KR100745144B1 - Polypropylene resin composite with improved mechanical and fire retardant properties and the cable using thereof - Google Patents
Polypropylene resin composite with improved mechanical and fire retardant properties and the cable using thereof Download PDFInfo
- Publication number
- KR100745144B1 KR100745144B1 KR1020040037000A KR20040037000A KR100745144B1 KR 100745144 B1 KR100745144 B1 KR 100745144B1 KR 1020040037000 A KR1020040037000 A KR 1020040037000A KR 20040037000 A KR20040037000 A KR 20040037000A KR 100745144 B1 KR100745144 B1 KR 100745144B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- polypropylene resin
- resin
- parts
- polypropylene
- Prior art date
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 64
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 58
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 58
- 239000003063 flame retardant Substances 0.000 title claims abstract description 29
- 239000000805 composite resin Substances 0.000 title description 4
- 229920005989 resin Polymers 0.000 claims abstract description 70
- 239000011347 resin Substances 0.000 claims abstract description 70
- 239000004927 clay Substances 0.000 claims abstract description 34
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011342 resin composition Substances 0.000 claims abstract description 27
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 19
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 9
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 5
- 238000009830 intercalation Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 150000004760 silicates Chemical class 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- 229920005673 polypropylene based resin Polymers 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- CXUJOBCFZQGUGO-UHFFFAOYSA-F calcium trimagnesium tetracarbonate Chemical compound [Mg++].[Mg++].[Mg++].[Ca++].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O CXUJOBCFZQGUGO-UHFFFAOYSA-F 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 3
- 229910000271 hectorite Inorganic materials 0.000 claims description 3
- 229910000515 huntite Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- 229910000273 nontronite Inorganic materials 0.000 claims description 3
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 3
- 229920005604 random copolymer Polymers 0.000 claims description 3
- 229910000275 saponite Inorganic materials 0.000 claims description 3
- 229910052902 vermiculite Inorganic materials 0.000 claims description 3
- 239000010455 vermiculite Substances 0.000 claims description 3
- 235000019354 vermiculite Nutrition 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229920001903 high density polyethylene Polymers 0.000 claims description 2
- 239000004700 high-density polyethylene Substances 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 229920001684 low density polyethylene Polymers 0.000 claims description 2
- 239000004702 low-density polyethylene Substances 0.000 claims description 2
- 229920001179 medium density polyethylene Polymers 0.000 claims description 2
- 239000004701 medium-density polyethylene Substances 0.000 claims description 2
- OVSQVDMCBVZWGM-QSOFNFLRSA-N quercetin 3-O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C(C=2C=C(O)C(O)=CC=2)OC2=CC(O)=CC(O)=C2C1=O OVSQVDMCBVZWGM-QSOFNFLRSA-N 0.000 claims description 2
- 150000004756 silanes Chemical class 0.000 claims description 2
- 229910052604 silicate mineral Inorganic materials 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002114 nanocomposite Substances 0.000 abstract description 11
- 229920005678 polyethylene based resin Polymers 0.000 abstract description 10
- 229910052736 halogen Inorganic materials 0.000 abstract description 8
- 150000002367 halogens Chemical class 0.000 abstract description 8
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000012796 inorganic flame retardant Substances 0.000 abstract description 4
- 230000032798 delamination Effects 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 239000000347 magnesium hydroxide Substances 0.000 description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000002341 toxic gas Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000007655 standard test method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- AQPHBYQUCKHJLT-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-(2,3,4,5,6-pentabromophenyl)benzene Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1C1=C(Br)C(Br)=C(Br)C(Br)=C1Br AQPHBYQUCKHJLT-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/1362—Active matrix addressed cells
- G02F1/136286—Wiring, e.g. gate line, drain line
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
- H01L31/1888—Manufacture of transparent electrodes, e.g. TCO, ITO methods for etching transparent electrodes
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/136—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit
- G02F1/13606—Liquid crystal cells structurally associated with a semi-conducting layer or substrate, e.g. cells forming part of an integrated circuit having means for reducing parasitic capacitance
Abstract
본 발명은 폴리프로필렌계 수지 및 폴리에틸렌계 수지로 이루어지는 베이스수지 50 중량부 내지 98 중량부; 무수 말레인산 그라프트 폴리프로필렌 수지 2 중량부 내지 50 중량부; 유기화 클레이 1 중량부 내지 25 중량부; 및 금속수산화물 난연제 50 중량부 내지 200 중량부를 포함하는 것을 특징으로 하는 폴리프로필렌계 수지 조성물을 제공한다. 본 발명은 폴리프로필렌계 수지에 1종 이상의 폴리에틸렌계 수지가 혼합된 수지에 유기화 처리된 나노 클레이를 나노 스케일로 분산시키고, 금속수산화물을 첨가하여 우수한 기계적 물성, 특히 우수한 신율을 가지면서 동시에 난연성이 획기적으로 향상된 폴리프로필렌계 수지 조성물 그리고 이를 이용하여 만들어진 전선을 제공한다. 본 발명은 기존의 무기계 난연제 사용량을 감소시키는 효과를 제공하여 최종 제품의 우수한 기계적 물성을 제공하며, 또한 할로겐계 난연제를 사용하지 않는 친환경적인 제품의 제조를 가능하게 하는 발명의 효과를 가진다.The present invention is 50 parts by weight to 98 parts by weight of a base resin consisting of a polypropylene resin and a polyethylene resin; 2 to 50 parts by weight of maleic anhydride graft polypropylene resin; 1 to 25 parts by weight of organic clay; And 50 parts by weight to 200 parts by weight of the metal hydroxide flame retardant. The present invention is to disperse organic clay nanoscaled on a resin mixed with at least one polyethylene-based resin in a polypropylene resin on a nano-scale, adding a metal hydroxide has excellent mechanical properties, in particular excellent elongation, and at the same time the flame retardancy is remarkable The present invention provides an improved polypropylene resin composition and an electric wire made using the same. The present invention provides the effect of reducing the amount of conventional inorganic flame retardant to provide excellent mechanical properties of the final product, and also has the effect of the invention to enable the production of environmentally friendly products that do not use a halogen-based flame retardant.
폴리프로필렌, 나노복합수지, 금속수산화물, 난연제, 무수말레인산, 그라프트, 유기화클레이, 실리케이트, 알킬암모늄, 인터컬레이션, 디라미네이션, 나노컴포지트Polypropylene, Nanocomposite Resin, Metal Hydroxide, Flame Retardant, Maleic Anhydride, Graft, Organic Clay, Silicate, Alkyl Ammonium, Intercalation, Delamination, Nanocomposite
Description
도 1은 본 발명의 일실시예에 따른 전선 재료가 적용된 전선의 단면도이다.1 is a cross-sectional view of an electric wire to which an electric wire material is applied according to an embodiment of the present invention.
