CN103865191A - Polyvinyl chloride resin composition and insulated wire using polyvinyl chloride resin composition - Google Patents
Polyvinyl chloride resin composition and insulated wire using polyvinyl chloride resin composition Download PDFInfo
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- CN103865191A CN103865191A CN201310349184.8A CN201310349184A CN103865191A CN 103865191 A CN103865191 A CN 103865191A CN 201310349184 A CN201310349184 A CN 201310349184A CN 103865191 A CN103865191 A CN 103865191A
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Abstract
A subject of the invention is to provide a polyvinyl chloride resin composition of excellent extrusion moldability, mechanical properties and cold resistance and an insulated wire using the polyvinyl chloride resin composition. The method to solve the problem of the invention relates to a polyvinyl chloride resin composition which comprises polyvinyl chloride resin (A), a plasticizer (B) and a non-lead stabilizer (C), and does not contain polymethyl methacrylate acting as a gelling agent. The non-lead stabilizer (C) comprises a zinc-containing metallic soap (c1) and hydrotalcite (c2). With respect to 100 mass% of the polyvinyl chloride resin composition, the following plasticizer (B) accounts for 19 mass% to 24 mass%, the non-lead stabilizer (C) accounts for 4 mass% or more, and a mass ratio (c2/c1) of the hydrotalcite (c2) to the zinc-containing metallic soap (c1) is above 3.5 and below 10.
Description
Technical field
The present invention relates to poly (vinyl chloride) resin composition and used the insulated line of this poly (vinyl chloride) resin composition.
Background technology
Insulated line possesses and has conductor and by insulation-coated (insulation layer) of conductor coating, as wiring in the equipment of such as electric installation etc.In equipment, wiring forms by many insulated lines are connected in to junctor.Connection about from insulated line to junctor, by insulated line is inserted in to junctor, is connected in the terminal of junctor and carries out.
Connection as from insulated line to junctor, has and is for example pressing connection (pressing Jie continued) or crimping to connect (Ya Jie Jie continued).Pressing to connect and be: the conductor terminal of insulated line exposed, the method that the conductor having exposed is connected singly with terminal.Crimping connects: insulated line is pressed between the terminal of bladed and gets into, puncture insulation layer on one side, method conductor being connected with terminal by terminal on one side.Crimping connects not to be needed as pressed connection, conductor terminal to be exposed, and many insulated lines side by side can be connected together.
But in recent years, corresponding to the miniaturization of electric installation, also carrying out the miniaturization of wiring in equipment, and tend to thin diameter for the insulated line connecting up in equipment, tend in addition for example, be connected in junctor with thin space (1.0mm～1.5mm).According to this tendency, in the connection of junctor, adopt the crimping that many insulated lines side by side can be connected together to connect at insulated line.
In the insulated line connecting in crimping, thereby get into and apply large pressure by being pressed between terminal.Thus, require this insulation layer to there is the mechanical characteristics of regulation, so that do not deform under the effect of pressure.When the mechanical characteristics of insulation layer is low, insulation layer deforms, be difficult for insulated line to be held in junctor, thereby have from junctor come off and cause poor flow may.
As the resin that forms such insulation layer, have polyvinyl chloride (PVC) RESINS.Polyvinyl chloride (PVC) RESINS is polar polymer, and intermolecular forces is strong, thereby becomes the forming composition of hard, but becomes soft forming composition by adding softening agent.That is, in polyvinyl chloride (PVC) RESINS, in the time adding softening agent more, become soft PVC resin, manifest flexibility, become semi-rigid polyvinyl chloride (PVC) RESINS when fewer while adding softening agent on the other hand, manifest the mechanical characteristics of regulation.
Insulation layer is required in the situation of high mechanical characteristics, in insulation layer, can use the semi-rigid polyvinyl chloride (PVC) RESINS that plasticizer loading is few.Formed by semi-rigid polyvinyl chloride (PVC) RESINS in the situation of insulation layer, by add a small amount of softening agent in polyvinyl chloride (PVC) RESINS, carry out mixing thereby softening agent being disperseed to make resin combination, then utilize heating by this resin combination melting, thus by melting resin combination extrude on conductor and to form.In the time that resin combination melting is heated polyvinyl chloride (PVC) RESINS occur deteriorated, add the non-lead stabilizer of metal soap, the hydrotalcites etc. such as fatty acid zinc as thermo-stabilizer (for example, with reference to patent documentation 1) according to the mode that does not make the reductions such as mechanical characteristics.
But, using semi-rigid polyvinyl chloride (PVC) RESINS and manufacturing in the situation of insulated line, the production rate that has insulated line is slow, the low such problem of productivity.About the production rate of insulated line, resin extruded speed (extruded velocity) on conductor is more more uprised, but for example at the extruded velocity take in semi-rigid polyvinyl chloride (PVC) RESINS being extruded below wall thickness 0.15mm as 350m/min becomes the upper limit, be difficult to increase extruded velocity and boost productivity.This be due to, in semi-rigid polyvinyl chloride (PVC) RESINS, contain more a small amount of softening agent, the viscosity under the state of melting is high, forming process (extrusion moulding) is low.When for example extruded velocity 400m/min extrudes semi-rigid polyvinyl chloride (PVC) RESINS low extrusion moulding, have the insulation layer of formation appearance shark skin shape the possibility of chapping.This phenomenon is so-called melt fracture, not only hinders insulated line to connect to the crimping of junctor, and working (machining) efficiency is reduced, and becomes the major cause that causes the coating of printing ink (ink) to reduce.
In order to improve the extrusion moulding of semi-rigid polyvinyl chloride (PVC) RESINS, improve the productivity of insulated line, can consider to improve the Heating temperature of semi-rigid polyvinyl chloride (PVC) RESINS heating is adjusted to viscosity, but when Heating temperature uprises, exist polyvinyl chloride (PVC) RESINS itself occur deteriorated and cannot obtain the possibility of the characteristic of acquisition originally.In addition, can consider to increase the content of the softening agent that will add, turn down viscosity, but have polyvinyl chloride (PVC) RESINS generation softening, the possibility that the mechanical characteristics of the insulation layer obtaining is reduced.
