, be preferably hydrogen atom or methyl.
Each R
2Be that independently to be selected from hydrogen atom and carbonatoms be atom or group in 1～4 the alkyl, be preferably hydrogen atom or methyl.
Ar is phenyl or is that 1～4 alkyl and carbonatoms are the phenyl that 1～5 substituting group in 1～4 the haloalkyl replaces with being selected from halogen atom, carbonatoms.
N is 0～4 integer, is preferably 0～2, most preferably is 0.
Specific examples as aromatic series list ethene or single inferior vinyl monomer has vinylbenzene, Vinyl toluene, alpha-methyl styrene, t-butyl styrene, chloro-styrene etc., also comprises the isomer of all these compounds.As the specific examples of particularly preferred aromatic series list ethene or single inferior vinyl monomer, there are vinylbenzene and its low alkyl group or halogen atom to replace redundant organism.Preferred monomer has: vinylbenzene, alpha-methyl styrene, cinnamic low alkyl group (carbonatoms is 1～4 alkyl) or phenyl ring replace redundant organism, for example adjacent,, p-methylstyrene, ring substituted phenylethylene, right-Vinyl toluene or its mixture.Preferred aromatic series list ethene or single inferior vinyl monomer are vinylbenzene.
The meaning of above-mentioned term " aliphatics of being obstructed or annular aliphatic ethene or vinylidene compound " is: the ethene or the vinylidene monomer that are equivalent to the addition polymerization of the compound that following formula represents.
[Chemical formula 2]
In the formula, A
1Be sterically hindered high aliphatics or the annular aliphatic substituting group of carbonatoms below 20.
R
1Be that to be selected from hydrogen atom and carbonatoms be atom or group in 1～4 the alkyl, be preferably hydrogen atom or methyl.
Each R
2Be that independently to be selected from hydrogen atom and carbonatoms be 1～4 alkane atom or group wherein, be preferably hydrogen atom or methyl.
Also can be by R
1And A
1Form ring compound together.
The meaning of above-mentioned " sterically hindered height " is: have the substituent monomer of this aliphatics or annular aliphatic, utilize the Ziegler-Natta catalyst of standard, with speed of response that vinyl polymerization is equal to mutually under, can not carry out common addition polymerization.
The aliphatics of preferably being obstructed or annular aliphatic ethene or vinylidene compound are the monomers that one of carbon atom with vinyl unsaturated link(age) carries out 3 grades or 4 grades replacements.As these substituent examples, have: the annular aliphatic base of cyclohexyl, cyclohexenyl, ring octyl group etc., or the cycloalkyl of these groups or aryl replacement redundant organism.The most preferred aliphatics or annular aliphatic ethene or vinylidene compound of being obstructed is: the various isomer shape ethene of cyclohexyl and substituted cyclohexyl-ring replaces redundant organism, and 5-ethylidene-2-is with bornylene.Particularly preferably be 1-, 3-and 4-vinyl cyclohexane.
The alpha-olefin more than 1 that the present invention is used and 1 above aromatic vinyl or vinylidene monomer and/or be obstructed aliphatics or annular aliphatic ethene or vinylidene monomer more than 1 are carried out the multipolymer that polymerization generates, and are to be essentially random multipolymer.These multipolymers contain 1～99 mole of % usually, are preferably 5～65 moles of %, more preferably at least one aromatic vinyl or vinylidene monomer and/or be obstructed aliphatics or annular aliphatic ethene or the vinylidene monomer of 5～50 moles of %, and 1～99 mole of %, be preferably 35～95 moles of %, more preferably at least a carbonatoms of 50～95 moles of % is 2～20 alpha-olefin.
The number-average molecular weight (Mn) of multipolymer (A) is generally more than 10,000, is preferably 20,000～1,000,000, and more preferably 50,000～500,000.