<도면의 주요 부분에 대한 부호의 설명><Explanation of symbols for the main parts of the drawings>
1 : 도체1: conductor
2 : 난연 절연 조성물2: flame retardant insulation composition
본 발명은 폴리프로필렌계 수지에 분산된 유기화 클레이 입자와 금속수산화물 난연제를 첨가함으로써 두 성분간의 시너지 효과로 인하여 난연성과 기계적 물성이 향상된 폴리프로필렌계 수지 조성물 및 이를 이용한 전선에 관한 것이다. 더욱 상세하게는 폴리프로필렌 수지에 1종 이상의 폴리에틸렌계 수지가 혼합된 수지를 주성분으로 하고, 특정 비율의 무수말레인산 그라프트 폴리프로필렌 수지, 유기화 클레이 및 금속수산화물 난연제를 포함하는 난연성이 우수하며 기계적 물성이 뛰어난 폴리프로필렌 수지 조성물 및 이를 이용한 전선에 관한 것이다.The present invention relates to a polypropylene resin composition having improved flame retardancy and mechanical properties due to synergistic effects between two components by adding organic clay particles and a metal hydroxide flame retardant dispersed in a polypropylene resin, and an electric wire using the same. More specifically, the main component is a resin in which at least one polyethylene-based resin is mixed with a polypropylene resin, and has excellent flame retardancy and mechanical properties including a specific ratio of maleic anhydride graft polypropylene resin, an organic clay and a metal hydroxide flame retardant. An excellent polypropylene resin composition and an electric wire using the same.
폴리프로필렌 수지는 우수한 가공특성, 내약품성, 내후성, 기계적 강도로 인해 가정용 전기제품, 건축자재, 내부 장식재, 자동차부품 등의 분야에서 폭넓게 사용되고 있으며, 전선재료로서도 점차 그 응용범위를 확대해 가고 있다. 이러한 폴리프로필렌 수지는 난연에 매우 취약한 재료이므로 난연특성을 부여하기 위하여 각종 유기계 또는 무기계 난연제를 첨가하여 사용하고 있다.Polypropylene resins are widely used in the fields of household electrical appliances, building materials, interior decoration, automotive parts, etc. due to their excellent processing characteristics, chemical resistance, weather resistance, and mechanical strength, and are gradually expanding their application range as wire materials. Since these polypropylene resins are very fragile materials for flame retardancy, various organic or inorganic flame retardants are added and used to impart flame retardant properties.
난연제를 포함하는 난연성 폴리프로필렌 수지 조성물의 예로서는 수산화마그네슘, 수산화알루미늄 같은 금속 수산화물을 폴리프로필렌 수지에 첨가하여 수득한 조성물(일본 공개특허공보 제53-92855호, 제54-29350호, 제54-77685호, 제56-26945호, 미합중국 특허 제4,322,575호, 제4,732,939호, 제4,769,179호, 제4,853,154호 및 유럽특허 제212,575호, 제446,169호), 할로겐계 화합물(예 : 데카브로모디페닐, 에테르 또는 도데카클로로-도데카클로로-도데카하이드로메타노디벤조사이클로옥텐) 및 분말활석, 고령토, 천청석, 실리카 및 규조암으로 이루어진 그룹 중에서 선택된 하나 이상의 무기충전재를 폴리프로필렌 수지에 첨가하여 수득한 조성물(일본 특허공보 제55-30739호) 등이 있다.Examples of the flame retardant polypropylene resin composition comprising a flame retardant include compositions obtained by adding metal hydroxides such as magnesium hydroxide and aluminum hydroxide to a polypropylene resin (Japanese Patent Laid-Open Nos. 53-92855, 54-29350, 54-77685). No. 56-26945, US Pat. Nos. 4,322,575, 4,732,939, 4,769,179, 4,853,154 and European Patents 212,575,446,169, halogenated compounds (e.g., decabromodiphenyl, ether or Dodecachloro-dodecachloro-dodecahydromethanodibenzocyclooctene) and a composition obtained by adding at least one inorganic filler selected from the group consisting of powder talc, kaolin, celestial stone, silica and diatomite to the polypropylene resin ( Japanese Patent Publication No. 55-30739).
또한 최근에는 난연성을 부여하는 새로운 방법으로 나노복합체를 제조하는 방법이 개시되고 있는데, 점토를 개질하여 폴리올레핀과의 상용성을 향상시켜 나노복합체를 제조하는 방법(미합중국특허 제5,910,523호), 폴리프로필렌과 점토 사이의 친화력을 증가시키기 위하여 무수말레인산을 그라프트시킨 폴리프로필렌 올리고머를 점토와 혼합한 후, 폴리프로필렌과 브렌딩하여 폴리프로필렌과 점토의 나노복합체를 제조하는 방법(N. Hasegawa et al., Journal of applied polymer science, 67, 87, 1998) 등이 있다.In addition, recently, a method of preparing nanocomposites has been disclosed as a new method of imparting flame retardancy. The method of preparing nanocomposites by modifying clay to improve compatibility with polyolefins (US Pat. No. 5,910,523), and polypropylene Method for preparing nanocomposites of polypropylene and clay by mixing polypropylene oligomers grafted with maleic anhydride with clay to increase affinity between clays and blending with polypropylene (N. Hasegawa et al., Journal of applied polymer science, 67, 87, 1998).
고분자 수지의 난연성은 난연제의 종류에 따라 크게 좌우되는데 종래 기술에서는 주로 염소 또는 브롬과 같은 할로겐을 함유하는 난연제를 사용하였다. 이 경우 할로겐 원소들이 연소시 활성화된 고분자의 분해물을 안정화시킴으로서 고분자수지에 대한 난연성을 얻을 수 있었다. 할로겐을 함유하는 난연재료는 연소시 인체에 유해하고 설비의 부식을 초래하는 독성가스를 발생시켜 사용에 대한 규제를 하고 있으나, 아직까지 높은 난연성을 요구하는 케이블의 난연재료에 대하여 다양하게 사용되고 있다.The flame retardancy of the polymer resin largely depends on the type of the flame retardant. In the prior art, a flame retardant mainly containing halogen such as chlorine or bromine was used. In this case, flame retardance of the polymer resin was obtained by stabilizing the decomposition products of the activated polymer when the halogen elements were burned. Although halogen-containing flame retardant materials are regulated for use by generating toxic gases that are harmful to humans and cause corrosion of equipment during combustion, they are still used in various flame retardant materials for cables that require high flame retardancy.
최근들어 이상과 같은 할로겐 난연재료의 문제점들을 해결하기 위하여 금속 수산화물 및 난연보조제를 다양하게 사용함으로써 난연성과 저발연 특성들이 매우 향상되었다.In recent years, in order to solve the above problems of halogen flame retardant materials, various uses of metal hydroxides and flame retardant aids have greatly improved flame retardancy and low smoke retardation properties.