In this wise, use semi-rigid polyvinyl chloride (PVC) RESINS and manufacturing in the situation of insulated line, the viscosity of semi-rigid polyvinyl chloride (PVC) RESINS is high, and extrusion moulding is low, thereby extruded velocity is restricted, is difficult to improve the productivity of insulated line.
In this, in patent documentation 2～4, propose: to improve extrusion moulding as object, in polyvinyl chloride (PVC) RESINS, add the polymethylmethacrylate scheme of (being also called below PMMA).According to patent documentation 2～4, can improve the extrusion moulding of poly (vinyl chloride) resin composition, improve the productivity of insulated line.
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2004-193138 communique
Patent documentation 2: TOHKEMY 2003-327762 communique
Patent documentation 3: TOHKEMY 2005-89604 communique
Patent documentation 4: TOHKEMY 2005-89605 communique
Summary of the invention
The problem that invention will solve
But, according to the poly (vinyl chloride) resin composition of patent documentation 2～4, by adding PMMA etc. as gelation promotor, can maintain mechanical characteristics and improve extrusion moulding on one side, be still difficult to realize the further high speed of extruded velocity.That is, extrusion moulding is insufficient, and while making the further high speed of extruded velocity, the outward appearance of extruding that has the insulation layer of formation becomes bad situation., and according to the poly (vinyl chloride) resin composition of patent documentation 2～4, due to the PMMA containing as low-molecular(weight)polymer, thereby exist winter hardiness to reduce such problem moreover.
The present invention completes in view of above-mentioned problem, and its object is to provide the poly (vinyl chloride) resin composition of extrusion moulding, mechanical characteristics and winter hardiness excellence.Object is to provide that to have mechanical characteristics and winter hardiness excellent and extrude the insulated line of the good insulation layer of outward appearance in addition.
For the method for dealing with problems
According to the 1st embodiment of the present invention, a kind of poly (vinyl chloride) resin composition is provided, it contains polyvinyl chloride (PVC) RESINS (A), softening agent (B), non-lead stabilizer (C), and not containing the polymethylmethacrylate as gelation promotor, aforementioned non-lead stabilizer (C) comprises zinc metallic soap (c1) and hydrotalcite (c2), with respect to aforementioned poly (vinyl chloride) resin composition 100 quality %, contain the aforementioned softening agent (B) below the above 24 quality % of 19 quality %, aforementioned non-lead stabilizers (C) more than 4 quality %, aforementioned hydrotalcite (c2) is more than 3.5 below 10 with respect to the mass ratio (c2/c1) of aforementioned zinc metallic soap (c1).
According to the 2nd embodiment of the present invention, the poly (vinyl chloride) resin composition of the 1st embodiment is provided, it contains the aforementioned non-lead stabilizer (C) below the above 20 quality % of 4 quality %.
According to the 3rd embodiment of the present invention, the poly (vinyl chloride) resin composition of the 1st embodiment or the 2nd embodiment is provided, aforementioned non-lead stabilizer (C) further comprises at least a kind in the group of selecting free beta-diketone compounds, antioxidant, polyvalent alcohol, metal hydrate composition, they add up to below 50% of aforementioned non-lead stabilizer (C).
According to the 4th embodiment of the present invention, the poly (vinyl chloride) resin composition of any one in the 1st～3rd embodiment is provided, it further contains at least a kind of additive (D) in the group of selecting free weighting agent, tinting material composition, and contains the aforementioned additive (D) below 10 quality %.
According to the 5th embodiment of the present invention, a kind of insulated line is provided, it has the insulation layer being made up of the poly (vinyl chloride) resin composition of any one in the 1st～4th embodiment.
According to the 6th embodiment of the present invention, the insulated line of the 5th embodiment is provided, it connects for junctor crimping, and the thickness of aforementioned dielectric layer is below 0.2mm.
The effect of invention
According to the present invention, can obtain the poly (vinyl chloride) resin composition of extrusion moulding, mechanical characteristics and winter hardiness excellence.In addition, can obtain that to have mechanical characteristics and winter hardiness excellent and extrude the insulated line of the good insulation layer of outward appearance.
Accompanying drawing explanation
Fig. 1 is the figure that represents the section of the insulated line of an embodiment of the invention.
Description of reference numerals
1 insulated line
11 conductors
12 insulation layers
Embodiment
The opinion > that the < inventor obtains
Before explanation an embodiment of the invention, the opinion that the inventor is obtained describes.
As described above, only by added the polymethylmethacrylate (being also called below PMMA) as gelation promotor in semi-rigid polyvinyl chloride (PVC) RESINS, make extrusion moulding insufficient, in the time making the further high speed of extruded velocity, make the outward appearance of extruding of insulation layer worsen.The low reason of extrusion moulding of semi-rigid polyvinyl chloride (PVC) RESINS is, softening agent etc. are not dispersed, viscosity while making heating and melting inhomogeneous (viscosity inhomogeneous).And can think, make in the situation of extruded velocity high speed, the inhomogeneous impact of viscosity becomes large, makes to extrude outward appearance and worsens.In this, the inventor has attempted by mixing condition (structure of screw rod, cylinder body (cylinder) etc.) is suitably changed, by dispersed softening agent etc., thereby improve the outward appearance of extruding of the extrusion moulding of poly (vinyl chloride) resin composition and insulation layer, but cannot realize in the situation that making extruded velocity high speed.
Only cannot improve extrusion moulding by changing mixing condition, thereby the inventor thinks, except mixing, become major cause aspect the dispersion efficiency in the assimilated efficiency of softening agent, while using gelation promotor etc., conduct in-depth research.Its result is thought, has the variation of the porosity (porosity) in polyvinyl chloride (PVC) RESINS in these major causes.
