CN101570617B - Halogen-free flame-retardant resin composition and electric wire/cable using the resin composition - Google Patents
Halogen-free flame-retardant resin composition and electric wire/cable using the resin composition Download PDFInfo
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- CN101570617B CN101570617B CN2009101374129A CN200910137412A CN101570617B CN 101570617 B CN101570617 B CN 101570617B CN 2009101374129 A CN2009101374129 A CN 2009101374129A CN 200910137412 A CN200910137412 A CN 200910137412A CN 101570617 B CN101570617 B CN 101570617B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 37
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
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- 239000004925 Acrylic resin Substances 0.000 claims abstract description 18
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 18
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000004014 plasticizer Substances 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 13
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- 238000001816 cooling Methods 0.000 claims description 9
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- 150000003503 terephthalic acid derivatives Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 238000004898 kneading Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 abstract description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract 1
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- 150000002367 halogens Chemical class 0.000 description 11
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- 102100035474 DNA polymerase kappa Human genes 0.000 description 5
- 101710108091 DNA polymerase kappa Proteins 0.000 description 5
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- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
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- 238000010438 heat treatment Methods 0.000 description 3
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- 150000000182 1,3,5-triazines Chemical class 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 150000002632 lipids Chemical class 0.000 description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 235000019628 coolness Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- LERGDXJITDVDBZ-UHFFFAOYSA-N dioctyl benzene-1,3-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=CC(C(=O)OCCCCCCCC)=C1 LERGDXJITDVDBZ-UHFFFAOYSA-N 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
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- 239000012764 mineral filler Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
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- 238000005496 tempering Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Organic Insulating Materials (AREA)
- Insulated Conductors (AREA)
Abstract
本发明提供一种可以直接使用以往的PVC捏合设备和电线挤出设备，并且不会降低生产效率的无卤阻燃树脂组合物，以及使用该树脂组合物的电线·电缆。其相对于100重量份由丙烯酸、甲基丙烯酸或其衍生物聚合或共聚所形成的丙烯酸系树脂(A)，含有60重量份以下由烷基链为C10以下的邻苯二甲酸、间苯二甲酸、对苯二甲酸酯所形成的苯二甲酸酯，作为增塑剂(B)，以及含有60重量份以下不含卤素的阻燃剂(C)。The present invention provides a halogen-free flame-retardant resin composition that can be directly used in conventional PVC kneading equipment and electric wire extrusion equipment without lowering production efficiency, and electric wires and cables using the resin composition. With respect to 100 parts by weight of the acrylic resin (A) formed by the polymerization or copolymerization of acrylic acid, methacrylic acid or derivatives thereof, it contains 60 parts by weight or less of phthalic acid, isophthalic acid and isophthalic acid whose alkyl chain is C10 or less. Formic acid and a phthalate formed from a terephthalate, as a plasticizer (B), and a halogen-free flame retardant (C) are contained in an amount of 60 parts by weight or less.
Description
Technical field
The present invention relates to halogen-free fire-proof resin composition, and the electric wire that uses this resin combination.
Background technology
Along with the raising of environment in recent years consciousness, the exploitation practicability that is adapted to the environmental consideration type electric wire of circular form society is just becoming the task of top priority.
At present; Be suitable for indoor or switchboard in, and in the permanent wiring field such as control instruments purposes, use the halogen-free fire-proof resin composition of not halogen-containing or harmful heavy metal; Replace in the past SE (PVC) as coating material, the employing of so-called non halogen wire and cable develops.
In patent documentation 1,2, proposed to use the halogen-free resin composition of vinyl resin, phthalic acid ester, halogen-free flame retardants and inhibitor here.
The not halogen-containing halogen-free fire-proof resin composition that in using patent documentation 1,2, is proposed; When replacing PVC to make electric wire or cable; Directly use PVC device fabrication halogen-free fire-proof resin composition particle in the past, and to use this granule manufacture electric wire be Utopian.
