KR100627512B1 - Non-halogen cold-resistant flame retardant insulation composition - Google Patents
Non-halogen cold-resistant flame retardant insulation composition Download PDFInfo
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- KR100627512B1 KR100627512B1 KR1020050008684A KR20050008684A KR100627512B1 KR 100627512 B1 KR100627512 B1 KR 100627512B1 KR 1020050008684 A KR1020050008684 A KR 1020050008684A KR 20050008684 A KR20050008684 A KR 20050008684A KR 100627512 B1 KR100627512 B1 KR 100627512B1
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 47
- 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 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 27
- 238000009413 insulation Methods 0.000 title claims abstract description 12
- 239000004698 Polyethylene Substances 0.000 claims abstract description 30
- 229920000573 polyethylene Polymers 0.000 claims abstract description 30
- 150000002367 halogens Chemical class 0.000 claims abstract description 25
- -1 polyethylene Polymers 0.000 claims abstract description 22
- 239000011810 insulating material Substances 0.000 claims abstract description 20
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 13
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 13
- 230000009477 glass transition Effects 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011247 coating layer Substances 0.000 claims abstract description 11
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 10
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 7
- 239000012796 inorganic flame retardant Substances 0.000 claims abstract description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005977 Ethylene Substances 0.000 claims abstract description 4
- 229920006026 co-polymeric resin Polymers 0.000 claims abstract description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 10
- 239000004702 low-density polyethylene Substances 0.000 claims description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QLZJUIZVJLSNDD-UHFFFAOYSA-N 2-(2-methylidenebutanoyloxy)ethyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OCCOC(=O)C(=C)CC QLZJUIZVJLSNDD-UHFFFAOYSA-N 0.000 claims description 4
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 claims description 4
- 239000005042 ethylene-ethyl acrylate Substances 0.000 claims description 4
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 4
- 239000005043 ethylene-methyl acrylate Substances 0.000 claims description 4
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 2
- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical compound C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000012774 insulation material Substances 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 230000032683 aging Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 6
- 229920001038 ethylene copolymer Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 4
- 239000011342 resin composition Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 101100389815 Caenorhabditis elegans eva-1 gene Proteins 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical group [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
- C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
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Abstract
본 발명은 비할로겐계 내한 난연성 절연재 제조용 조성물에 관한 것이다. 본 발명은 폴리에틸렌(PE)계 수지와 에틸렌계 공중합체 수지의 블랜드비 1:9 내지 3:7로 이루어지며, 유리전이온도(Tg)가 -20℃ 이하로 조절된 베이스수지 100 중량부;에 대하여, 금속수산화물계 무기난연제 100 내지 150 중량부; 및 실리콘산화물계 난연조제 1 내지 10 중량부;를 포함하여 이루어지는 것을 특징으로 한다. 본 발명에 따르면, 사용된 조성물 성분 내에 할로겐 원소가 포함되어 있지 않아 연소시 종래의 할로겐계 제품에 비해 친환경적이라 할 수 있으며, 난연성, 가공유연성, 기계적 특성이 요구되는 조건을 충분하게 만족시킴은 물론, 저온 지역이나 선박 등에 사용되는 전선(cable)용 절연피복층에 요구되는 내한성까지 충분하게 확보됨으로 인해, 저온에서 절연재가 깨짐으로써 발생되는 제품이나 설비의 고장, 불량 등을 방지할 수 있으므로, 전선용 절연피복층과 같은 절연재가 사용되는 장소의 기후나, 온도 조건에 최적화된 물성을 구비한 절연제품을 생산할 수 있어 바람직하다.The present invention relates to a composition for producing a non-halogen cold-resistant flame retardant insulating material. The present invention comprises a blend ratio of polyethylene (PE) -based resin and ethylene-based copolymer resin 1: 9 to 3: 7, 100 parts by weight of the base resin glass transition temperature (Tg) is adjusted to -20 ℃ or less; 100 to 150 parts by weight of the metal hydroxide inorganic flame retardant; And 1 to 10 parts by weight of the silicon oxide flame retardant aid. According to the present invention, since it does not contain a halogen element in the composition composition used, it can be said to be environmentally friendly compared to the conventional halogen-based products when burning, satisfies the requirements that the flame retardancy, process flexibility, mechanical properties are required as well as By securing sufficient cold resistance required for the insulation coating layer for cables used in low-temperature areas or ships, it is possible to prevent breakdowns or defects in products or facilities caused by breakdown of insulation materials at low temperatures. It is preferable to produce an insulation product having properties optimized for the climate and temperature conditions where an insulation material such as an insulation coating layer is used.