Yet, being essentially in the random multipolymer in preparation, the aromatic vinyl under the utilization heating or the independent polymerization of vinylidene monomer can generate a certain amount of atactic aromatic vinyl or vinylidene homopolymer.In general, can not ignore existence to disadvantageous aromatic vinyl of purpose of the present invention or vinylidene homopolymer.According to required, the non-solvent by using any usefulness in multipolymer or aromatic vinyl or the vinylidene homopolymer, in solution, carry out purification techniques such as selective precipitation, can from multipolymer, isolate aromatic vinyl or vinylidene homopolymer.According to purpose of the present invention, the content of aromatic vinyl or vinylidene homopolymer is below the 20 weight % of multipolymer total amount, is preferably below the 15 weight %.
Being essentially random multipolymer can be according to EP-A-0, and 416,815 and 5,703,187 described preparations of United States Patent (USP).Quote these open reports in all above-mentioned U. S. applications at this.The preferred operations condition of these polyreactions is: pressure is 1 normal atmosphere～3,000 normal atmosphere: temperature is-30～20 ℃.If under the temperature that is higher than each monomeric spontaneous polymerization temperature, carry out polyreaction and remove unreacted monomer, can generate a certain amount of homopolymerization resultant by radical polymerization.
Being used to make the used preferred catalyst that is essentially random multipolymer of the present invention and the example of method is disclosed in: EP-A-416,815; EP-A-514,828; EP-A-520,732; United States Patent (USP) 5,470,993; United States Patent (USP) 5,055,438; 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,189,192; 5,321,106; 5,347,024; 5,350,723; 5,374,696; Among 5,399,635 and 5,556,928.
Quote all these open reports at this.
Announce at European patent and to disclose the used pseudo-random copolymers that constitutes by aliphatics alpha-olefin and aromatic series list ethene or single inferior vinyl compound among the present invention in No. 0416815.
These multipolymers can be under-30～250 ℃ temperature, and at catalyzer with in the presence of according to required and preferred co-catalyst, carries out the manufacturing of polyreaction system.
For the catalyzer for preparing the pseudo-random copolymers that is applicable to that the present invention is used and the example of method, at No. the 0416815th, European patent communique, No. the 468651st, European patent communique, No. the 514828th, European patent communique, No. the 520732nd, European patent communique, United States Patent (USP) 5,374,696, in the specification sheets of WO95/00526 open elaboration is arranged, these are quoted as a reference by the present invention all.
The multipolymer (A) that the present invention is used preferably carries out the silane grafting.
This multipolymer (A) after the silane grafting when using the organosilane coupler, also uses superoxide to modulate for promoting the silane grafting simultaneously.In the present invention, in the thermoplastic resin composition of the present invention that multipolymer (A), magnesium hydroxide (B), lubricant (C), organosilane coupler and superoxide melting mixing by will not connect skill by silane with various existing well-known methods obtain to this multipolymer (A) after the silane grafting, contain the multipolymer after the silane grafting (A) of generation.
As above-mentioned organosilane coupler, can enumerate vinyltrimethoxy silane, vinyltriethoxysilane, γ-metacryloxy propyl group methyl dimethoxysilane, γ-metacryloxy propyl trimethoxy silicane, γ-metacryloxy propyl group methyldiethoxysilane, γ-metacryloxy propyl-triethoxysilicane, vinyl three butoxy silanes, vinyl three ('beta '-methoxy Ethoxysilane), vinyltriacetoxy silane, methyltrimethoxy silane etc. particularly.Wherein, be preferably vinyltrimethoxy silane, vinyltriethoxysilane, γ-metacryloxy propyl trimethoxy silicane.
The consumption of organosilane coupler is 100% with the total weight of multipolymer (A) and magnesium hydroxide (B), is generally 0.1～2.5 weight %, is preferably the ratio of 0.2～2 weight %.If use the organosilane coupler with aforementioned proportion, then can obtain containing the thermoplastic resin composition of multipolymer (A), magnesium hydroxide (B) and lubricant (C) with the speed of silane grafting rapidly, and obtain the silane graft(ing) degree of appropriateness, its result, can form tensile elongation and the good moulded products of tensile break strength balance, for example electric wire coating layer.