Fig. 3 representes the manufacturing line of PVC, and wherein, the PVC with powder shaped is fed into by in the formed mixing machine 30 of ribbon blender by hopper 31, and drops into the buttery softening agent by hopper 32; Drop into powders such as stablizer, additive by hopper 33, in mixing machine 30,, this mixture is supplied to feedway 34 after their mixing; And be fed into continuous extruding granulator (kneader) 35 by this feedway 34, in extruding granulator 35 continuously, mediate this mixture; And it is extruded be pencil, cut simultaneously, form particle; With this pellet supply to cooling sorting machine (pellet cooler) 36, cooling sorting forms goods and packs 37.
Patent documentation 1: TOHKEMY 2005-120194 communique
Patent documentation 2: TOHKEMY 2006-63229 communique
Summary of the invention
But, when halogen-free fire-proof resin composition is made up of polymkeric substance and fire retardant etc., and when directly using the described used so far PVC production unit of Fig. 3, produced following problem, and be absorbed in must the investment new installation the condition.
That is to say; Compare with PVC; Because the difference of the formation of compounding ingredient and the characteristic of compsn is if use mixing machine 30 in the past and continuous extruding granulator 35 then have the supply inequality of Synergist S-421 95, the problem that particle is adhered mutually when mediating deficiency, granulation.In addition, powders such as fire retardant remain in the connection portion of feedway 34 and continuous extruding granulator 35 grades, and when cleaning or replacing kind, have expended the time in order to be removed, and therefore have the problem that production efficiency reduces.
In addition, extruding in the operation of electric wire, PVC is excellent in cleaning or the isochronous operability of replacing kind, and on the contrary, halogen-free fire-proof resin composition because its compsn has binding property etc., therefore when cleaning or replacing kind, expends time in.In addition, when extruding operation, foreign matter accumulates in extrusion die or core iron place, so its production efficiency reduces.
As stated, because halogen-free flame-retardance resin combination in the past uses powder and granular polymkeric substance as fire retardant; Therefore because the bridge joint (bridge) of material etc. when mediating; Supply with inhomogeneously and produced, and quality is unstable, thereby can't directly use PVC equipment.
Therefore, as the kneader device of halogen-free fire-proof resin composition, can consider the closed kneading device (Ban Buli mixing machine or kneader) that the materials used supply is carried out through manual operation.Yet, mediate device to closed and drop into material, it is artificial generally to use poidometer to replace, so facility investment increases greatly.In addition, owing to do not have automatic flushing device, so production efficiency is poor.
In addition; Material in the feedway generally is supplied to tablets press through screw rod, blade or travelling belt; But halogen-free flame-retardance resin combination; In order to have suppressed the bridge joint of material, therefore need and make the whisking appliance etc. of material movement with vibrator, knocker etc., and still not preferred aspect facility investment.
In addition, halogen-free flame-retardance resin combination in the past needs sufficient shearing force and kneading time when mediating, and therefore as this kneader device, must adopt the big continuous kneading extruder of L/D value (L/D big=mediate regional length).
Yet if increase L/D, not only mediating needs high torque (HT) when extruding, and owing to shear heating, in compsn, produces foaming, therefore can't obtain stable quality.
In addition,,, and cause the particle after the granulation to connect adhesion between mutually, therefore can't obtain good particle then because its character if mediate the halogen-free flame-retardance resin combination with in the past PVC kneader device.
Therefore, when the kneader device of using PVC was mediated, (water is cooling extruded to be zonal compsn must to carry out water-cooled bundle mode; And form granular method with tablets press), thus, need to remove the moisture of attachment removal; And an end formed band shape, this causes productivity poor.
As stated, when using the PVC kneader device to mediate halogen-free flame-retardance resin combination in the past, not only need the more equipment investment, cause process cost to improve, and its productivity has also reduced.
The invention reside in provides a kind of PVC kneader device and electric wire extrusion equipment that can directly use in the past, and can not reduce the halogen-free fire-proof resin composition of production efficiency, and the electric wire that uses this resin combination.
To achieve these goals; The invention of technical scheme 1 is a kind of halogen-free fire-proof resin composition; It is characterized in that; Carry out polymerization or copolymerization and the acrylic resin (A) that forms with respect to 100 weight parts by vinylformic acid, methylacrylic acid or their verivate; What contain 25～60 weight parts is that the formed phthalic acid ester of phthalic acid, m-phthalic acid, terephthalate below the C10 is used as softening agent (B) by alkyl chain, and the not halogen-containing fire retardant (C) that contains 30～60 weight parts.