내한성, 열가소성, 폴리에틸렌, 할로겐, 전선Cold Resistance, Thermoplastic, Polyethylene, Halogen, Wires
Description
본 발명은 비할로겐계 내한 난연성 절연재 제조용 조성물에 관한 것으로서, 보다 상세하게는 내한성이 있는 폴리에틸렌계 수지와 에틸렌계 공중합 수지를 적정하게 블랜딩하되, 난연제로 사용되는 금속수산화물의 양을 종래에 알려진 양보다 적게 첨가시킴으로써 유리전이온도를 -20℃이하로 낮춘 비할로겐계 내한 난연성 절연재 제조용 조성물에 관한 것이다.The present invention relates to a composition for producing a non-halogen cold-resistant flame retardant insulating material, and more particularly to blending a cold-resistant polyethylene resin and an ethylene copolymer resin appropriately, the amount of the metal hydroxide used as a flame retardant than conventionally known amounts The present invention relates to a composition for producing a non-halogen-based cold-resistant flame retardant insulation material having a low glass transition temperature of less than -20 ° C by adding less.
전선의 절연재료로 이용되기 위해서는 일정 정도 이상의 난연성이 요구되고 있으며, 이러한 난연성 개선을 위한 목적으로 개발된 것이 할로겐 원소를 포함하고 있는 수지 조성물을 이용하는 방법이 알려져 있다. 한편, 할로겐 원소를 함유한 수지 조성물을 이용하여 제조된 절연재의 경우에는 연소시 불연의 무거운 할로겐 가스를 발생시키고 첨가제와 반응함으로써 고형화된 재를 형성시킴으로써 재료의 연소를 억제하는 것으로 알려져 있다. 따라서, 할로겐계 수지를 이용하여 제조된 절연재의 경우에는 기본적으로 난연성이 보유되어 있으며, 보다 개선된 난연성 확보 를 목적으로 각종 난연제를 첨가하고 있다. 이렇게 첨가되는 각종 난연제는 소량만이 사용되므로 베이스수지의 기본 물성에 큰 영향을 미치지 아니하며, 절연재료의 점도 상승을 유발시키지도 않으므로 우수한 압출가공성을 발현하는 장점이 있다.In order to be used as an insulating material for electric wires, a flame retardance of a certain degree or more is required, and a method of using a resin composition containing a halogen element is known that has been developed for the purpose of improving the flame retardancy. On the other hand, in the case of an insulating material manufactured using a resin composition containing a halogen element, it is known to suppress the combustion of materials by generating a non-flammable heavy halogen gas during combustion and forming a solidified ash by reacting with an additive. Therefore, in the case of the insulating material manufactured using a halogen-based resin, flame retardancy is basically retained, and various flame retardants are added for the purpose of securing more improved flame retardancy. The various flame retardants added in this way does not significantly affect the basic physical properties of the base resin, and does not cause an increase in the viscosity of the insulating material, and thus has an advantage of expressing excellent extrusion processability.
종래의 절연재료를 제조하기 위한 베이스수지에 첨가되는 난연제로서 사용되는 대표적인 물질로서, 폴리비닐클로라이드(PVC)를 들 수 있으나, 상기 물질이 포함된 수지 조성물을 이용하여 제조된 절연재를 연소시키면 다이옥신과 같은 유독성 가스가 방출됨으로 인해, 인체는 물론 환경에도 유해한 영향을 끼치고 있는 것으로 알려지게 되었다. 이와 관련하여 환경보호를 위한 규제의 측면이나 친환경적인 대체 소재 개발의 관심의 측면 등과 더불어 상대적으로 유해성이 낮은 새로운 재료물질에 대한 개발이 진행되고 있다.As a representative material used as a flame retardant added to the base resin for manufacturing a conventional insulating material, polyvinyl chloride (PVC) may be mentioned, but when the insulating material produced by using the resin composition containing the material is burned, Due to the release of the same toxic gas, it is known to have a harmful effect on the human body and the environment. In connection with this, the development of new materials with relatively low hazards is being progressed along with regulations for environmental protection and interests in the development of environmentally friendly alternative materials.
친환경적 난연기술로서 대두되고 있는 기술에서는 무기계 금속수산화물이 사용되고 있으며, 난연성 향상을 위해서는 이들 물질이 상당한 양이 첨가되어야 하는 반면 그로 인하여 제조된 절연재의 인장강도나 신율 등의 기계적 특성이 열화되는 문제점이 지적되고 있다.Inorganic metal hydroxides are used in technologies that are emerging as environmentally friendly flame retardant technologies.In order to improve the flame retardancy, a considerable amount of these materials must be added, but the mechanical properties such as tensile strength and elongation of the manufactured insulation are deteriorated. It is becoming.