Herein, porosity represents the voidage in polyvinyl chloride (PVC) RESINS.In polyvinyl chloride (PVC) RESINS, there is space with the porosity (voidage) stipulating, in the time thering is sufficient space, contribute to the absorption of softening agent, make the dispersed possibility that becomes.In the time disperseing, in polyvinyl chloride (PVC) RESINS, add softening agent etc., use high-speed mixer and be absorbed in space, then carry out with the shearing (shear) (shearing force) of regulation mixing, thereby make polyvinyl chloride particles collapse (collapsing bad).
, in polyvinyl chloride (PVC) RESINS, when mixing with the shearing force that stipulates, space does not distribute mostly equably, and the collapse of locality occurs sometimes and porosity is changed.This situation is caused the dispersed inhomogeneous of softening agent sometimes.Result causes, the poly (vinyl chloride) resin composition obtaining in melting state under viscosity become inhomogeneous, extrusion moulding reduce.Particularly, when mixing polyvinyl chloride (PVC) RESINS, the part of space generation locality collapse becomes gel section, and the part of not collapsing on the other hand becomes not gel section.The compare optical density of softening agent of gel section and gel section is not low, even if melting is also inclined to as viscosity is high, thereby becomes and causes the viscosity of polyvinyl chloride (PVC) RESINS in the time of melting to become inhomogeneous major cause.
Particularly make semi-rigid polyvinyl chloride (PVC) RESINS in the case of disperseing a small amount of softening agent, mixing owing to being difficult for (mixing property is low), thereby tend to make shearing force grow, promote the collapse of the locality in space, extrusion moulding is further reduced.
In addition, using in the situation of disperseing as the PMMA of gelation promotor etc., PMMA self works to the particle collapse of polyvinyl chloride (PVC) RESINS, but in order to make melt viscosity increase, for example needing to carry out thick refining based on kneader and suppress heating while formally mixing (this Practice) of carrying out such two-stage mixing by mixing roll, is inefficient.In addition, the interpolation of PMMA raises the melting tension force of polyvinyl chloride (PVC) RESINS, thereby causes the outward appearance being caused by melt fracture and worsen, and is not suitable for the high speed extrusion of electric wire.
In this wise, add a small amount of softening agent, gelation promotor and make in the situation of semi-rigid polyvinyl chloride (PVC) RESINS, the collapse that locality occurs because of space in mixing forms not gel section, makes the dispersiveness of softening agent etc. become extrusion moulding (shaping speed, outward appearance) inhomogeneous, poly (vinyl chloride) resin composition that obtain and reduces.
In addition, gel section does not only reduce extrusion moulding and hinders the high speed of production rate, and the outward appearance of extruding of the insulation layer forming is worsened.In addition, gel section and gel section are not comparatively speaking difficult for absorbing softening agent, thermo-stabilizer etc., thermal degradation when speed is fast, therefore there is not gel section in polyvinyl chloride (PVC) RESINS time, cause chlorine to depart from because being derived from the not thermal degradation when of gel section, because the chlorine detaching promotes that resin globality ground is deteriorated.
Therefore, the inventor is being difficult to aspect mixing semi-rigid polyvinyl chloride (PVC) RESINS, for not only by lowering the collapse (variation of porosity) of the mixing locality that suppresses space but also the method for the dispersions such as softening agent being conducted in-depth research.Having found that of research, in order to be to make softening agent disperse on minimal basis by mixing inhibition, it is effective that the thermotolerance to polyvinyl chloride (PVC) RESINS and inside and outside oilness are controlled.That is, thermotolerance and inside and outside oilness affect the mixing property of poly (vinyl chloride) resin composition, thereby they are controlled to the dispersiveness that can improve mixing property and improve softening agent etc.Found, as this control, the zinc metallic soap of giving thermotolerance and inside and outside oilness by adjustment with augment the mass ratio of stable on heating hydrotalcite, thereby can make the dispersiveness of softening agent etc. evenly improve extrusion moulding.The present invention is based on above opinion and complete.
< an embodiment of the invention >
Below an embodiment of the invention are described.
(1) poly (vinyl chloride) resin composition
The poly (vinyl chloride) resin composition of present embodiment contains: polyvinyl chloride (PVC) RESINS (A), softening agent (B), the non-lead stabilizer (C) that comprises zinc metallic soap (c1) and hydrotalcite (c2), do not contain polymethylmethacrylate as gelation promotor.And, with respect to poly (vinyl chloride) resin composition 100 quality %, contain the softening agent (B) below the above 24 quality % of 19 quality %, non-lead stabilizers (C) more than 4 quality %, hydrotalcite (c2) is more than 3.5 below 10 with respect to the mass ratio (c2/c1) of zinc metallic soap (c1).
(polyvinyl chloride (PVC) RESINS (A))
As polyvinyl chloride (PVC) RESINS, except the homopolymer of vinylchlorid,, outside polyvinyl chloride, also list vinylchlorid and other can copolymerization the multipolymer of monomer and their mixture.As polyvinyl chloride (PVC) RESINS, the polyvinyl chloride (PVC) RESINS of preferred average degree of polymerization in 1000～3000 scope.When mean polymerisation degree less than 1000, mechanical characteristics, thermotolerance etc. reduce sometimes, and mean polymerisation degree exceedes at 3000 o'clock, make sometimes when the molten resin temperature in the time not improving forming process extrusion moulding reduce.
(softening agent (B))
Softening agent (B) is to give poly (vinyl chloride) resin composition with flexibility, the additive of easily processing.Softening agent (B) is not particularly limited, and can use known softening agent, but preferred trimellitate class.Specifically list trimellitic acid n-octyl, tri trimellitate-2-ethylhexyl, triisononyl trimellitate, triisodecyl trimellitate etc.Wherein, consider the trimellitic acid n-octyl that more preferably alkyl chain length is straight chain type from the viewpoint of giving winter hardiness.In order to control cost, also a part for trimellitic acid n-octyl can be replaced into the trimellitate of side chain type.