In the present invention, as mentioned above,, superoxide and organosilane coupler are used simultaneously for promoting the silane graft reaction of multipolymer (A).
As such superoxide, be meant organo-peroxide, can enumerate particularly: benzoyl peroxide, the dichloro acetylbenzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, 2,5-dimethyl-2,5-two (peroxide benzoate) hexin-3,1, two (the t-butyl peroxy sec.-propyl) benzene of 4-, lauroyl peroxide, t-butyl peracetic acid salt, 2,5-dimethyl-2,5-(t-butyl peroxyization) hexin-3,2,5-dimethyl-(t-butyl peroxyization) hexane, t-butyl perbenzoate, the t-butyl is crossed phenylacetate, the t-butyl is crossed isobutyrate, the t-butyl is crossed secondary octanoate, t-butyl pivalate, cumyl is crossed pivalate, the t-butyl is crossed the diethylacetic acid ester, Diisopropyl azodicarboxylate, dimethyl azo isobutyrate etc.
In above-mentioned these superoxide, preferred dicumyl peroxide, the ditertiary butyl peroxide, 2 of using, 5-dimethyl-2,5-(t-butyl peroxyization) hexin-3,2,5-dimethyl-2,5-(t-butyl peroxyization) hexane, 1, dialkyl peroxides such as two (the t-butyl peroxy sec.-propyl) benzene of 4-.
The consumption of superoxide is 100 weight % with the total weight of multipolymer (A) and magnesium hydroxide (B), is generally 0.005～0.15 weight %, is preferably 0.01～0.1 weight %.If use superoxide with aforementioned proportion, can the appropriate silane graft reaction that promotes organosilane coupler and multipolymer (A).
Magnesium hydroxide (B)
As the used magnesium hydroxide of the present invention (B), can enumerate the magnesium hydroxide handled through lubricant particularly, carry out the surface-treated magnesium hydroxide through the magnesium hydroxide of silane treatment etc., and surface treated magnesium hydroxide etc. not.Wherein, preferably not surface treated magnesium hydroxide.
These magnesium hydroxides both can use a kind separately, also can be used in combination more than 2 kinds.
If the magnesium hydroxide (B-1) that will handle through lubricant and undressed magnesium hydroxide (B-2) is used in combination or the magnesium hydroxide (B-1) that will handle through lubricant and be used in combination through the magnesium hydroxide (B-3) of silane treatment, then can modulate the brittle resistance excellence under the low temperature and the moulded products that balance is good, traumatic resistance is excellent of tensile elongation and tensile break strength, be preferred therefore.
Weight ratio (B-1)/(B-2) is generally 5/95～95/5, is preferably 20/80～80/20, and more preferably 20/80～50/50.
Weight ratio (B-1)/(B-3) is generally 5/95～95/5, is preferably 20/80～80/20, and more preferably 20/80～50/50.
Then do not have specific restriction as used lubricant when magnesium hydroxide being lubricated the agent processing, for example can enumerate: hydro carbons lubricants such as paraffinic hydrocarbons, paraffin, polyethylene wax;
Fatty acid lubricants such as stearic acid, oleic acid, 12-oxystearic acid;
Senior alcohols lubricant such as stearyl alcohol;
Fatty amide series lubricant agents such as stearylamide, oleylamide, erucicamide;
Metallic soap series lubricant agents such as Zinic stearas, calcium stearate, Magnesium Stearate;
Ester series lubricant agents such as butyl stearate, glyceryl monostearate, monoolein etc.
In these lubricants, be preferably fatty acid lubricants such as stearic acid, oleic acid, metallic soap series lubricant agents such as calcium stearate.
Lubricant treatment process as magnesium hydroxide, can enumerate currently known method, for example, while making the method that the Henschel mixer that magnesium hydroxide is arranged rotates, the lubricant jet that dissolves is sprayed to Henschel mixer inside that drops into, perhaps, contain to henry and drop into magnesium hydroxide in your mixing machine and lubricant stirs, with lubricator apply the method etc. on the surface of magnesium hydroxide again by its heating.