한편, 낮은 온도의 해수의 영향을 상시적으로 받을 수 있는 선박이나 극지방 등의 저온 환경에서 사용되는 전선의 절연피복층은 저온에 대한 내성을 갖고 있지 않는 경우에는 절연재에 깨짐현상 등이 발생하여 제품에 손상이 발생되거나 설비물로부터 누전 등이 발생할 수 있으므로 이에 대한 적절한 조치가 이루어져야 한다.On the other hand, the insulation coating layer of wires used in low temperature environment such as ships or polar regions that can be affected by low temperature seawater at all times, if it is not resistant to low temperature, breakage phenomenon occurs in the insulating material, etc. Appropriate measures should be taken because damage may occur or short circuits may occur from the installation.
이와 관련하여, 내한성의 관점에서 절연재 제조용 조성물의 베이스수지를 선택한다면, 유리전이온도가 낮고 결정성이 높은 폴리에틸렌이 적절한 선택일 수 있 으나, 폴리에틸렌은 그 가공성 측면에서 다른 수지에 비해 불량하며, 난연성을 충분하게 확보하기 위해 사용하는 난연제를 다량 충전시킬 수 없는 문제점이 발생하고 있다. 따라서, 폴리에틸렌이 갖는 내한성과 관련된 장점을 유지하면서, 다른 물성도 충분하게 구현할 수 있는 절연재를 제조하기 위한 여러 방안들이 관련분야에서 연구되고 있으며, 이러한 기술적 배경하에서 본 발명이 안출된 것이다.In this regard, if the base resin of the composition for producing an insulating material is selected from the viewpoint of cold resistance, polyethylene having a low glass transition temperature and high crystallinity may be an appropriate choice, but polyethylene is poor compared to other resins in terms of processability and flame retardancy. There is a problem that can not be filled with a large amount of flame retardant used to ensure a sufficient amount. Therefore, while maintaining the advantages associated with the cold resistance possessed by polyethylene, various methods for producing an insulating material that can sufficiently implement other physical properties have been studied in the related art, the present invention has been devised in this technical background.
전술한 종래의 문제점에 기초하여 본 발명이 이루고자 하는 기술적 과제는, 환경적인 문제를 해결하기 위해서 할로겐 원소를 포함하지 않는 조성물을 구성하고, 난연특성이나 전선의 기계적 특성 등이 양호하게 유지됨은 물론 저온에서도 충분한 내성을 확보하고자 함에 있으며, 이러한 기술적 과제를 달성할 수 있는 내한성 열가소성 비할로겐계 난연성 절연재 제조용 조성물을 제공함에 본 발명이 있다.The technical problem to be solved by the present invention based on the above-mentioned conventional problems is to solve the environmental problems, to form a composition containing no halogen element, and to maintain a good flame retardant characteristics and mechanical properties of the wire, as well as low temperature In order to ensure sufficient resistance to the present invention, there is provided a cold-resistant thermoplastic non-halogen-based flame retardant insulation composition for achieving the above technical problem.
본 발명이 이루고자 하는 기술적 과제의 달성을 위해 본 발명에 따른 내한 난연성 비할로겐계 절연재 제조용 조성물은, 폴리에틸렌(PE)계 수지와 에틸렌계 공중합체 수지의 블랜드비가 1:9 내지 3:7로 이루어지며, 유리전이온도(Tg)가 -20℃ 이하로 조절된 베이스수지 100 중량부;에 대하여, 금속수산화물계 무기난연제 100 내지 150 중량부; 및 실리콘산화물계 난연조제 1 내지 10 중량부;를 포함하여 이루어지는 것을 특징으로 한다.In order to achieve the technical problem to be achieved by the present invention, the composition for producing a cold-resistant flame-retardant non-halogen-based insulating material according to the present invention, the blend ratio of polyethylene (PE) -based resin and ethylene-based copolymer resin is 1: 9 to 3: 7 100 parts by weight of the base resin having a glass transition temperature (Tg) of -20 ° C. or less; relative to 100 to 150 parts by weight of the metal hydroxide inorganic flame retardant; And 1 to 10 parts by weight of the silicon oxide flame retardant aid.