난연제로서 일반적으로 다량으로 첨가되는 금속 수산화물은 연소과정 중에 탈수되면서 흡열하는 효과에 의하여 연소를 억제함으로써 고분자 복합수지에 난연성을 부여한다. 또한, 연소과정중에 독성가스의 배출이 없으며 저발연 특성도 우수하다. 훈타이트와 마그네슘 카보네이트는 흡열 효과 뿐만 아니라 다양한 열분해 거동을 거치면서 고분자 재료의 연소를 억제하는 효과를 발휘한다.Metal hydroxides, which are generally added in a large amount as a flame retardant, impart flame retardancy to a polymer composite resin by suppressing combustion by the endothermic effect of dehydration during combustion. In addition, there is no emission of toxic gas during the combustion process and excellent low smoke characteristics. Huntite and magnesium carbonate not only have an endothermic effect but also have a variety of pyrolysis behaviors to suppress the combustion of polymer materials.
종전의 기술에서는 난연성이 높은 조성물을 제조하기 위해 폴리프로필렌 수지에 수산화 마그네슘이나 무기충전재를 다량 첨가하였는데, 이렇게 제조된 복합수지는 성형성 및 기계적 물성이 매우 저하되며, 기계적 물성 특히 신장율이 기본 수지에 비하여 매우 나빠져 일정 이상의 인장강도 및 신장율을 요구하는 전선용 등의 산업적 이용시 큰 난점으로 작용되고 있다.In the prior art, a large amount of magnesium hydroxide or an inorganic filler was added to a polypropylene resin to prepare a high flame retardant composition. The composite resin thus prepared has a very low moldability and mechanical properties. Compared to this, it is very bad, and it is a big difficulty in industrial use such as wires that require a certain tensile strength and elongation rate.
최근에 소개된 난연성을 부여하는 새로운 방법으로 나노복합체를 제조하는 방법이 제시되고 있는데, 이 역시 단독으로 사용될 경우 획득할 수 있는 난연 최대치의 한계가 있는 실정이다.Recently, a method of preparing a nanocomposite has been proposed as a new method of imparting flame retardancy, which also has a limit of the maximum flame retardancy that can be obtained when used alone.
또한 할로겐계 화합물을 폴리프로필렌에 가함으로써 수득한 조성물은 가공시 및 연소시 유독기체가 생성되는 환경문제를 가지고 있어 이미 선진국에서는 할로겐계 난연제의 사용을 규제하고 있는 실정이다.In addition, the composition obtained by adding the halogen-based compound to the polypropylene has an environmental problem that toxic gases are generated during processing and combustion, which has already regulated the use of halogen-based flame retardants in developed countries.
본 발명은 상기 문제점을 해결하기 위하여 고안된 것으로서, 본 발명은 폴리프로필렌계 수지에 1종 이상의 폴리에틸렌계 수지가 혼합된 수지에 유기화 처리된 나노 클레이를 나노 스케일로 분산시키고, 금속수산화물을 첨가하여 우수한 기계적 물성, 특히 우수한 신율을 가지면서 동시에 난연성이 획기적으로 향상된 폴리프로필렌계 수지 조성물 그리고 이를 이용하여 만들어진 전선을 제공하는 것을 목적으로 한다.The present invention has been devised to solve the above problems, the present invention is excellent in mechanical properties by dispersing the organic clay nano-scaled to a resin mixed with at least one polyethylene-based resin in a polypropylene resin, the addition of metal hydroxide An object of the present invention is to provide a polypropylene-based resin composition having excellent physical properties, particularly excellent elongation and at the same time significantly improving flame retardancy, and an electric wire made using the same.
본 발명은 폴리프로필렌계 수지 및 폴리에틸렌계 수지로 이루어지는 베이스수지 50 중량부 내지 98 중량부; 무수 말레인산 그라프트 폴리프로필렌 수지 2 중량부 내지 50 중량부; 유기화 클레이 1 중량부 내지 25 중량부; 및 금속수산화물 난연제 50 중량부 내지 200 중량부를 포함하는 것을 특징으로 하는 폴리프로필렌계 수지 조성물을 제공함으로써 상기 기술적 과제를 달성할 수 있다.The present invention is 50 parts by weight to 98 parts by weight of a base resin consisting of a polypropylene resin and a polyethylene resin; 2 to 50 parts by weight of maleic anhydride graft polypropylene resin; 1 to 25 parts by weight of organic clay; And 50 parts by weight to 200 parts by weight of the metal hydroxide flame retardant, the technical problem can be achieved by providing a polypropylene-based resin composition.
본 발명의 그 밖의 모양, 특정한 장점들 및 신규한 특징들은 첨부된 도면들 과 연관되어지는 이하의 상세한 설명과 바람직한 실시예들로부터 더욱 분명해질 것이다.Other aspects, specific advantages, and novel features of the present invention will become more apparent from the following detailed description and the preferred embodiments associated with the accompanying drawings.
이하에서는 기계적 물성, 특히 인장특성등과 난연특성이 획기적으로 향상된 폴리프로필렌계 수지 조성물 및 이를 적용한 전선에 관하여 첨부된 도면을 참조하여 상세히 설명한다.Hereinafter will be described in detail with reference to the accompanying drawings with respect to the mechanical properties, in particular the tensile properties and flame retardant properties improved polypropylene resin composition and the wire applied thereto.
우선, 본 명세서에서 사용되는 용어를 다음과 같이 정의한다.First, the terms used in the present specification are defined as follows.
'나노클레이'는 클레이의 층간 간격이 합성 수지나 화학 물질이 들어갈 수 있는 공간인 나노크기(10-9m)를 가지는 클레이를 통상 칭하는 것으로 정의한다.'Nanoclay' is defined as commonly referring to a clay having a nano-sized (10 -9 m) in which the interlayer spacing of the clay is a space where synthetic resin or chemicals can enter.
'유기화'는 무기물인 층상 실리케이트의 극성을 감소시키기 위해 유기화제인 알킬 암모늄 등으로 처리하는 것으로 정의한다.'Organization' is defined as treatment with organic ammonium or the like to reduce the polarity of inorganic layered silicates.
'나노복합수지'는 매트릭스 화합물에 나노크기(10-9m)의 충진제가 복합된 화합물을 말하는 것으로 정의한다. 'Nano composite resin' is defined as referring to a compound in which a nano-sized (10 -9 m) filler is combined with a matrix compound.
'인터칼레이션'은 수지 사슬들이 클레이 층간 사이로 침투하여 클레이 층간이 사이가 벌어진 구조를 이루는 것으로 정의한다.'Intercalation' is defined as the resin chains penetrating between the clay layers to form a structure between the clay layers.