The invention of technical scheme 2 is; Like technical scheme 1 described halogen-free fire-proof resin composition, wherein, aforementioned acrylic resin (A); With butyl acrylate rubber as nuclear, and by TEB 3K and n-butyl acrylate copolymerization and the multipolymer that forms as shell.
The invention of technical scheme 3 is; Like technical scheme 1 or 2 described halogen-free fire-proof resin compositions; It mixes through acrylic resin (A), softening agent (B) and fire retardant (C) are dropped into mixing machine, with continuous this mixture of extruding granulator kneading, and when extruding with its severing; Form particle, re-use the cooling sorting machine and these particles are carried out cooling sorting and obtain.
The invention of technical scheme 4 is that a kind of electric wire is characterized in that, the described halogen-free fire-proof resin composition of each in the use technology scheme 1～3, the isolator of formation coating conductor.
The invention of technical scheme 5 is, a kind of cable is characterized in that, use technology scheme 1～3 each described halogen-free fire-proof resin composition forms the outermost layer sheath of the twisted electric wire that is formed by many wires twisted.
When using material of the present invention, can directly use in the past PVC kneader device and electric wire extrusion equipment, production efficiency can be do not reduced, and the electric wire production of halogen-free fire-proof resin composition can be used.Even material is non-halogen, also can directly use PVC equipment in the past.
Description of drawings
Fig. 1 is the figure that the example of PVC device fabrication halogen-free flame-retardance resin combination of the present invention is in the past used in expression.
Fig. 2 is the sectional view of electric wire of the present invention.
Fig. 3 representes the figure of PVC equipment in the past.
The explanation of symbol
1 copper conductor
2 isolators
3 electric wires
4 media
5 take-up straps
6 sheaths
Embodiment
Below, based on accompanying drawing a preferred implementation of the present invention is elaborated.
The present invention is a kind of halogen-free fire-proof resin composition; It carries out polymerization or copolymerization and the acrylic resin (A) that forms with respect to 100 weight parts (mass parts) by vinylformic acid, methylacrylic acid or their verivate; Contain more than 25 weight parts (mass parts); Below above 60 weight parts (mass parts) of preferred 40 weight parts (mass parts) is that the formed phthalic acid ester of phthalic acid, m-phthalic acid, terephthalate below the C10 is used as softening agent (B) by alkyl chain; And contain more than 30 weight parts; Not halogen-containing fire retardant (C) below above 60 weight parts (mass parts) of preferred 40 weight parts (mass parts), and the electric wire that uses this resin combination.
Halogen-free fire-proof resin composition of the present invention can directly use in the past PVC kneader device and prilling, simultaneously, can use electric wire extrusion equipment in the past to make electric wire with this particle.
Use this PVC kneader device, the halogen-free flame-retardance resin combination is formed the particulate method describe by Fig. 1.
Be fed into by in the formed mixing machine 10 of ribbon blender by the acrylic resin (A) of hopper 11, and drop into buttery softening agent (B), drop into powders such as fire retardant (C) or inhibitor by hopper 13 by hopper 12 with powder shaped; In mixing machine 10,, this mixture is supplied to feedway 14, and is fed into continuous extruding granulator 15 by this feedway 14 with after their mixing; In continuous extruding granulator 15; Mediate this mixture, and it is extruded be pencil, cut simultaneously; Form particle; With this pellet supply to cooling sorting machine (pellet cooler) 16, cooling sorting, and will carry out packing 17 by the formed particle product of halogen-free fire-proof resin composition.
Use this granular halogen-free fire-proof resin composition, and use electric wire extrusion equipment in the past to make electric wire.
Fig. 2 representes isolator 2 is coated on formation electric wire 3 on the copper conductor 1, and with 3 these electric wires 3 and medium 4 twisted together, applies take-up strap (giving as security え volume I) 5, and outermost layer is extruded the also figure of the cable of coating as sheath 6.
Make this isolator 2 and sheath 6 through halogen-free flame-retardance resin combination of the present invention.
Then, specify halogen-free flame-retardance resin combination of the present invention.