상기 폴리에틸렌(PE)은 통상의 폴리에틸렌(PE), 선형 저밀도 폴리에틸렌(LLDPE), 저밀도 폴리에틸렌(LDPE), 고밀도 폴리에틸렌(HDPE) 및 변성 폴리에틸렌 중 선택된 하나의 단일물 또는 둘 이상의 혼용물이면 바람직하다. 상기 폴리에틸렌은 유리전이온도가 -80℃로서, 다른 일반적인 고분자수지에 비해 결정성이 높으며 내한성이 우수하다. 그러나, 폴리에틸렌을 단독으로 하여 베이스수지를 조성하는 경우에는 유연성이 약하여 가공성이 취약하며, 난연제를 많이 충진시킬 수 없으므로, 통상 다른 수지와 혼합하여 사용하는 것이 바람직하다. 특히, 말레인산 무수물이 도입된 변성 폴리에틸렌은 말레인산이 중진제와의 혼합성을 증가시키므로, 폴리에틸렌 자체가 갖는 난연제와의 혼합성이 취약한 점을 보완할 수 있어 더욱 바람직하다.The polyethylene (PE) is preferably a single or a mixture of two or more selected from conventional polyethylene (PE), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE) and modified polyethylene. The polyethylene has a glass transition temperature of −80 ° C., which is higher in crystallinity and better in cold resistance than other general polymer resins. However, when the base resin is composed of polyethylene alone, the flexibility is weak, the processability is weak, and many flame retardants cannot be filled. Therefore, it is generally preferable to use a mixture with other resins. In particular, the modified polyethylene in which maleic anhydride is introduced is more preferable because maleic acid increases the miscibility with the neutralizing agent, and thus the weakness of miscibility with the flame retardant possessed by the polyethylene itself can be compensated.
상기 폴리에틸렌계 수지와 블랜딩되어 베이스수지를 조성하기 위해 사용되는 에틸렌계 공중합체는 에틸렌 비닐 아세테이트(EVA), 에틸렌 에틸 아크릴레이트(EEA) 및 에틸렌 메틸 아크릴레이트(EMA)로 이루어진 물질군 중에서 선택된 하나의 단일물 또는 둘 이상의 혼용물이면 바람직하다.The ethylene copolymer used in blending with the polyethylene resin to form a base resin is one selected from the group consisting of ethylene vinyl acetate (EVA), ethylene ethyl acrylate (EEA), and ethylene methyl acrylate (EMA). It is preferable if it is a single thing or a mixture of two or more.
이때, 상기 베이스수지를 조정하기 위한 폴리에틸렌계 수지와 에틸렌계 공중합체 간의 블랜딩비에 관하여, 상기 수치한정에 미달하는 경우에는 내한성이 나쁘고 강도가 떨어지며, 상기 수치한정을 초과하는 경우에는 난연제의 충진율이 떨어져 난연성이 나빠지므로 바람직하지 못하다.At this time, with respect to the blending ratio between the polyethylene resin and the ethylene copolymer for adjusting the base resin, the cold resistance is poor and the strength is lowered when the numerical limit is not exceeded, and the filling rate of the flame retardant is exceeded when the numerical limit is exceeded. It is not preferable because it is worse in flame retardancy.
상기 베이스수지의 유리전이온도는 상기 폴리에틸렌계 수지와 에틸렌계 공중합체 간의 블랜딩비에 의해 조절될 수 있으며, 에틸렌계공중합체, 예컨대 에틸렌 비닐 아세테이트(유리온도 : -10℃)의 함량이 상대적으로 증가하면 전체적인 베이스수지의 유리전이온도는 폴리에틸렌계 유리전이온도(-80℃)보다 상승하게 되며, 요구되는 내한성을 확보하기 위해서는 -20℃ 이하의 유리전이온도를 갖도록 하여야 하므로, 블랜딩비의 조절에 주의가 요망된다. 이러한 베이스수지의 유리전이온도는 결정성과 연동되며, 유리전이온도가 낮을수록 결정성은 높아지게 되며 결과적으로 내한성이 증가하게 된다.The glass transition temperature of the base resin can be controlled by the blending ratio between the polyethylene resin and the ethylene copolymer, the content of the ethylene copolymer, such as ethylene vinyl acetate (glass temperature: -10 ℃) is relatively increased If the overall glass transition temperature of the base resin is higher than the polyethylene-based glass transition temperature (-80 ℃), in order to ensure the required cold resistance should be set to have a glass transition temperature of less than -20 ℃, careful to control the blending ratio Is desired. The glass transition temperature of the base resin is linked to the crystallinity, the lower the glass transition temperature, the higher the crystallinity, and consequently, the cold resistance increases.