In addition, as silicoorganic compound used when magnesium hydroxide is carried out silane treatment, can enumerate silicoorganic compound, be so-called organosilane coupler, for example gamma-amino propyl trimethoxy silicane, γ-metacryloxy propyl trimethoxy silicane, vinyltrimethoxy silane etc. with alkoxyl group.
Silane treatment method as magnesium hydroxide, can enumerate currently known method, for example, the organosilane coupler that is dissolved in water or the solvent is being heated below 100 ℃, in this solution, add magnesium hydroxide, make the slurries of favorable dispersity, with these slurries from treatment solution, separate, after the drying, after carrying out temporary transient heat treated below 150 ℃, and then in method that heats below 300 ℃ etc.
The used magnesium hydroxide of handling through lubricant of the present invention, surface-treated magnesium hydroxide and undressed magnesium hydroxide have been carried out through the magnesium hydroxide of silane treatment etc., its average particle size is respectively 0.5～10 μ m, be preferably 0.5～5 μ m, from mechanical properties aspects such as tensile elongation and tensile break strengths, this is desirable.
Lubricant (C)
The used lubricant (C) of the present invention is to be made of at least a compound that is selected from aliphatic category tensio-active agent (C-1) and the fatty amide (C-2).
As aliphatic category tensio-active agent (C-1), can enumerate particularly: glycerine monofatty esters such as lauric monoglyceride, tetradecanoic acid direactive glyceride, hexadecanoic acid direactive glyceride, glyceryl monostearate.
In addition, as fatty amide (C-2), can enumerate particularly: the two erucicamides of ethylene, the two oleylamide of ethylene, ethylene bis stearamide, oleylamide, stearylamide, erucicamide etc.Wherein, be preferably glyceryl monostearate, the two erucicamides of ethylene, the two oleylamide of ethylene, ethylene bis stearamide, be preferably the two erucicamides of ethylene especially.
The thermoplastic resin composition
Thermoplastic resin composition of the present invention, the weight ratio { [(A)+(B)]: (C) } of above-mentioned multipolymer (A) and magnesium hydroxide (B) and lubricant (C) is 97.0～99.9: 0.1～3.0, be preferably 98.0～99.9: 0.1～2.0, more preferably 98.0～99.5: 0.5～2.0.If above-mentioned weight ratio within above-mentioned scope, just can be modulated into the moulded products of metal-stripping excellence, for example be formed on electric wire coating layer on every side, and, can also obtain preventing that the thermoplastic resin of gum from appearring in the mould outlet place of forcing machine.
The content of magnesium hydroxide (B) is 100 weight parts with the total weight of multipolymer (A), magnesium hydroxide (B) and lubricant (C), is generally 20～80 weight parts, is preferably 40～80 weight parts, more preferably 50～70 weight parts.If use magnesium hydroxide (B), just can access the adjustable thermoplastic resin composition who makes the good moulded products of tensile elongation and tensile break strength balance with the amount in the above-mentioned scope.
In thermoplastic resin composition of the present invention, except above-mentioned multipolymer (A), magnesium hydroxide (B) and lubricant (C), or beyond multipolymer (A), magnesium hydroxide (B), lubricant (C), organosilane coupler and the superoxide, can limit according to needs, in not damaging purpose scope of the present invention, cooperate additives such as adding oxidation inhibitor, UV light absorber, weathering resistance stablizer, heat-resisting stabilizing agent, antistatic agent, fire retardant, pigment, dyestuff.
Thermoplastic resin composition of the present invention is modulated into by dissolve the additive that mixes above-mentioned multipolymer (A), magnesium hydroxide (B), lubricant (C) and cooperate as required with various existing well-known methods.
Promptly, thermoplastic resin composition of the present invention is by with above-mentioned each composition simultaneously or for example add in Henschel mixer, V-Mixer, drum mixer, the ribbon blender etc. successively and after mixing, utilize melting mixings such as single screw extrusion machine, multiple screw extruder, kneader, Banbury to obtain again.