Acrylic resin (A) is by vinylformic acid, methylacrylic acid or their verivate polymerization or copolymerization and (for example form; With butyl acrylate rubber as nuclear (core); And be that 9.04 TEB 3K and SP value are 8.25 the formed polymkeric substance of the n-butyl acrylate copolymerization acrylic resin as the shell that encases above-mentioned nuclear with SP value (solubility parameter)), the alkyl chain that the composition of this polymkeric substance is adjusted near softening agent (B) is the SP value (8.6～8.9) of the phthalic acid ester of C8-10.
This acrylic resin (A); Its molecular weight is adjusted into about 700,000; MWD has 2 peaks, the low molecular domains of one of them peak position in about 20～400,000, the flowability when it helps to plastify; The HMW zone of another peak position in about 1,000,000, its maintenance to softening agent (B) has effect.
The present invention is different with patent documentation 1, the vinyl resin shown in 2 through using; And by vinylformic acid, methylacrylic acid or their verivate polymerization or the formed acrylic resin of copolymerization (A); Can with and the SP (SP value) of softening agent (B) be adjusted into same degree; Thus, even use PVC equipment, also can mediate without barrier and extrude processing.
Softening agent (B) is the phthalic acid ester that common employed alkyl chain is C8-10 in the flexible PVC; For example, can enumerate dinoctyl phthalate (n-DOP), dimixo-octyl phthalate, phthalic acid two 2-ethylhexyls (DOP), DINP (DINP), Di Iso Decyl Phthalate, dioctyl terephthalate, dioctyl isophthalate, m-phthalic acid two 2-ethylhexyls (DOIP) etc.
Among the present invention, the addition of softening agent (B) is more than 25 weight parts, be preferably more than 40 weight parts, and more preferably below 60 weight parts.If it surpasses 60 weight parts, then can't obtain necessary tensile strength.
Not halogen-containing fire retardant (C) can be enumerated metal hydroxides, zinc based compound, 1,3,5-triazines verivate etc.They can use separately, also can two or more mixing use.
As metal hydroxides, can enumerate these metal hydroxidess of Marinco H, white lake, calcium hydroxide and nickel solid solution.These metal hydroxidess are lipid acid such as coupling agent, stearate or calcium stearate even use through silane coupling agent, titanic acid ester, or fatty acid metal salt etc. has carried out the surface-treated material, and also it doesn't matter.
The zinc based compound can be enumerated zinc oxide, zinc borate, zinc etc.These zinc based compounds are lipid acid such as coupling agent, stearate or calcium stearate even use through silane coupling agent, titanic acid ester, or fatty acid metal salt etc. has carried out the surface-treated material, and also it doesn't matter.
As the 1,3,5-triazines verivate, can enumerate trimeric cyanamide, cyanuric acid, tricarbimide, melamine cyanurate, sulfuric acid trimeric cyanamide etc.More preferably melamine cyanurate.They also can carry out surface treatment through nonionic surfactant or various coupling agent.
Among the present invention, the addition of fire retardant (C) is more than 30 weight parts, is preferably more than 40 weight parts, and is preferably below 60 weight parts.If addition is more than 60 weight parts, then tension values significantly reduces, and is therefore not preferred.
In addition, at above-mentioned Synergist S-421 95 (A)～(C) in addition, can also add additives such as inhibitor, lubricant, tenderizer, softening agent, mineral filler, compatilizer, stablizer, carbon black, tinting material as required.
Further, also can carry out crosslinkedly, or carry out crosslinked through the electron rays isoradial through organo-peroxide.
So said; In the present invention; Through using with butyl acrylate rubber as nuclear (core); And be that 9.04 TEB 3K and SP value are 8.25 the formed polymkeric substance of n-butyl acrylate copolymerization acrylic resin (A) and the softening agent (B) as the shell that encases above-mentioned nuclear with SP value (solubility parameter), can need not doing any improvement and directly used by mixing machine and the formed PVC equipment of extruding granulator continuously in the past, and make the halogen-free flame-retardance resin combination; Simultaneously, can use this resin combination and by in the past electric wire forcing machine device fabrication electric wire.
Embodiment
Then, based on table 1 illustrative embodiment 1～5 and comparative example 1～4.
Table 1
(weight part)
*The beautiful positive manufactured YM-017 of acrylic resin Mitsubishi
Resin formed product and cable, the following making.