With respect to poly (vinyl chloride) resin composition 100 quality %, the content that makes softening agent (B) is below the above 24 quality % of 19 quality %.When content exceedes 24 quality %, the mechanical characteristics of poly (vinyl chloride) resin composition is low, and the insulation layer of formation is easily because pressure is out of shape.On the other hand, during containing quantity not sufficient 19 quality %, not only mechanical characteristics is high, and the insulation layer of formation is difficult to carry out crimping connection, and winter hardiness (embrittlement temperature) is according to UL specification (758), has the possibility (likelihood) higher than-15 ℃.
(non-lead stabilizer (C))
Non-lead stabilizer (C) is thermo-stabilizer, when mixing heating, for hydrogenchloride from poly (vinyl chloride) resin composition depart from and deteriorated situation suppresses.With respect to poly (vinyl chloride) resin composition 100 quality %, the content that makes non-lead stabilizer (C) is more than 4 quality %.When the quantity not sufficient 4 quality %, while being difficult to keep poly (vinyl chloride) resin composition mixing or the thermostability in the time of extruding, the insulation layer generation coking of formation, causes bad order.In addition, the higher limit of the content of non-lead stabilizer (C) is not particularly limited, but is preferably below 20 quality %.By being below 20 quality %, thereby can suppress the foaming, painted of formed insulation layer.
In the present embodiment, as described above, according to can by mixing inhibition be on MIN basis by the homodisperse mode of softening agent (B), control thermotolerance and the inside and outside oilness of poly (vinyl chloride) resin composition.
In order to realize this control, non-lead stabilizer (C) comprise give thermotolerance and inside and outside oilness zinc metallic soap (c1) and, augment stable on heating hydrotalcite (c2).Below, describe respectively.
Zinc metallic soap (c1) is main stabilizer, is formed by aliphatic carboxylic acid (lipid acid) and zinc.Zinc metallic soap (c1) is high with the consistency of poly (vinyl chloride) resin composition, and favorable dispersity.In addition, give poly (vinyl chloride) resin composition with inside and outside oilness, and give the thermotolerance of regulation.Zinc metallic soap (c1) is not particularly limited, but the zinc metallic soap that the lipid acid that to be preferably by carbonatoms be 12～24 and zinc form for example lists Zinic stearas, zinc laurate.According to such zinc metallic soap (c1), zinc content is below the above 15 quality % of 7 quality %, in the situation of adding with the content stipulating, also can exceedingly not increase the zinc content in resin combination., can suppress the stable on heating reduction that caused by the increase of the zinc content in resin combination.Be explained, zinc metallic soap also can and be used two or more.
Hydrotalcite (c2) is stabilization aid, suppresses deteriorated by hydrogenchloride seizure effect, improves the thermotolerance of poly (vinyl chloride) resin composition.Hydrotalcite (c2) is by being combined in zinc metallic soap (c1), thereby augments the thermotolerance being obtained by zinc metallic soap (c1).Hydrotalcite (c2) is not particularly limited, and is between 1～1.2 but preferably the strength ratio (Mg/Al) of the magnesium obtaining based on x-ray fluorescence analysis (Mg) and aluminium (Al) is controlled.Its reason is that easily painted when magnesium part becomes many, the starting point of dewatering when Al part becomes many becomes early, causes foaming.
In non-lead stabilizer (C), hydrotalcite (c2) is more than 3.5 below 10 with respect to the mass ratio (c2/c1) of zinc metallic soap (c1).Be preferably more than 3.5 below 7.5.(c2/c1) when less than 3.5, the content of zinc metallic soap (c1) relatively increases, excessive thereby the outer oilness of poly (vinyl chloride) resin composition becomes, and poly (vinyl chloride) resin composition is difficult for gelation equably.That is, the viscosity of poly (vinyl chloride) resin composition becomes inhomogeneous, and extrusion moulding reduces, and the outward appearance of extruding of the insulation layer of formation etc. becomes bad.On the other hand, (c2/c1) exceed at 10 o'clock, have the possibility that foaming occurs in the time that poly (vinyl chloride) resin composition is extruded, need in the time extruding, adjust temperature.
In this wise, in the scope of the mass ratio of the poly (vinyl chloride) resin composition of present embodiment (c2/c1) for regulation, thermotolerance and inside and outside oilness have been adjusted.Thus, (C) is dispersed for softening agent (B), non-lead stabilizer, inhomogeneous (viscosity inhomogeneous) of the viscosity while having suppressed melting, extrusion moulding excellence.And the outward appearance of extruding of the insulation layer of formation becomes good.
Be explained, about non-lead stabilizer (C), except above-mentioned zinc metallic soap (c1) and hydrotalcite (c2), also can further comprise at least a kind in the group (compound (c3)) of selecting free beta-diketone compounds, antioxidant, polyvalent alcohol, metal hydrate composition.Compound (c3) by with the combination of zinc metallic soap (c1), hydrotalcite (c2), thereby can further augment thermostability, can further improve the extrusion moulding of poly (vinyl chloride) resin composition.Particularly, the consistency of beta-diketone compounds and poly (vinyl chloride) resin composition is high, can improve in addition the stability of zinc metallic soap (c1), therefore preferably adds.The total of the content of compound (c3) is preferably below 50% of non-lead stabilizer (C)., the total of zinc metallic soap (c1) and hydrotalcite (c2) is preferably the more than 50% of non-lead stabilizer (C).
Beta-diketone compounds is not particularly limited, for example, list diphenylpropane-1,3-dione(DPPO) (DBM), stearoyl benzoyl methane (SBM).The photosensitivity of the insulation layer that consideration will form, the content of beta-diketone compounds is preferably below 0.5 quality %.
Antioxidant is not particularly limited, and has to have the main anti-oxidants such as the phenol system of radical-scavenging effect, have the secondary antioxidants such as the sulphur system of peroxide breakdown effect, and they can be used alone, and also can and use them.Preferably also with any number of.About the content of antioxidant, according to the mode that does not generate bloom (blooming) in poly (vinyl chloride) resin composition, be preferably below 0.5 quality %.