Wherein, if use the device of mixing behavior excellences such as multiple screw extruder, kneader, Banbury, can access and make each composition high-quality thermoplastic resin composition of dispersive more equably.
In addition, can add above-mentioned additive as required, for example oxidation inhibitor etc. in above-mentioned arbitrary stage.
Moulded products
Moulded products of the present invention, can use thermoplastic resin composition that obtain according to the method described above, of the present invention, utilize methods such as various well-known melt molding methods, for example extrusion moulding, rotational molding moulding, calendering formation, injection molding, compressed moulding, blow molding, be shaped to various shapes.
When thermoplastic resin composition of the present invention being used for the purposes of electric wire foreskin and electric wire coating, moulded products of the present invention is meant electric wire foreskin and coating layer, this electric wire foreskin and coating layer utilize existing well-known method for example extruding forming method be formed on around the electric wire.
The moulded products of the present invention that obtains as described above, its tensile elongation (JIS K6301) is preferably 300～800% especially to serve as preferred more than 300%.
Tensile break strength (Ts) (JIS K6301) is serving as preferred more than the 10Mpa.In addition, embrittlement temperature (JIS C3005) is preferably-15 ℃ especially to serve as preferred below 0 ℃.
And the Ma Dengsi hardness of the moulded products that the present invention relates to (index of traumatic resistance) is (1/mm) more than 8, is preferably (1/mm) more than 10.
[use Tokyo to impact the Ma Dengsi hardness stretching deflection testing machine of corporate system, load the stretching deflection counterweight of 20g in the test piece of thickness 3mm, the furrow width that produces when measuring stretching deflection test piece calculates its inverse, and this value is Ma Dengsi hardness (1/mm)].
The effect of invention
According to the present invention, can provide a kind of thermoplastic resin, and the moulded products of the above-mentioned coating layer that forms by said composition etc., its metal-stripping for example when formation is coating coating layer around the electric wire, the electric wire excellent in workability can be easily coating layer peeled off from electric wire with cutter etc., and, can also prevent that the phenomenon of gum from appearring in the forcing machine mould exit when electric wire is Overmolded.
Thermoplastic resin composition of the present invention, because have aforesaid effect, so be applicable in the purposes such as the desired various moulded products of metal-stripping, the coating of for example electric wire, insulating tape, film, thin plate, pipeline, blow molding goods, be specially adapted in the purposes of electric wire foreskin and electric wire coating.
[embodiment]
Below, according to embodiment the present invention is described, but the present invention is not limited to these embodiment.
In addition, metal-stripping in embodiments of the invention 1～4, the comparative example 1～2 and the evaluation that prevents gum are carried out according to following method.
(1) metal-stripping
The evaluation of metal-stripping is with from the separability of laboratory plastic mixer screw rod and adopt following 5 grades of judgement criterias to carry out.
＜judgement criteria 〉
A: can peel off by enough hands
B: use scraper to peel off easily
C: use scraper to peel off
D: use scraper partly to peel off, and be difficult to all peel off
E: use scraper to be difficult to peel off
What (2) gum occurred prevents
The evaluation that prevents that gum occurs is the result according to the mould outlet place of visual observations forcing machine, adopts following 5 grades of judgement criterias to carry out.
＜judgement criteria 〉
A: begin through also not occurring gum more than 8 hours from extrusion moulding.