'디라미네이션'은 수지 사슬들이 클레이 층간 사이로 침투하여 클레이 층간구조가 완전히 사라진 구조를 이루는 것으로 정의한다.Delamination is defined as the resin chains penetrating between the clay layers to completely eliminate the clay layers.
'금속수산화물'는 수산화알루미늄, 수산화마그네슘 등과 같은 수화금속화합물로서 금속원자에 수산기가 결합되어 있는 무기물을 말한다.'Metal hydroxide' is a hydrated metal compound such as aluminum hydroxide or magnesium hydroxide, and refers to an inorganic material having a hydroxyl group bonded to a metal atom.
본 발명에 의한 폴리프로필렌계 수지 조성물의 구성은 폴리프로필렌계 수지와 폴리에틸렌계 수지로 이루어지는 베이스수지, 무수말레인산 그라프트 폴리프로필렌계 수지, 유기화 클레이 그리고 금속수산화물 난연제로 이루어진다.The polypropylene resin composition according to the present invention comprises a base resin composed of a polypropylene resin and a polyethylene resin, a maleic anhydride graft polypropylene resin, an organic clay, and a metal hydroxide flame retardant.
본 발명은 폴리프로필렌 수지 및 1종 이상의 폴리에틸렌계 수지가 혼합된 베이스수지가 50 중량부 내지 98 중량부를 포함된 수지 혼합물을 이용한다. 폴리에틸렌계 수지의 함량은 폴리프로필렌계 수지와 폴리에틸렌계 수지 혼합물의 10중량%에서 70중량%이다. 폴리에틸렌계 수지가 10중량%보다 작으면 신율이 열등하며 70중량% 이상이면 인장강도가 열등하다. 또한 폴리에틸렌계 수지 중 메탈로센 촉매로 중합된 폴리에틸렌 엘라스토머 수지는 통상적으로 에틸렌-옥텐 공중합체를 주로 사용하며 이때 옥텐의 중합단위는 30중량% 이하이다. 에틸렌-옥텐 공중합체에서 옥텐의 중합단위가 30중량%보다 크면 수지의 인장강도가 열등하여 상업적으로 효용이 없다. 엘라스토머 수지는 상기의 에틸렌-옥텐 공중합체에 한정되지 않으며 동일한 기능을 하는 수지면 그 종류에 제한을 받지 않음은 물론이다. 에틸렌-부텐 공중합체가 에틸렌-옥텐 공중합체를 대신하여 쓰일 수 있으며 또한 함께 사용하는 것도 가능하다.The present invention uses a resin mixture containing 50 parts by weight to 98 parts by weight of a base resin mixed with a polypropylene resin and at least one polyethylene-based resin. The content of the polyethylene resin is 10% to 70% by weight of the polypropylene resin and the polyethylene resin mixture. If the polyethylene-based resin is less than 10% by weight, the elongation is inferior. If it is 70% by weight or more, the tensile strength is inferior. In addition, polyethylene elastomer resin polymerized with a metallocene catalyst in the polyethylene-based resin is usually mainly ethylene-octene copolymer, wherein the polymerization unit of octene is 30% by weight or less. If the polymer unit of octene in the ethylene-octene copolymer is greater than 30% by weight, the tensile strength of the resin is inferior and it is not commercially useful. Elastomer resin is not limited to the above ethylene-octene copolymer, and of course, it is not limited to the kinds of resins having the same function. Ethylene-butene copolymers may be used in place of ethylene-octene copolymers and may also be used together.
본 발명에서 베이스 수지로 사용한 수지는 프로필렌 단독 중합체, 랜덤 공중합체 및 블록 공중합체중에서 1 또는 2 이상의 폴리에틸렌계 수지를 혼합 사용한다. 폴리에틸렌계 수지로서 저밀도 폴리에틸렌, 선형저밀도 폴리에틸렌, 중밀도 폴리에틸렌, 고밀도 폴리에틸렌, 및 메탈로센 촉매를 이용하여 합성한 폴리올레핀 엘라스토머(Polyolefin Elastomer)로 이루어진 군중에서 1 또는 2 이상을 사용한다. The resin used as the base resin in the present invention is a mixture of one or two or more polyethylene-based resins in a propylene homopolymer, a random copolymer and a block copolymer. As the polyethylene-based resin, one or two or more are used in a crowd consisting of low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, and polyolefin elastomers synthesized using a metallocene catalyst.
본 발명에 의한 수지 조성물은 무수 말레인산 그라프트 폴리프로필렌 수지를 2 중량부 내지 50 중량부 포함한다. 무수말레인산 그라프트 폴리프로필렌 수지가 2 중량부보다 작으면 반응성이 떨어져 유기화 클레이가 나노 스케일로 분산되지 않으며, 50 중량부보다 크면 분자량이 저하하여 기계적 물성이 저하한다. The resin composition according to the present invention contains 2 parts by weight to 50 parts by weight of maleic anhydride graft polypropylene resin. When the maleic anhydride graft polypropylene resin is less than 2 parts by weight, the reactivity is poor, and the organic clay is not dispersed on a nano scale. When the maleic anhydride graft polypropylene resin is less than 50 parts by weight, the molecular weight is lowered and mechanical properties are lowered.
본 발명에서 상기한 무수 말레인산 그라프트 폴리프로필렌 수지는 유기화 클레이가 폴리프로필렌 수지내에서 나노 입자로 분산시켜 주는 역할을 하는 수지로서, 무수말레인산 단위가 0.1 중량% 내지 8 중량% 그라프트 되어있는 폴리프로필렌 수지이다. 그라프트 되어있는 무수 말레인산 단위가 0.1 중량%보다 작으면 반응성이 작아 나노입자의 분산효과를 기대하기 어려우며 8 중량% 보다 크면 무수 말레인산이 불순물로 작용하여 물성 저하를 초래한다. In the present invention, the maleic anhydride graft polypropylene resin is a resin in which organic clay disperses the nanoparticles in the polypropylene resin, and a polypropylene in which the maleic anhydride unit is grafted from 0.1 wt% to 8 wt% Resin. If the grafted maleic anhydride unit is less than 0.1% by weight, the reactivity is low, so it is difficult to expect the dispersion effect of the nanoparticles. If the maleic anhydride unit is larger than 8% by weight, the maleic anhydride acts as an impurity to cause deterioration of physical properties.
본 발명에 의한 수지 조성물은 유기화 클레이를 1 중량부 내지 25 중량부 포함하는 것이 바람직하다. 유기화 클레이가 1 중량부보다 작으면 나노분산에 대한 효과가 없으며, 25 중량부 이상에서는 더 이상의 상승효과를 기대할 수 없다. It is preferable that the resin composition by this invention contains 1 weight part-25 weight part of organic clay. If the organic clay is less than 1 part by weight, there is no effect on nanodispersion, and at 25 parts by weight or more, no synergistic effect can be expected.