In the main anti-oxidant of phenol system, have and be categorized into respectively the main anti-oxidant that single phenol is, bis-phenol is and polyphenol is.The main anti-oxidant that single phenol is for example lists: 2, and 2 '-di-tert-butyl-4-methy phenol, 2,6-di-t-butyl-4-ethylphenol or single (Alpha-Methyl phenyl) phenol etc.In addition, the main anti-oxidant of bis-phenol system for example lists: 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol), 4,4 '-butylidene-bis(3-methyl-6-t-butyl phenol), 4, butylation reaction product or two (Alpha-Methyl phenyl) phenol of 4 '-thiobis (3 methy 6 tert butyl phenol), p-cresol and dicyclopentadiene etc.Further, the main anti-oxidant of polyphenol system for example lists 2,5 '-di-tert-butyl hydroquinone, 2,5 '-bis--amyl hydroquinone, three (Alpha-Methyl phenyl) phenol etc.
In the secondary antioxidants of sulphur system, there is the secondary antioxidants that is categorized into respectively benzoglyoxaline system, dithiocar-bamate system, thiocarbamide system and organic thioic acid sulfoacid system.The secondary antioxidants of benzoglyoxaline system for example lists the zinc salt of 2-mercaptobenzimidazole, 2 mercaptomethyl benzimidazole or 2-mercaptobenzimidazole etc.In addition, the secondary antioxidants of dithiocar-bamate system for example lists nickel diethyldithiocarbamate or nickel dibutyl dithiocarbamate etc.Further, the secondary antioxidants of thiocarbamide system for example lists two (the dimethylaminopropyl)-2-thiocarbamides of 1,3-or tributyl thiourea etc.Further, the secondary antioxidants that organic thioic acid sulfoacid is lists Tyox B etc.
Polyvalent alcohol is not particularly limited, for example, list tetramethylolmethane, Dipentaerythritol, tripentaerythritol, four tetramethylolmethanes, sorbyl alcohol, glycerine, Polyglycerine etc.In addition, also can list the material that a part for the hydroxyl of these polyvalent alcohols is carried out to esterification, etherificate and obtain.About the content of polyvalent alcohol, according to the mode of not oozing out in the time forming insulation layer etc., be preferably below 0.5 quality %.
Metal hydrate is not particularly limited, for example, list calcium hydroxide, aluminium hydroxide, magnesium hydroxide etc.Consider from the painted viewpoint that suppresses insulation layer, preferably aluminium hydroxide.In addition, consider preferably calcium hydroxide, magnesium hydroxide from the viewpoint of the hydrogenchloride seizure effect that adds man-hour of poly (vinyl chloride) resin composition.They can not use a kind, also can and use two or more.Be explained, the content of metal hydrate is not particularly limited, and can suitably change.
(additive (D))
In the poly (vinyl chloride) resin composition of present embodiment, except softening agent (B), non-lead stabilizer (C), also can contain at least a kind of additive (D) in the group of selecting free weighting agent, tinting material composition.The content of additive (D) is preferably below 10 quality %.When the content of additive (D) exceedes 10 quality %, the viscosity when extrusion moulding of poly (vinyl chloride) resin composition increases, thereby the outward appearance of extruding of the insulation layer forming etc. becomes bad sometimes.
As weighting agent, if the content of the poly (vinyl chloride) resin composition in reduced insulation layer and the such weighting agent of inhibition cost are not particularly limited.For example list calcium carbonate, silicic acid (silicate compound) etc.Calcium carbonate can use any in heavy or lightweight.In the situation of water-ground limestone, in order to make the outward appearance of insulation layer for good, preferably making median size is below 10 μ m.About silicic acid (silicate compound), if the material of making by synthesis method is not particularly limited, also can use the pure aluminium silicate (calcined clay) kaolinite sintering being obtained at high temperature.
Tinting material is not particularly limited, for example, list granular processed pigment, colored masterbatch etc.
(2) manufacture method of poly (vinyl chloride) resin composition
The manufacture method of the poly (vinyl chloride) resin composition to above-mentioned embodiment describes.
First,, with respect to polyvinyl chloride (PVC) RESINS (A), softening agent (B) and non-lead stabilizer (C) are added according to the mode of the content that becomes regulation.Now, as non-lead stabilizer (C), use zinc metallic soap (c1) and hydrotalcite (c2), but be more than 3.5 below 10, be preferably more than 3.5 mode below 7.5 according to the mass ratio (c2/c1) that makes them, determine addition separately.
Then, manufacture poly (vinyl chloride) resin composition by mixing said mixture.In mixing, use internal mixer (internal mixer), kneader and slightly refine.As the mixing condition of thick refining, 110 ℃ of chamber (chamber) temperature are above below 140 ℃, for example, if rotating shaft (rotor) (screw rod) can be made as below 30rpm, if internal mixer can be made as below 60rpm.In the present embodiment, the mass ratio of zinc metallic soap (c1) and hydrotalcite (c2) is made as to the numerical range of regulation, thereby controls thermotolerance and the inside and outside oilness of poly (vinyl chloride) resin composition.Thus, need in thick refining and formal mixing two-stage, not carry out mixingly, softening agent (B) can be disperseed.
In addition, by the mixing inferior limit that is made as, can suppress the collapse of the locality in space, thereby can make the dispersion of softening agent (B) etc. become evenly., in the present embodiment, can, by dispersed softening agent (B) etc., can obtain the poly (vinyl chloride) resin composition of extrusion moulding excellence.And, can omit in the past essential formally mixingly, manufacturing process is simplified.
Be explained, softening agent (B) and non-lead stabilizer (C) also can side by side add, but also can by non-lead stabilizer (C) add, mix, then by softening agent (B) add and mixing.In addition, additive (D) also can side by side add with softening agent (B), also can add softening agent (B) interpolation in advance before.