B: begin at 8 hours with the interior gum that occurs from extrusion moulding
C: begin at 4 hours with the interior gum that occurs from extrusion moulding
D: begin at 1 hour with the interior gum that occurs from extrusion moulding
E: begin at 30 minutes with the interior gum that occurs from extrusion moulding
And, used multipolymer (ethylene-styrene copolymer) in embodiment 1～4, the comparative example 1,2, magnesium hydroxide, the siloxanes handled through lubricant, coupling agent, initiator (superoxide) and lubricant are as follows:
Multipolymer
Ethylene-styrene copolymer (multipolymer interpolymer) (ESI-30)
Styrene content: 30 weight %
MI (1238,190 ℃ of ASTM D, 2.16 load): 1g/10 minute
Magnesium hydroxide through the lubricant processing
Trade(brand)name: KISHIMA5B, consonance chemical industry (strain) system
Median size: 0.6 μ m
Siloxanes
Organopolysiloxane;
Trade(brand)name: SH6018, Toray Dow Lorning (strain) system
Coupler
Vinyltrimethoxy silane;
Trade(brand)name: SZ6300, Toray Dow Lorning (strain) system
Initiator
1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane;
Trade(brand)name: PERHEXA3M, Japanese grease (strain) system
Lubricant
(1) lubricant (a)
The two erucicamides of ethylene
(2) lubricant (b)
The two oleylamide of ethylene
(3) lubricant (c)
Ethylene bis stearamide
(4) lubricant (d)
Glyceryl monostearate
(5) lubricant (e)
Trade(brand)name: DynamarFX5920A
The viton of Sumitomo 3M (strain) system
[embodiment 1]
Just ethylene-styrene copolymer (ESI-30) 36 weight parts, above-mentioned magnesium hydroxide 61 weight parts of handling through lubricant, above-mentioned siloxanes 3 weight parts, above-mentioned coupling agent 0.8 weight part, above-mentioned initiator 0.03 weight part, and above-mentioned lubricant (a) (the two erucicamides of trade(brand)name ethylene) 1 weight part, use Banbury, under 190 ℃ of resin temperatures, carry out melting mixing, granulation obtains thermoplastic resin composition's particle.
Then, thermoplastic resin composition's particle of obtaining is added single screw extrusion machine, under 200 ℃ of resin temperatures, carry out melting mixing, this melts is extruded range estimation mould outlet place, the generation state of observation gum from mould, according to aforesaid method, preventing of occurring of gum estimated.
In addition, with above-mentioned thermoplastic resin composition's particle, drop into the laboratory plastic mixer, under 200 ℃ of resin temperatures, carry out melting mixing, after the melting mixing thing cooling that obtains, according to the mixing thing of the state of cooling of adhering on the plastic mixer screw rod of laboratory, metal-stripping is estimated according to aforesaid method.Its result is as shown in table 1.
[embodiment 2～4 and comparative example l～2]
In embodiment 1, except that the proportion of composing shown in the table l, with the method enforcement same with EXAMPLE l.The result is as shown in table 1.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |||
| Thermoplastic resin composition's composition (weight part) | Multipolymer ESI-30 | 36 | 36 | 36 | 36 | 36 | 36 | |
| Mg(OH) 2 | 61 | 61 | 61 | 61 | 61 | 61 | ||
| Siloxanes | 3 | 3 | 3 | 3 | 3 | 3 | ||
| Coupler | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | ||
| Initiator | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | ||
| Lubricant | (a) | 1 | ||||||
| (b) | 1 | |||||||
| (c) | 1 | |||||||
| (d) | 1 | |||||||
| (e) | 0.1 | |||||||
| Metal-stripping | A | A | A | A | E | E | ||
| Prevent mould outlet place gum | A | A | A | A | E | E | ||
The tensile elongation of thermoplastic resin composition among the embodiment 5～10, tensile break strength, Ma Dengsi hardness and embrittlement temperature are to measure according to following test method.Metal-stripping, prevent that the effect of gum from estimating according to the method described above.
(1) tensile elongation and tensile break strength
With JIS K 6301 is standard, with No. 3 dumbbell-shaped test pieces of JIS, carries out tension test with spacing 20mm, draw speed 200mm/ branch, measures tensile elongation and tensile break strength.
(2) Ma Dengsi hardness (index of traumatic resistance)
Use Tokyo to impact the Ma Dengsi hardness stretching deflection testing machine of corporate system, in the test piece of thickness 3mm, load the heavy burden of 10g, 20g, 30g, 50g, the furrow width that produces when measuring stretching deflection test piece calculates its inverse, and this value is Ma Dengsi hardness (1/mm).