본 발명에서 상기한 유기화 클레이는 층상 구조를 가지는 실리케이트 광물로서 몬트모릴로나이트, 헥토라이트, 사포나이트, 베이데라이트, 논트로나이트, 버미큘라이트 및 할로이사이트로 이루어진 군에서 1 또는 2 이상 선택되는 것이 바람직하다. 또한, 유기화제는 탄소 사슬수가 10 내지 18인 알킬 암모늄인 것이 바람직하다. 유기화제의 탄소 사슬수가 10보다 작으며 올레핀과의 상용성이 낮아 유기화제의 효과를 낮으며, 18이상에서는 더 이상의 효과를 기대할 수 없다. In the present invention, the organic clay is preferably selected from the group consisting of montmorillonite, hectorite, saponite, baderite, nontronite, vermiculite and halosite as a silicate mineral having a layered structure. Do. In addition, the organic agent is preferably alkyl ammonium having 10 to 18 carbon chains. The number of carbon chains of the organic agent is less than 10, and the compatibility with the olefin is low, the effect of the organic agent is low, more than 18 can not be expected more effects.
알킬 암모늄에 의해 양이온 몬트모릴로나이트, 헥토라이트, 사포나이트, 베 이데라이트, 논트로나이트, 버미큘라이트 및 할로이사이트에 상응하는 양성자화된 1차 아민간의 양이온 교환 반응으로 층상 실리케이트가 유기화된다. 층상 실리케이트의 기본 구조는 실리카 테트라헤드랄 시트(silica tetrahedral sheet)와 알루미나 옥타헤드랄 시트(alumina octahedral sheet)의 조합으로 이루어져 있는데, 그 층간에는 Na+, Li+ 등의 이온으로 채워져 있다. 또한 시트의 말단에는 OH-기가 존재한다. 따라서 매우 극성인 친수성 구조이므로 친유성 수지인 폴리프로필렌 수지와의 극성차이가 심하여 프로필렌수지가 인터칼레이션되거나 층상 실리케이트가 디라미네이션 되어 수지 안으로 분산될 수 없다. Layered silicates are organicized by alkyl ammonium by cation exchange reactions between the protonated primary amines corresponding to cationic montmorillonite, hectorite, saponite, baderite, nontronite, vermiculite and halosite. The basic structure of the layered silicate consists of a combination of silica tetrahedral sheet and alumina octahedral sheet, which are filled with ions such as Na + and Li + . There is also an OH - group at the end of the sheet. Therefore, since the polarity is very polar hydrophilic structure and polypropylene resin is a lipophilic resin propylene resin is not intercalated or layered silicate can not be dispersed into the resin.
그러므로 수지의 인터칼레이션 또는 층상 실리케이트의 분산을 위해서는 극성을 감소시킨 층상 실리케이트를 사용하여야 하는데, 이를 위해서 본 발명에서는 유기화제로 처리된 유기화된 층상 실리케이트(OLS : Organically modified Layered Silicate)를 사용한다. 본 발명에서는 층간 거리를 넓히기 위해 분자 크기가 큰 알킬 암모늄으로 유기화된 층상 실리케이트를 사용한다. Therefore, in order to intercalate resins or disperse layered silicates, polarized layered silicates should be used. For this purpose, organically modified layered silicates (OLS) are used in the present invention. In the present invention, layered silicates organicized with alkylammonium having a large molecular size are used to increase the interlayer distance.
상기 수지 조성물은 상기 층상 실리케이트의 층간에 폴리프로필렌 수지가 인터칼레이션되거나 디라미네이션되어 나노복합수지화된 것임을 특징으로 한다. 본 발명에서는 상기 유기화된 층상 실리케이트와 폴리프로필렌 수지 혼합물이 상기 인터칼레이션 또는 상기 디라미네이션을 통해 나노복합수지 구조가 형성되었음을 X-레이 회절에 의하여 확인한다. X-레이 회절에 의해 층상 실리케이트의 층간 거리의 변화를 측정하여 확인하는 것이다. 나노복합수지가 형성되면 클레이 층간 거리가 변화하지만 나노복합수지가 형성되지 않은 경우에는 클레이 층간 거리가 변화하지 않는다.The resin composition is characterized in that the polypropylene resin is intercalated or delaminated between the layers of the layered silicate is nanocomposite resin. In the present invention, the organic layered silicate and the polypropylene resin mixture is confirmed by X-ray diffraction that the nanocomposite structure is formed through the intercalation or the delamination. It is confirmed by measuring the change in the interlayer distance of the layered silicate by X-ray diffraction. The clay interlayer distance changes when the nanocomposite is formed, but the clay interlayer distance does not change when the nanocomposite is not formed.
금속수산화물은 지방산, 실란 또는 고분자중 1 또는 2 이상으로 표면 처리되거나 비표면 처리된 수산화 알루미늄, 훈타이트 및 마그네슘하이드로사이드로 이루어진 그룹에서 선택되는 1 또는 2 이상을 혼용하여 사용한다.The metal hydroxide is used in combination with one or two or more selected from the group consisting of aluminum hydroxide, huntite and magnesium hydroside surface-treated or unsurfaced with one or two or more of fatty acids, silanes or polymers.
본 발명에서는 필요에 따라 열안정제, 산화방지제, 광안정제 등을 첨가할 수 있으며, 유기 또는 무기안료 및 염료 등을 첨가할 수 있다.In the present invention, a heat stabilizer, an antioxidant, a light stabilizer, and the like may be added, if necessary, and an organic or inorganic pigment and a dye may be added.
본 발명의 수지 조성물은 하기 방법에 의해 제조될 수 있다. 즉, 지정된 양의 폴리프로필렌 수지에 폴리에틸렌계 수지가 혼합된 수지, 무수 말레인산 그라프트 폴리프로필렌 수지, 유기화 클레이 및 상기한 여러 첨가제를 교반-혼합장치에서 교반-혼합 시키고, 180℃에서 믹서를 사용하여 용융 및 혼련시켜 중간단계 혼합수지를 수득한다. 수득된 복합수지 및 금속수산화물을 교반-혼합장치에서 교반-혼합 시키고, 180℃에서 믹서를 사용하여 용융 및 혼련시켜 최종 혼합수지를 수득한다. 본 발명에서는 또한 상기 유기와 클레이와 금속수산화물을 교반-혼합시키는 광정을 동시에 진행하여도 동등한 효과를 얻을 수 있다.The resin composition of this invention can be manufactured by the following method. That is, a resin in which a polyethylene-based resin is mixed with a specified amount of polypropylene resin, maleic anhydride graft polypropylene resin, organic clay, and various additives described above are stirred-mixed in a stirring-mixing apparatus, using a mixer at 180 ° C. Melting and kneading to obtain an intermediate mixed resin. The obtained composite resin and metal hydroxide are stirred-mixed in a stirring-mixing apparatus and melted and kneaded using a mixer at 180 ° C. to obtain a final mixed resin. In the present invention, an equivalent effect can also be obtained by simultaneously carrying out the above-described light mixing of organic, clay and metal hydroxide.