In addition, mixing time is not particularly limited.According to the poly (vinyl chloride) resin composition of present embodiment, due to being absorbed as evenly of softening agent, that is, and can softening agent is dispersed, thereby impact based on mixing time is few.As mixing time, be more for example within 600 seconds, to be more benchmark, but also can be early 120～180 seconds, in addition also can slow 240～300 seconds degree.
(3) insulated line
Then, the insulated line of an embodiment of the invention is described.The insulated line of present embodiment has the insulation layer being made up of above-mentioned poly (vinyl chloride) resin composition.Particularly, as shown in Figure 1, insulated line 1 has conductor 11, be formed in the periphery of conductor 11 and the insulation layer 12 being formed by above-mentioned poly (vinyl chloride) resin composition.
The material of conductor 11 is not particularly limited, for example, formed by the metallic substance such as copper or copper alloy.In addition, its conductor diameter is not particularly limited, and can suitably select optimum diameter according to purposes.Crimping is connected in the situation of junctor, and conductor diameter is preferably thin footpath, for example, be preferably below the above 0.6mm of 0.2mm.
The thickness of insulation layer 12 is not particularly limited, and selects optimum thickness according to purposes.Crimping is connected in the situation of junctor, and the external diameter of insulated line 1 is preferably thin footpath, thereby preferably the thickness of insulation layer 12 is below 0.2mm, more preferably below the above 0.2mm of 0.1mm.Insulation layer 12 is formed by the poly (vinyl chloride) resin composition that manifests high mechanical characteristics, even thereby the in the situation that of thin thickness, also show not the mechanical characteristics of the degree that deform under the effect of the pressure that can connect in crimping.
The effect > of < embodiments of the present invention
According to present embodiment, play one or more effects shown below.
According to present embodiment, poly (vinyl chloride) resin composition contains the softening agent (B) below the above 24 quality % of 19 quality %, non-lead stabilizers (C) more than 4 quality %.In addition, contain zinc metallic soap (c1) and the hydrotalcite (c2) that mass ratio (c2/c1) is the non-lead stabilizer of more than 3.5 conduct below 10 (C).Thus, softening agent (B) etc. is scattered here and there equably, thus melting state under viscosity even, extrusion moulding excellence.And, owing to not containing the low-molecular(weight)polymers such as gelation promotor, thereby winter hardiness excellence not only, and the content of softening agent (B) is fewer, therefore mechanical characteristics excellence.
In addition, according to present embodiment, poly (vinyl chloride) resin composition preferably contains the non-lead stabilizer (C) below the above 20 quality % of 4 quality %.Thus, can suppress, by foaming, the deterioration of extruding outward appearance causing such as painted, to make to extrude outward appearance good.
In addition, according to present embodiment, non-lead stabilizer (C) further comprises at least a kind in the group of selecting free beta-diketone compounds, antioxidant, polyvalent alcohol, metal hydrate composition, and their total is preferably below 50% of non-lead stabilizer (C).Thus, can further improve extrusion moulding.
In addition, according to present embodiment, further contain at least a kind of additive (D) in the group of selecting free weighting agent, tinting material composition, preferably contain the aforementioned additive (D) below 10 quality %.According to weighting agent, can lower the ratio of poly (vinyl chloride) resin composition, thereby can reduce the cost.In addition, according to tinting material, can suitably change the outward appearance of insulation layer etc.
In addition, according to present embodiment, mass ratio has in accordance with regulations added zinc metallic soap (c1) and hydrotalcite (c2), has adjusted thermotolerance and the inside and outside oilness of poly (vinyl chloride) resin composition, therefore can be only with thick refining, softening agent (B) etc. is dispersed.That is, can omit in the past essential formally mixingly, can make manufacturing process simplify.
In addition, according to present embodiment, insulated line has the insulation layer being made up of above-mentioned poly (vinyl chloride) resin composition.Thus, can obtain mechanical characteristics and winter hardiness excellence and extrude the good insulated line of outward appearance.In addition, insulation layer is owing to being formed by the poly (vinyl chloride) resin composition of mechanical characteristics excellence, even thereby thickness is made as below 0.2mm, be also difficult for deforming under the effect of the pressure connecting in crimping.That is, in the insulated line of present embodiment, suppressed to come off from junctor, be difficult for occurring poor flow.
Embodiment
Below embodiments of the invention are described.In the present embodiment, modulation poly (vinyl chloride) resin composition, uses it and has manufactured insulated line.And, measure the insulated line that obtains winter hardiness, extrude the crimping of outward appearance and insulated line, thereby poly (vinyl chloride) resin composition is evaluated.These embodiment are examples of the present invention, and the present invention is not limited to the examples.
The material using in following embodiment and comparative example is summarized as follows.
As polyvinyl chloride (PVC) RESINS (A), use material below.
Polyvinyl chloride (PVC) RESINS: SHIN-ETSU HANTOTAI's chemistry system " TK-1300 " (mean polymerisation degree 1300)
As softening agent (B), use material below.
Tri trimellitate n-octyl: flower king's system " N-08 "
Tri trimellitate-2-ethylhexyl: flower king's system " T-08 "
As the zinc metallic soap (c1) of non-lead stabilizer (C), use material below.
Zinc laurate: day east changes into system " ZS-3 " (zinc content 14%)
Zinic stearas: day east changes into system " Zn-St " (zinc content 10.7%)
As the hydrotalcite (c2) of non-lead stabilizer (C), use material below.
Hydrotalcite: Sakai chemistry " HT-1 "
As the beta-diketone compounds of non-lead stabilizer (C), use material below.
Diphenylpropane-1,3-dione(DPPO) (DBM): Tokyo changes into system
As the antioxidant of non-lead stabilizer (C), use material below.
Phenol is antioxidant: BASF system " 1010 "
As the polyvalent alcohol of non-lead stabilizer (C), use material below.
Dipentaerythritol: wide flourish chemical industry system
As the metal hydrate of non-lead stabilizer (C), use material below.