(3) embrittlement temperature (index of brittle resistance under the low temperature)
Embrittlement temperature is a standard with JIS C 3005, tests and measures.
And used multipolymer (ethylene-styrene copolymer) among the embodiment 5～10, magnesium hydroxide, the magnesium hydroxide through silane treatment, undressed magnesium hydroxide, siloxanes, coupler, initiator (superoxide) and the lubricant handled through lubricant are as follows.
Multipolymer
Ethylene-styrene copolymer (multipolymer interpolymer) (ESI-30);
Styrene content: 30 weight %
MI (1238,190 ℃ of ASTM D, 2.16 bear a heavy burden): 1g/10 minute
Magnesium hydroxide through the lubricant processing
(1) magnesium hydroxide (B-1-1);
Trade(brand)name: KISHIMA5B, consonance chemical industry (strain) system
Median size: 0.6 μ m
(2) magnesium hydroxide (B-1-2);
Trade(brand)name MagseedsN-1, refreshing island chemistry (strain) system
Median size: 4 μ m
Undressed magnesium hydroxide
Magnesium hydroxide (B-2-1);
Trade(brand)name: UD-650, space portion material (strain) system
Median size: 2 μ m
Magnesium hydroxide through silane treatment
Magnesium hydroxide (B-3-1)
Trade(brand)name: KISHIMA5LH, consonance chemical industry (strain) system
Median size: 0.6 μ m
Siloxanes
Organopolysiloxane;
Trade(brand)name: SH6018, Toray Dow Lorning (strain) system
Coupler
Vinyltrimethoxy silane
Trade(brand)name: SZ6300, Toray Dow Lorning (strain) system
Initiator
1,1-di-tert-butyl peroxide-3,3,5-trimethyl-cyclohexane;
Trade(brand)name: PERHEXA3M, Japanese grease (strain) system
Lubricant
(1) lubricant (a)
The two erucicamides of ethylene
(2) lubricant (b)
Glyceryl monostearate (trade(brand)name: Off ァ Le パ ッ Network L-1014, Japanese grease (strain) system)
[embodiment 5]
With ethylene-styrene copolymer (ESI-30) 36 weight parts, magnesium hydroxide (B-1-1) 20 weight parts, magnesium hydroxide (B-3-1) 40 weight parts, above-mentioned siloxanes 3 weight parts, above-mentioned coupling agent 0.8 weight part, above-mentioned initiator 0.03 weight part and above-mentioned lubricant (a) 1 weight part through silane treatment through the lubricant processing, use Banbury, under 190 ℃ of resin temperatures, carry out melting mixing, granulation obtains thermoplastic resin composition's particle.
Thermoplastic resin composition's particle that use obtains carries out impact briquetting under 190 ℃, obtain products of press forming.
As the moulded products that obtains, its tensile elongation, tensile break strength, Ma Dengsi hardness, embrittlement temperature are measured according to the method described above.
Its result is as shown in table 2.
[embodiment 6～10]
In embodiment 5, except that the proportion of composing shown in the table 2, with method similarly to Example 5, modulation thermoplastic resin composition particle, products of press forming.
As the moulded products that obtains, its tensile elongation, tensile break strength, Ma Dengsi hardness, embrittlement temperature are measured according to the method described above.Its result is as shown in table 2.