Resin combination; Be to cooperate various compositions with the cooperation ratio shown in the table 1; And mixed at normal temperatures 5 minutes through the described ribbon blender of Fig. 1 (mixing machine 10); Then mixture is supplied to the continuous extruding granulator 15 of equidirectional twin shaft and mediates granulation, and then, form the particle of 3 Φ * 3mm by pellet cooler 16 coolings.Ribbon blender 10 uses the machine of capacity used in PVC as 500L, and the continuous extruding granulator 15 of twin shaft uses the tablets press of diameter as 87mm, L/D=36 too.
Use used 80mm single shaft forcing machine in PVC, under 180 ℃, this particle being extruded into wall thickness is that 1mm comes coating, with its sheath 6 as the cable described in Fig. 2.
At this moment processibility evaluation and evaluation of physical property are estimated by following key element.
For the processibility evaluation;
Mixing machine flexibility
Use ribbon blender, can uniform mixing.Will the discharge from ribbon blender do not have to be detained and carry out as judgment standard, and with zero * estimate.
Extrude kneader flexibility continuously
PVC in the past compares, and discharging equal discharge-amount (is 140kg/hr) in φ 30mm twin shaft continuous extruder, and particle do not have adhesion each other, can single-sizeization, then between the particle no adhesion as judgment standard, and with zero * estimate.
Production line cleaning property
With the mean time of production line cleaning time when the PVC operation be in 20 minutes, and when disassembling the head of extruding kneader continuously, be detained resin and peel off easily, as judgment standard, and with zero * estimate.
Mould, core iron foreign matter
When extruding the coating operation with 60m/MIN equally with PVC, move 3hr continuously, whether whether Visual Confirmation generates cable nuclear because of the core iron foreign matter, and on die surface, be detained foreign matter is arranged, and with zero * estimate.
Production line cleaning property
To be in 30 minutes mean time through similar color PVC, production line cleaning when unidimensional cable is extruded in cooperation not of the same race, as judgment standard, and with zero * estimate.
For evaluation of physical property;
Evaluation of physical property is to be benchmark with JCS specification 4512; Elongation, tensile strength, oil resistant characteristic, flame retardant resistance, heating deformability after mensuration elongation, tensile strength, the heating; And with zero * it is estimated (for the specification value of above-mentioned specification, qualified note is done zero, underproof note do *).
(embodiment 1)
(embodiment 2)
(embodiment 3)
(embodiment 4)
(embodiment 5)
(comparative example 1)
Comparative example 1 is the example of the halogen-free flame-retardance resin combination used of the general electric wire of expression, this be with EVA (ethene-vinyl acetate copolymer) as basic, and add the system of 50 parts by weight of flame retardant.
In this comparative example 1, rerum natura can satisfy above-mentioned specification, but mediates processibility, extrude processibility and can't satisfy above-mentioned condition.In kneading, because the proterties of raw material is different, therefore when this mixture was supplied to kneading extruder, generation was supplied with uneven, can't obtain the feed rate same with PVC.In addition, in extruding, adhere to the metallic contact face during owing to the compound fusion, therefore can't prevent the foreign body retention of mould, core iron, and need spended time for removing the resin that stops up in the breaker plate.
(comparative example 2)
Comparative example 2 is with respect to embodiment 2, has increased by 15 parts by weight of flame retardant (C), and is added into the system of 65 weight parts.
In this comparative example 2, though mediate processibility, to extrude processibility good, the elongation residual rate of the stretch value of tensile properties, oil resistant characteristic is not enough.
(comparative example 3)
Comparative example 3 is to have increased DINP, and is added into the system of 65 weight parts.
In this comparative example 3, though can obtain mediating processibility, extrude the good result of processibility, for rerum natura, the intensity level of tensile properties is not enough.
Can know by this comparative example 2,3,, preferably use softening agent (B), these two kinds of compositions of not halogen-containing fire retardant (C) with the amount below 60 weight parts with respect to acrylic resin (A).