Calcium hydroxide: lucky damp lime industry system " Calmue Mesox "
As additive (D), use material below.
Calcium carbonate: standby northern efflorescence industry system " Softon2200 "
Silicon-dioxide: Japanese Aerosil system " R972 "
Colored masterbatch: the large day system of refining " MS series "
(2) modulation of poly (vinyl chloride) resin composition
Use above-mentioned materials and modulate the poly (vinyl chloride) resin composition of embodiment 1～5.Modulation condition is shown in to following table 1.
Table 1
In embodiment 1～5, modulate poly (vinyl chloride) resin composition according to the modulation condition shown in table 1.Particularly, by add the material except softening agent in polyvinyl chloride (PVC) RESINS, utilize 200L high-speed mixer (KAWATA system) to mix at 60 ℃, thereby made resin compound.Then, in resin compound, add softening agent, make poly (vinyl chloride) resin composition, resin temperature is increased to 100 ℃ and dried up.Utilize 3L kneader (MORIYAMA system) by 600 seconds degree of the thick refining of the poly (vinyl chloride) resin composition of having dried up, utilize cooler and the air cooling tablets press (MORIYAMA system) to have obtained pellet forming composition.Be explained, mixing condition be made as to 170 ℃ of screw speed 30rpm, the resin outflow temperatures of 130 ℃ of chamber temps, kneader.
In addition, use above-mentioned materials, modulated the poly (vinyl chloride) resin composition of comparative example 1～6.Modulation condition is shown in to following table 2.
Table 2
In comparative example 1 and comparative example 2, add the polymethylmethacrylate (the beautiful sun system of Mitsubishi, P-710) as gelation promotor, in addition, modulation similarly to Example 1.
In comparative example 3, change the mixing condition of comparative example 1, on the basis of thick refining, append formal mixingly, in addition, similarly modulate with comparative example 1.Particularly; utilize mixing roll (western village work mechanism 8 inches of rollers) by formal the poly (vinyl chloride) resin composition of the comparative example being obtained by thick refining 1 mixing 300 seconds degree, utilize cooler and air cooling tablets press (MORIYAMA system) and obtained pellet forming composition.
In comparative example 4, make the content of softening agent (B) be greater than 24 quality %, in addition, modulation similarly to Example 1.
In comparative example 5, according to the mode that makes hydrotalcite (c2) with respect to mass ratio (c2/c1) less than 3.5 of zinc metallic soap (c1), change the content of zinc metallic soap (c1) and hydrotalcite (c2), in addition, modulation similarly to Example 1.
In comparative example 6, make non-lead stabilizer (C) containing quantity not sufficient 4 quality %, in addition, modulation similarly to Example 1.
(3) manufacture of insulated line
Secondly, use the poly (vinyl chloride) resin composition by above-mentioned acquisition, thereby manufactured insulated line.Particularly, linear speed using regulation is sent the tinned conductor as conductor (the size 26AWG of external diameter 0.48mm, formation 7/0.16), and in its periphery, the mode that is 0.15mm according to the thickness of insulation layer, utilize the 50mmEXT forcing machine (large palace essence mechanism) above-mentioned poly (vinyl chloride) resin composition is extruded, the insulated line that to have manufactured external diameter be 0.78mm.Be explained, in the present embodiment, the linear speed of sending of conductor be made as to 400m/min, extruded velocity is made as to 400m/min.
(4) evaluation method
Secondly, evaluated by the poly (vinyl chloride) resin composition of above-mentioned acquisition and used the insulated line of this poly (vinyl chloride) resin composition according to following methods.Below evaluation method is separately described.
(winter hardiness)
Utilize mixing roll that poly (vinyl chloride) resin composition is carried out to sheet material, prepared to be compressed to the sheet material of 0.5mm thickness, thereby measured the embrittlement temperature of this sheet material.As the determinating reference of embrittlement temperature, by according to UL specification (758) ,-15 ℃ of following situations are made as "○".
(extrusion moulding)
As the evaluation of extrusion moulding, measure the higher limit of the extruded velocity of resin combination.
(extruding outward appearance)
About obtained insulated line, no problem on the coating of printing-ink, hand is touched to outward appearance good and do not occur that 1 hour above continuous particulate comes off (spark drop), the situation of tie a knot bad (コ Block is bad) is made as "○".Be explained, the bad order being caused by coking etc. also becomes the index of extruding outward appearance.
(crimping)
For obtained insulated line, crimping is connected in CZ junctor (1.5mm spacing), by do not produce crack, distortion and aspect pull-out test all qualified situation be made as "○", either party is become to underproof situation and is made as "×".
(5) evaluation result
The evaluation result of embodiment 1～5, comparative example 1～6 is shown in following table 3.
Table 3
Confirmed in embodiment 1～5, embrittlement temperature is all lower than-15 ℃, winter hardiness excellence.In addition, about the higher limit of extruded velocity, embodiment 1 is 500m/min, and embodiment 2 is 400m/min, and embodiment 3 is 400m/min, and embodiment 4 is 400m/min, and embodiment 5 is 400m/min.Thus, even in the situation that extruded velocity is at a high speed turned to 400m/min, also confirm the insulation layer that forms to extrude outward appearance good, extrusion moulding excellence.Confirmed in addition, the mechanical characteristics of the insulation layer of the insulated line of manufacture is high, thereby does not produce crack, distortion, crimping excellence.
In comparative example 1 and comparative example 2, contain PMMA as gelation promotor, thereby confirmed that embrittlement temperature is higher than-15 ℃, winter hardiness is poor.Confirmed in addition, the outward appearance of extruding of the insulation layer of formation is bad.In comparative example 1 and comparative example 2, contain PMMA and improved extrusion moulding, but about the higher limit of extruded velocity, confirmed that comparative example 1 is for 150m/min, comparative example 2 is 150m/min, extrusion moulding is insufficient.Confirmed thus, in the situation that extruded velocity is turned to 400m/min at a high speed, the outward appearance of extruding of the insulation layer of formation worsens.Be explained, confirmed due to the mechanical characteristics with regulation, thereby crimping be good.