[table 2]
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |||
| Thermoplastic resin composition's composition (weight part) | Multipolymer ESI-30 | 36 | 36 | 36 | 36 | 36 | 36 | |
| Mg(OH) 2 | Lubricant item for disposal (B-1-1) | 20 | 61 | 0 | ||||
| Lubricant item for disposal (B-1-2) | 15 | 61 | 0 | |||||
| Product (B-2-1) are untreated | 46 | 0 | 61 | |||||
| Silane treatment product (B-3-1) | 40 | 0 | 61 | |||||
| Siloxanes | 3 | 3 | 3 | 3 | 3 | 3 | ||
| Coupler | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | 0.8 | ||
| Initiator | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | 0.03 | ||
| Lubricant | (a) | 1 | 1 | 1 | ||||
| (b) | 1 | 1 | 1 | |||||
| The character of moulded products | Tensile elongation (%) | 460 | 480 | 440 | 480 | 480 | 450 | |
| Tensile break strength (MPa) | 11.0 | 12.2 | 10.8 | 15.7 | 11.6 | 11.6 | ||
| Ma Dengsi hardness (mm -1) | Heavy burden 10g | 12.6 | 11.6 | 14.1 | 13.1 | 8.9 | 12.8 | |
| Heavy burden 20g | 10.1 | 9.1 | 11.3 | 10.3 | 6.5 | 10.2 | ||
| Heavy burden 30g | 7.5 | 6.5 | 8.5 | 7.4 | 4.1 | 7.6 | ||
| Heavy burden 50g | 5.3 | 5.2 | 6.8 | 5.6 | 3.3 | 6.1 | ||
| Embrittlement temperature (℃) | -40.7 | -31.7 | -13.8 | -30.5 | -18.2 | -12.9 | ||
| Metal-stripping | A | A | A | A | A | A | ||
| Prevent that gum from appearring in the mould outlet place | A | A | A | A | A | A | ||
Arbitrary example of embodiment 1～10 has all shown metal-stripping, has prevented the goods of gum effect excellence.And, as magnesium hydroxide, and used the embodiment 5 of lubricant item for disposal and silane treatment product and the embodiment 6 that uses separately respectively, embodiment 7 to compare, shown low temperature good, traumatic resistance (Ma Dengsi hardness) excellence of balance of excellent brittle resistance, tensile elongation and tensile break strength down.As and used through lubricant and handled and the embodiment 8 and the embodiment 9 that uses respectively, embodiment 10 comparisons of undressed magnesium hydroxide, shown same result.
Claims (3)
1. thermoplastic resin composition is characterized in that:
With 97.0～99.9: it is 20～80 weight parts that 0.1～3.0 weight ratio { [(A)+(B)]: (C) } and composition (B) are measured 100 weight parts with respect to composition (A), (B) and total (C), contains:
(A) by (1) (a) at least a aromatic vinyl or vinylidene monomer; Or
(b) at least a aliphatics or annular aliphatic ethene or the vinylidene monomer of being obstructed; Or
(c) combination of at least a aromatic vinyl or vinylidene monomer and at least a be obstructed aliphatics or annular aliphatic ethene or vinylidene monomer;
1～99 mole of % of deutero-polymerized unit and
(2) 1～99 mole of % of the alpha-olefin derived polymerized unit of at least a carbonatoms 2～20 constitute, at least a be random multipolymer;
(B) magnesium hydroxide;
(C) be selected from the lubricant that at least a compound among aliphatic category tensio-active agent C-1 and the fatty amide C-2 constitutes.
2. moulded products of making by the described thermoplastic resin composition of claim 1.
3. moulded products as claimed in claim 2 is characterized in that: moulded products is electric wire foreskin or wire covering materials.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001-364026 | 2001-11-29 | ||
| JP2001364026A JP2003165880A (en) | 2001-11-29 | 2001-11-29 | Thermoplastic resin composition and molded product |
| JP2001364026 | 2001-11-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1422895A CN1422895A (en) | 2003-06-11 |
| CN1238416C true CN1238416C (en) | 2006-01-25 |
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| CN 02153041 Expired - Fee Related CN1238416C (en) | 2001-11-29 | 2002-11-29 | Thermal plastic resin composition and formed articles |
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| CN (1) | CN1238416C (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1665888A (en) * | 2002-07-01 | 2005-09-07 | 三井化学株式会社 | Thermoplastic resin composition and molding consisting of the composition |
| CN114350061B (en) * | 2021-11-30 | 2023-09-26 | 金发科技股份有限公司 | Polypropylene composition and preparation method and application thereof |
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