이하에 실시예를 들어 본 발명을 더욱 설명하고자 하나 하기의 실시예는 본 발명의 예시 목적을 위한 것이며, 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The following examples are intended to further illustrate the present invention with reference to the following examples, which are intended for purposes of illustration of the invention, and are not intended to limit the scope of protection defined by the appended claims.
도 1은 본 발명의 일실시예에 따른 전선 재료가 적용된 전선 단면을 나타내는 개략도이다. 도 1에서 보는 바와 같이 안쪽에 전류를 흐르게 하는 도체(1)가 있 으며 바깥쪽에 본 발명에 의하여 개발된 난연 절연 조성물(2)로 절연되어 있는 구조이다.1 is a schematic diagram showing a wire cross section to which a wire material is applied according to an embodiment of the present invention. As shown in Figure 1 there is a conductor (1) for flowing a current inside and is insulated with a flame retardant insulation composition (2) developed by the present invention on the outside.
[표 1]에서는 하기의 6가지 성분들을 혼련한 표이다. 본 발명에 의한 실시예와 비교예에서의 함량은 아래의 성분 A, B, C, D, E를 100중량부로 하여 성분 F, G를 중량부로 첨가하여 혼련한 것이다.In Table 1, the following six components are kneaded. The content in Examples and Comparative Examples according to the present invention is kneaded by adding components F, G in parts by weight with 100 parts by weight of components A, B, C, D, and E below.
성분 A: 폴리프로필렌 단독 중합체 [H710(상품명); 한국 LG-Caltex(주)제조] Component A: polypropylene homopolymer [H710 (trade name); Korea LG-Caltex Co., Ltd.]
성분 B: 폴리프로필렌 에틸렌 블록 공중합 수지 [M710(상품명) ; 한국 LG-Caltex(주) 제조]Component B: polypropylene ethylene block copolymer resin [M710 (brand name); Korea LG-Caltex Co., Ltd. manufacture]
성분 C: 폴리프로필렌 에틸렌 랜덤 공중합 수지[R724J (상품명) ; 한국 LG-Caltex㈜ 제조]Component C: polypropylene ethylene random copolymer resin [R724J (brand name); Manufacture of LG-Caltex, Korea]
성분 D: 메탈로센 촉매에 의해 중합된 폴리올레핀 엘라스토머 수지[Engage 8150(상품명) ; 미국 Dupont Dow Elastomer 제조]Component D: polyolefin elastomer resin polymerized with a metallocene catalyst [Engage 8150 (trade name); Dupont Dow Elastomer, USA]
성분 E : 무수말레인산 그라프트 폴리프로필렌 수지[PH-200 (상품명) ; 한국 호남석유화학㈜ 제조]Component E: Maleic anhydride graft polypropylene resin [PH-200 (brand name); Manufacture of Honam Petrochemical Co., Ltd. in Korea]
성분 F : 유기화 클레이[Cloisite 20A (상품명) ; 미국 Southern Clay Products Inc. 제조]Component F: organic clay [Cloisite 20A (trade name); Southern Clay Products Inc. Produce]
성분 G : 마그네슘하이드로옥사이드[Magnifin (상품명) ; 미국 Albemarle Corp. 제조] Component G: magnesium hydrooxide [Magnifin (brand name); Albemarle Corp. Produce]
비교예 1 내지 비교예 4에서 나타난 성분 및 조성비를 사용하여 상기 실시예와 동등한 방법으로 혼련하여 수지 조성물을 얻어 표 2에 표기하였다.Using the components and the composition ratio shown in Comparative Examples 1 to 4 were kneaded in the same manner as in the above Example to obtain a resin composition is shown in Table 2.
실시예 및 비교예에서 난연성, 발연성, 인장강도, 신장율, 열안정성등의 평가방법은 다음과 같으며 그 평가결과를 표 3에 나타내었다.In Examples and Comparative Examples, evaluation methods such as flame retardancy, smoke resistance, tensile strength, elongation rate, thermal stability, and the like are as follows, and the evaluation results are shown in Table 3.
물성측정방법Property measurement method
인장특성 측정Tensile Properties Measurement
ASTM D 638 (Standard Test Method for Tensile Properties of Plastics)에 의거하여 측정용 시편을 만들어 만능시험기를 사용, 인장강도(Tensile Strength) 및 신율(Elongation@Break) 값을 측정하였다. (인장강도 [Pa] = 최대 load [N] / 초기 시료의 단면적 [m2], 신율 [%] = 파단점까지의 늘어난 길이 / 초기 길이)Measurement specimens were made according to ASTM D 638 (Standard Test Method for Tensile Properties of Plastics), and the tensile test (tensile strength) and elongation (Elongation @ Break) values were measured using a universal testing machine. Tensile strength [Pa] = maximum load [N] / cross sectional area of initial sample [m 2 ], elongation [%] = extended length to break point / initial length)
난연성 측정Flame Retardant Measurement
ASTM E 1394 (Standard Test Method for Heat and Visible Smoke Release Rates for Materials and Products Using an Oxygen Consumption Calorimeter) 에 의거하여 Cone 열량계 기기를 사용하여 열 유량 (Heat Flux) 35 kW/m2 조건에서 수지의 열 방출 속도(HRR, heat release rate)를 비교하였다. 상기 측정 조건 중 열 유량 35 kW/m2 조건은 실제 화재시 방출되는 열량과 매우 유사한 조건이며, 이 조건에서 연소되는 물질의 배출 방출 속도는 실제 화재시 물질의 난연성을 평가할 수 있는 지표로 인정되고 있다. 사용된 시편 사이즈는 가로 100 mm x 세로 100 mm x 두께 3 mm 이다.Heat release of resin under Heat Flux 35 kW / m 2 using a Cone Calorimeter instrument in accordance with ASTM E 1394 (Standard Test Method for Heat and Visible Smoke Release Rates for Materials and Products Using an Oxygen Consumption Calorimeter) The rate of heat release (HRR) was compared. The heat flow rate of 35 kW / m 2 of the above measurement conditions is very similar to the amount of heat released during an actual fire. have. The specimen size used is 100 mm wide x 100 mm long x 3 mm thick.
실시예 1 내지 실시예 6의 재료는 우수한 인장강도 및 신율을 나타내었다. 또한 최대 열방출속도도 200 kW/m2 미만으로 우수하였으며 평균 열방출속도도 50 kW/m2미만으로 기존 재료 대비 우수한 난연특성을 나타냈다. The materials of Examples 1-6 showed excellent tensile strength and elongation. In addition, the maximum heat release rate was excellent at less than 200 kW / m 2 and the average heat release rate was also less than 50 kW / m 2 , which showed superior flame retardant properties compared to existing materials.