In comparative example 3, the poly (vinyl chloride) resin composition of comparative example 1 is applied formally mixing, thereby improved winter hardiness, but cannot improve and extrude outward appearance.In comparative example 3, the higher limit of confirming extruded velocity is 250m/min.
In comparative example 4, confirm, because the content of softening agent is many, the mechanical properties of the insulation layer that therefore obtained, crimping is bad.In comparative example 4, the higher limit of confirming extruded velocity is 400m/min.
In comparative example 5, make mass ratio (c2/c1) less than 3.5 of hydrotalcite (c2) with respect to zinc metallic soap (c1), the content of zinc metallic soap (c1) is many.Thus, in comparative example 5, by zinc metallic soap (c1), outer oilness is become excessive, poly (vinyl chloride) resin composition is gelation equably not, therefore can think that extrusion moulding reduces, and the outward appearance of extruding of the insulation layer of formation becomes bad.In comparative example 5, the higher limit of confirming extruded velocity is 100m/min.
In comparative example 6, because the content of non-lead stabilizer (C) is few, thereby can think that extrusion moulding reduces, the outward appearance of extruding of the insulation layer of formation becomes bad.In comparative example 6, the higher limit of confirming extruded velocity is 200m/min.
In this wise, according to the present invention, softening agent (B) and non-lead stabilizer (C) are made as to the content of regulation, and making zinc metallic soap (c1) and the mass ratio of hydrotalcite (c2) is the numerical range of regulation, thereby can obtain the poly (vinyl chloride) resin composition of extrusion moulding, mechanical characteristics and winter hardiness excellence.In addition, the insulation layer being formed by it to extrude outward appearance good, mechanical characteristics and winter hardiness excellence.And, even if it is not the insulated line with this insulation layer is in the situation that crimping has connected, yielding yet, thereby be difficult for the poor flow that generation causes by coming off.
Claims (6)
1. a poly (vinyl chloride) resin composition, is characterized in that, it contains polyvinyl chloride (PVC) RESINS (A), softening agent (B), non-lead stabilizer (C), and not containing the polymethylmethacrylate as gelation promotor,
Described non-lead stabilizer (C) comprises zinc metallic soap (c1) and hydrotalcite (c2),
With respect to described poly (vinyl chloride) resin composition 100 quality %, contain the described softening agent (B) below the above 24 quality % of 19 quality %, described non-lead stabilizers (C) more than 4 quality %,
Described hydrotalcite (c2) is more than 3.5 below 10 with respect to the mass ratio (c2/c1) of described zinc metallic soap (c1).
2. poly (vinyl chloride) resin composition according to claim 1, is characterized in that, contains the described non-lead stabilizer (C) below the above 20 quality % of 4 quality %.
3. poly (vinyl chloride) resin composition according to claim 1 and 2, it is characterized in that, described non-lead stabilizer (C) further comprises at least a kind in the group of selecting free beta-diketone compounds, antioxidant, polyvalent alcohol, metal hydrate composition, they add up to below 50% of described non-lead stabilizer (C).
4. according to the poly (vinyl chloride) resin composition described in any one in claim 1～3, it is characterized in that, it further contains at least a kind of additive (D) in the group of selecting free weighting agent, tinting material composition, and contains the described additive (D) below 10 quality %.
5. an insulated line, is characterized in that, has the insulation layer being made up of the poly (vinyl chloride) resin composition described in any one in claim 1～4 in the periphery of conductor.
6. insulated line according to claim 5, is characterized in that, it connects for junctor crimping, and the thickness of described insulation layer is below 0.2mm.
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| JP2012-272481 | 2012-12-13 | ||
| JP2012272481 | 2012-12-13 | ||
| JP2013-022819 | 2013-02-08 | ||
| JP2013022819A JP6011381B2 (en) | 2012-12-13 | 2013-02-08 | Insulated wire for connector pressure connection using polyvinyl chloride resin composition |
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| CN103865191B CN103865191B (en) | 2017-06-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106243547A (en) * | 2015-06-11 | 2016-12-21 | 日立金属株式会社 | Vinyl chloride resin composition and employ insulated electric conductor and the cable of said composition |
| CN107099105A (en) * | 2015-05-13 | 2017-08-29 | 日立金属株式会社 | Vinyl chloride resin composition and insulated electric conductor and the manufacture method of insulated electric conductor using it |
| CN107710338A (en) * | 2015-07-09 | 2018-02-16 | 住友精化株式会社 | Resistant to partial discharges electricity consumption insualtion resin composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| AU7765394A (en) * | 1993-12-03 | 1995-06-08 | Geon Company, The | Lead-free conductor coverings |
| JP3967094B2 (en) * | 2001-05-29 | 2007-08-29 | 日立電線株式会社 | Polyvinyl chloride resin composition-coated wires and cables |
| JP5346861B2 (en) * | 2010-03-29 | 2013-11-20 | 日立電線株式会社 | PVC master batch for recycled vinyl chloride resin composition, vinyl chloride resin composition and electric wire / cable, method for producing recycled vinyl chloride resin composition, and method for producing electric wire / cable |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099105A (en) * | 2015-05-13 | 2017-08-29 | 日立金属株式会社 | Vinyl chloride resin composition and insulated electric conductor and the manufacture method of insulated electric conductor using it |
| CN107099105B (en) * | 2015-05-13 | 2019-07-26 | 日立金属株式会社 | Vinyl chloride resin composition and using its insulated electric conductor and insulated electric conductor manufacturing method |
| CN106243547A (en) * | 2015-06-11 | 2016-12-21 | 日立金属株式会社 | Vinyl chloride resin composition and employ insulated electric conductor and the cable of said composition |
| CN107710338A (en) * | 2015-07-09 | 2018-02-16 | 住友精化株式会社 | Resistant to partial discharges electricity consumption insualtion resin composition |
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