Keep softening agent with respect to PVC through electric bonding force, acrylic resin (A) keeps softening agent through acrylic acid composition, and this is estimated as on softening agent addition and filler addition and has produced boundary value.Aspect processibility, with respect to PVC, intermolecular forces reduces, and intermolecular distance increases, and makes the softening agent invasive become easy.Not adding in the system of not halogen-containing fire retardant (C), can in the shorter time, mediate with the shearing force lower than PVC.In addition, in order to keep the flame retardant resistance with the PVC grade, and when adding the fire retardants such as Marinco H of necessary amounts, can observe viscosity has some to rise, and this expression can keep the characteristic of or better processibility identical with PVC.
In order to improve compatible degree to softening agent (phthalic acid ester); And obtain the rerum natura more approaching with flexible PVC, have and improve the n-butyl acrylate containing ratio, or new co-polypropylene acid 2-ethylhexyl and control the method for SP value; Even and this containing ratio changes as required, also it doesn't matter.
By on can know that in acrylic acid series halogen-free flame-retardance resin combination of the present invention, the addition of softening agent (B) is preferably 25～60 weight parts shown in the table 1, fire retardant (C) is preferably 30～60 weight parts.
Yet,, in embodiment 1～5, on the cleaning time of mediating production line, produced following difference though do not express in the table 1.
With respect to cleaning time of PVC in the past be average 20 minutes, embodiment 1 is 12 minutes, embodiment 2 is 13 minutes, embodiment 3 is 13 minutes, embodiment 4 is 11 minutes, embodiment 5 is 19 minutes.
The cleaning property of embodiment 5; Slow with respect to other embodiment 1～4; Be because the addition of the addition of softening agent (B) and not halogen-containing fire retardant (C) is few; And since powder because of static attached on the wall of ribbon blender tempering tank or attached to discharging on the chute, therefore in cleaning work, need the time.
To this; Because the addition of softening agent (B) is 40～60 weight parts among the embodiment 1～4, and the addition of not halogen-containing fire retardant (C) is adjusted between 40～60 weight parts, so mixture has formed appropriate wet type state; Do not produce static, and effectively clean.
Therefore, in acrylic acid series halogen-free flame-retardance resin combination of the present invention, the addition of softening agent (B) is 40～60 weight parts, and the addition of fire retardant (C) is 40～60 weight parts, aspect cleaning property more preferably.
Claims (4)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2008118829A JP5167931B2 (en) | 2008-04-30 | 2008-04-30 | Non-halogen flame retardant resin composition and electric wire / cable using the same |
| JP2008-118829 | 2008-04-30 | ||
| JP2008118829 | 2008-04-30 |
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| CN101570617A CN101570617A (en) | 2009-11-04 |
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| JP2011195793A (en) * | 2010-03-24 | 2011-10-06 | Tokyo Electronics Chemicals Corp | Releasable resin composition |
| CN102127275B (en) * | 2011-03-16 | 2012-11-14 | 上海元琦能源科技发展有限公司 | Composition for flame-retardant polyvinyl chloride (PVC) plastic foam board, product prepared from same, and preparation method thereof |
| CN103724883B (en) * | 2014-01-10 | 2016-03-23 | 安徽瑞升电气科技有限公司 | A kind of polyvinyl chloride wire cable material of halogen-free flameproof of crosslinked with silicane |
| CN110734579A (en) * | 2014-02-07 | 2020-01-31 | Lg化学株式会社 | Plasticizer, resin composition, and method for producing same |
| CN108250642A (en) * | 2017-12-23 | 2018-07-06 | 董晓 | A kind of preparation method of cable filler |
| CN118899130A (en) * | 2024-08-08 | 2024-11-05 | 广东金源宇电线电缆有限公司 | A method for manufacturing a low-smoke, halogen-free, flame-retardant, fire-resistant B1-grade power cable |
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| JP4879407B2 (en) * | 2001-06-11 | 2012-02-22 | 株式会社カネカ | Resin composition for extrusion molding |
| JP2003096306A (en) * | 2001-09-20 | 2003-04-03 | Fujikura Ltd | Flame-retardant resin composition |
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| WO2005013291A1 (en) * | 2003-07-30 | 2005-02-10 | Sumitomo Electric Industries, Limited | Nonhalogenated flame resistant cable |
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Also Published As
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| JP2009269939A (en) | 2009-11-19 |
| CN101570617A (en) | 2009-11-04 |
| JP5167931B2 (en) | 2013-03-21 |
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