반면 폴리프로필렌 수지를 단독으로 사용한 비교예 1 내지 비교예 3에서는 신율이 매우 열등하였으며, 비교예 4의 경우와 같이 무기난연제를 사용하지 않은 경우는 난연성이 산업적으로 이용할 만큼의 수준이 되지 않는다.On the other hand, in Comparative Examples 1 to 3 using polypropylene resin alone, the elongation was very inferior, and when the inorganic flame retardant was not used as in the case of Comparative Example 4, the flame retardancy did not become as high as industrial use.
본 발명은 상기 수지 조성물, 상기 수지 조성물을 이용하여 만들어진 전선뿐만 아니라 이를 이용한 자동차부품, 비행기부품은 물론 수지 조성물의 사용이 예측 가능한 전기, 전자, 통신, 기계, 화학 등 다양한 분야에서 사용될 수 있다. 이 경우 상기 수지 조성물을 이용하여 만들어진 제품은 변형된 형태에 관계없이 본 발명에 의한 권리범위에 포함된다고 할 것이다.The present invention can be used in various fields such as electrical, electronic, telecommunications, machinery, chemistry, as well as the resin composition, the electric wire made using the resin composition, as well as automotive parts, airplane parts using the resin composition can be predicted. In this case, products made using the resin composition will be said to fall within the scope of the present invention regardless of the modified form.
본 발명의 바람직한 실시예 및 비교예를 설명함으로써 본 발명을 더욱 상세하게 설명하였다. 그러나 본 발명의 권리범위는 상기 실시예에 한정되는 것은 아니라 첨부된 특허청구범위내에서 다양한 형태의 실시예로 구현될 수 있다. 특허청구범위에서 청구하는 본 발명의 요지를 벗어남이 없이 당해 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 누구든지 가능한 다양한 변형 가능한 범위까지 본 발명의 청구 범위 기재의 범위 내에 있는 것으로 본다.The present invention has been described in more detail by describing preferred embodiments and comparative examples of the present invention. However, the scope of the present invention is not limited to the above embodiments but may be embodied in various forms of embodiments within the appended claims. Without departing from the gist of the invention as claimed in the claims, any person of ordinary skill in the art is considered to be within the scope of the claims described in the present invention to the extent possible to vary.
따라서, 본 발명에 따르면, 폴리프로필렌 수지에 1종 이상의 폴리에틸렌계 수지가 혼합된 수지에 유기화 처리된 나노 클레이를 나노 스케일로 분산시키고, 금속수산화물을 첨가하여 우수한 기계적 물성, 특히 우수한 신율을 가지면서 동시에 난연성이 획기적으로 향상되는 효과가 있다.Therefore, according to the present invention, the organic clay is dispersed on a nano scale in a resin in which at least one polyethylene-based resin is mixed in a polypropylene resin, and a metal hydroxide is added to have excellent mechanical properties, particularly excellent elongation. The flame retardancy is significantly improved.
본 발명은 기존의 무기계 난연제 사용량을 감소시키는 효과를 제공하여 최종 제품의 우수한 기계적 물성을 제공하며, 또한 할로겐계 난연제를 사용하지 않는 친환경적인 제품의 제조를 가능하게 하는 발명의 효과를 가진다.The present invention provides the effect of reducing the amount of conventional inorganic flame retardant to provide excellent mechanical properties of the final product, and also has the effect of the invention to enable the production of environmentally friendly products that do not use a halogen-based flame retardant.
비록 발명이 상기에서 언급된 바람직한 실시예에 관해 설명되어졌으나, 발명의 요지와 범위를 벗어남이 없이 많은 다른 가능한 수정과 변형이 이루어질 수 있다. 따라서, 첨부된 청구범위는 발명의 진정한 범위내에서 속하는 이러한 수정과 변형을 포함할 것으로 예상된다.Although the invention has been described with reference to the preferred embodiments mentioned above, many other possible modifications and variations can be made without departing from the spirit and scope of the invention. Accordingly, the appended claims are intended to cover such modifications and variations as fall within the true scope of the invention.
Claims (12)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040037000A KR100745144B1 (en) | 2004-05-24 | 2004-05-24 | Polypropylene resin composite with improved mechanical and fire retardant properties and the cable using thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040037000A KR100745144B1 (en) | 2004-05-24 | 2004-05-24 | Polypropylene resin composite with improved mechanical and fire retardant properties and the cable using thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20050112145A KR20050112145A (en) | 2005-11-29 |
| KR100745144B1 true KR100745144B1 (en) | 2007-08-02 |
Family
ID=37287084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020040037000A KR100745144B1 (en) | 2004-05-24 | 2004-05-24 | Polypropylene resin composite with improved mechanical and fire retardant properties and the cable using thereof |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100745144B1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100867846B1 (en) | 2007-12-12 | 2008-11-10 | 현대자동차주식회사 | Manufacturing method of polypropylene-clay nanocomposites having high impact proof-strength manufacturing price |
| KR100903748B1 (en) * | 2007-09-04 | 2009-06-19 | 호서대학교 산학협력단 | Nanocomposite Composition With Flame Retardancy And Antistatic Properties and Preparation Method Thereof |
| DE102015223936A1 (en) | 2015-02-27 | 2016-09-01 | Hyundai Motor Company | Polypropylene and graphene composite and method of making same |
| CN109021363A (en) * | 2018-08-21 | 2018-12-18 | 张玉英 | A kind of polythene material and preparation method of halloysite nanotubes cooperative flame retardant |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100745320B1 (en) * | 2001-12-24 | 2007-08-01 | 삼성토탈 주식회사 | Flame Retardant Polypropylene Resin Composition |
| JP2009527620A (en) * | 2006-02-22 | 2009-07-30 | エルエス ケーブル リミテッド | Flame retardant polypropylene resin composition with wear resistance |
| KR100687363B1 (en) | 2006-02-22 | 2007-02-26 | 엘에스전선 주식회사 | Propylene composition with flame retardant and improved abrasion resistance |
| KR100855796B1 (en) * | 2007-02-15 | 2008-09-01 | 엘에스전선 주식회사 | Propylene composition with flame retardant and abrasion resistance |
| WO2009005249A1 (en) * | 2007-07-03 | 2009-01-08 | Ls Cable Ltd. | Flame retardant polymer composition |
| KR101143749B1 (en) * | 2007-12-05 | 2012-05-11 | 주식회사 엘지화학 | Flame Retardant Polypropylene Composition with Enhanced Long Term Heat Resistance |
| KR101454062B1 (en) * | 2011-04-12 | 2014-10-27 | 주식회사 엘지화학 | olefin thermoplastic elastomers composition |
| KR101278986B1 (en) * | 2012-04-27 | 2013-07-02 | 박용필 | Thermoplastic resin composition |
| ES2545428T3 (en) * | 2013-04-16 | 2015-09-10 | Borealis Ag | Insulating layer for cables |
| KR102152381B1 (en) * | 2019-12-06 | 2020-09-04 | 케이비아이코스모링크 주식회사 | High flame retardant power cable |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997872A (en) | 1988-09-08 | 1991-03-05 | Sumitomo Chemical Company, Ltd. | Resinous composition |
| KR19990041626A (en) * | 1997-11-24 | 1999-06-15 | 이정국 | Polyolefin composite resin composition for automobile interior |
| KR20020086647A (en) * | 2000-03-17 | 2002-11-18 | 다우 글로벌 테크놀로지스 인크. | Preparation of a macrocellular acoustic foam |
| KR20040018959A (en) * | 2002-08-27 | 2004-03-04 | 이엠에스-케미에 아게 | High-viscous moulding materials with nano-scale fillers |
| KR20040105823A (en) * | 2002-03-28 | 2004-12-16 | 콤프코 피티와이 엘티디 | Cross-linkable and/or cross-linked nanofiller compositions |
-
2004
- 2004-05-24 KR KR1020040037000A patent/KR100745144B1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4997872A (en) | 1988-09-08 | 1991-03-05 | Sumitomo Chemical Company, Ltd. | Resinous composition |
| KR19990041626A (en) * | 1997-11-24 | 1999-06-15 | 이정국 | Polyolefin composite resin composition for automobile interior |
| KR20020086647A (en) * | 2000-03-17 | 2002-11-18 | 다우 글로벌 테크놀로지스 인크. | Preparation of a macrocellular acoustic foam |
| KR20040105823A (en) * | 2002-03-28 | 2004-12-16 | 콤프코 피티와이 엘티디 | Cross-linkable and/or cross-linked nanofiller compositions |
| KR20040018959A (en) * | 2002-08-27 | 2004-03-04 | 이엠에스-케미에 아게 | High-viscous moulding materials with nano-scale fillers |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100903748B1 (en) * | 2007-09-04 | 2009-06-19 | 호서대학교 산학협력단 | Nanocomposite Composition With Flame Retardancy And Antistatic Properties and Preparation Method Thereof |
| KR100867846B1 (en) | 2007-12-12 | 2008-11-10 | 현대자동차주식회사 | Manufacturing method of polypropylene-clay nanocomposites having high impact proof-strength manufacturing price |
| DE102015223936A1 (en) | 2015-02-27 | 2016-09-01 | Hyundai Motor Company | Polypropylene and graphene composite and method of making same |
| CN109021363A (en) * | 2018-08-21 | 2018-12-18 | 张玉英 | A kind of polythene material and preparation method of halloysite nanotubes cooperative flame retardant |
| CN109021363B (en) * | 2018-08-21 | 2021-02-02 | 上海方北家居有限公司 | Halloysite nanotube synergistic flame-retardant polyethylene material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20050112145A (en) | 2005-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100745144B1 (en) | Polypropylene resin composite with improved mechanical and fire retardant properties and the cable using thereof | |
| US7851559B2 (en) | Soft zero halogen flame retardant thermoplastic elastomers | |
| Ramírez‐Vargas et al. | Structural characterization of LDPE/EVA blends containing nanoclay‐flame retardant combinations | |
| Zhang et al. | Influence of Fe‐MMT on the fire retarding behavior and mechanical property of (ethylene‐vinyl acetate copolymer/magnesium hydroxide) composite | |
| Utracki | Clay-containing polymeric nanocomposites and their properties | |
| CA3141484A1 (en) | Flame retardant polymer composition and methods of use | |
| Chang et al. | Preparation and properties of styrene–ethylene/butylene–styrene (SEBS)–clay hybrids | |
| Kannan et al. | Flame‐retardant properties of nanoclay‐filled thermoplastic polyurethane/polypropylene nanocomposites | |
| KR20100078821A (en) | Phosphorus-based polyolefin flame retardant composition containing nanoclay | |
| CN101437888A (en) | Halogen-free, flame-retardant wire-and-cable composition and related articles | |
| WO2005021641A1 (en) | Flame retardant polymer composition comprising nanofillers | |
| KR20020002786A (en) | Polypropylene polymer composite comprising a organic layered clay and production process therefor | |
| WO2009025711A1 (en) | Flame retardant thermoplastic elastomer compositions | |
| KR100612406B1 (en) | Polypropylene resin composite with improved mechanical and fire retardant properties using the clay and cable using thereof | |
| EP1215685A1 (en) | Electrical wire having a covering of a resin composition | |
| Boucard et al. | Processing of polypropylene‐clay hybrids | |
| Mahmoudi et al. | Electrical and mechanical characterization of high-density polyethylene/ethylene vinyl acetate/organoclay nanocomposite | |
| Hajibeygi et al. | Plasticized polyvinyl chloride/melamine‐cyanurate modified Mg (OH) 2@ bentonite nanocomposites; mechanical, thermal, and flame retardant properties | |
| Fang et al. | Preparation and investigation of ethylene–vinyl acetate copolymer/silicone rubber/clay nanocomposites | |
| KR100619642B1 (en) | Polyolefin Resin Composition | |
| Hong et al. | Tensile and flammability properties of polypropylene‐based RTPO/clay nanocomposites for cable insulating material | |
| EP1345989B1 (en) | Use of a nanofiller-containing polyolefin composition for the production of improved articles | |
| CA2729268C (en) | Method for exfoliating organoclay to produce a nanocomposite | |
| KR20100078823A (en) | Inorganic and melamine-based polyolefin flame retardant composition containing nanoclay | |
| WO2002006388A1 (en) | Polypropylene-clay composite having excellent flame-resistance and producing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| AMND | Amendment | ||
| E601 | Decision to refuse application | ||
| J201 | Request for trial against refusal decision | ||
| AMND | Amendment | ||
| B601 | Maintenance of original decision after re-examination before a trial | ||
| E801 | Decision on dismissal of amendment | ||
| J301 | Trial decision |
Free format text: TRIAL DECISION FOR APPEAL AGAINST DECISION TO DECLINE REFUSAL REQUESTED 20060330 Effective date: 20061129 |
|
| S901 | Examination by remand of revocation | ||
| E90F | Notification of reason for final refusal | ||
| GRNO | Decision to grant (after opposition) | ||
| GRNT | Written decision to grant | ||
| G170 | Publication of correction | ||
| FPAY | Annual fee payment |
Payment date: 20120611 Year of fee payment: 6 |
|
| LAPS | Lapse due to unpaid annual fee |