종래에는 상기 금속수산화물인 난연제는 150 중량부 이상이 사용되고 있었으나, 본 발명에서는 내한성 확보를 위해서는 그 양을 줄였으며, 이로 인한 난연성 보강을 위해 실리콘산화물계 난연조제를 첨가하였다. 이때, 상기 금속수산화물인 난연제 함량과 관련하여, 상기 수치한정에 미달하는 경우에는 난연성 확보에 어려움이 있으며, 상기 수치한정의 상한을 초과하는 경우에는 절연재의 기계적 특성이 나빠져 저온에서 깨짐 현상이 발생할 수 있어 내한성이 확보되지 않음으로 인해 바람직하지 못하다. 상기 난연제인 금속수산화물은 붕산아연과 같은 난연조제를 이용하여 표면처리하여 사용하기도 하지만, 본 발명에서는 난연성을 보강하기 위해 실리콘산화물계의 난연조제를 첨가함으로 인해, 금속산화물의 표면처리를 하지 않은 상태로 사용하여도 본 발명의 효과를 달성함에 무리가 없음은 자명하다. 한편, 상기 무기난연제인 금속수산화물은 120 내지 130 중량부인 경우에서 사용되면 본 발명에 따른 내한성 확보에 더욱 바람직하다. 한편, 상기 실리콘산화물계의 난연조제는 절연재의 연소시 고체막을 형성하여 난연성을 향상시키는 차르(char)의 용이한 형성에 영향을 미친다. 상기 실리콘산화물계의 난연조제 함량과 관련하여, 상기 수치한정의 하한에 미달하는 경우에는 난연성 강화목적에 부합되지 못하며, 상기 수치한정의 상한을 초과하는 경우에는 재료 구입을 위한 비용증가와 대비하여 난연성 향상이 미약함은 물론 혼련성이 약화되어 바람직하지 못하다.Conventionally, more than 150 parts by weight of the metal hydroxide flame retardant was used, but in the present invention, the amount thereof was reduced to secure cold resistance, and thus, a silicon oxide-based flame retardant aid was added to reinforce the flame retardancy. In this case, in relation to the flame retardant content of the metal hydroxide, it is difficult to secure flame retardancy when the numerical value is lower than the numerical limit, and when the upper limit of the numerical limit is exceeded, mechanical properties of the insulating material may be deteriorated, thereby causing cracking at low temperatures. It is not preferable because cold resistance is not secured. The metal hydroxide which is the flame retardant may be used by surface treatment using a flame retardant aid such as zinc borate, but in the present invention, a silicon oxide-based flame retardant is added to reinforce the flame retardancy, so that the surface of the metal oxide is not treated. It is obvious that there is no difficulty in achieving the effect of the present invention even when used as. On the other hand, the metal hydroxide which is the inorganic flame retardant is more preferable to ensure cold resistance according to the present invention when used in the case of 120 to 130 parts by weight. On the other hand, the silicon oxide-based flame retardant aids the formation of a solid film during combustion of the insulating material affects the easy formation of char (char) to improve the flame retardancy. With respect to the content of the flame retardant aid of the silicon oxide, if it falls below the lower limit of the numerical limit, it does not meet the purpose of reinforcing the flame retardancy, and if the upper limit of the numerical limit is exceeded, the flame retardancy in preparation for the increase in cost for the material purchase It is not preferable because the improvement is weak and the kneading property is weakened.
전술한 본 발명에 따른 조성물은 내한성 열가소성 비할로겐계 난연성 전선용 절연피복층을 제조하기 위해 이용되면 바람직하다. 상기 내한성 열가소성 비할로겐계 난연성 전선용 절연피복층으로 이용되는 내한성 열가소성 비할로겐계 난연성 절연재는, 그 신율이 120%이상이고, 그 인장강도는 10 내지 20 Mpa이며, 그 산소지수는 28이상이면 바람직하다. 상기의 물성치에 대한 수치한정은 내한성이 요구되는 절연재에 요구되는 조건에 부합되며, 신율 및 인장강도는 ASTM D412에 따른 수치이며, 산소지수는 ASTM D2863에 따른 수치로 표현된 것이다.The composition according to the present invention described above is preferably used to prepare an insulating coating layer for cold-resistant thermoplastic non-halogen-based flame-retardant wire. The cold-resistant thermoplastic non-halogen flame-retardant insulating material used as the insulating coating layer for the cold-resistant thermoplastic non-halogen flame-retardant wire has an elongation of 120% or more, a tensile strength of 10 to 20 Mpa, and an oxygen index of 28 or more. . The numerical limits for the above physical properties are in accordance with the requirements of the insulation material required cold resistance, elongation and tensile strength is a value according to ASTM D412, oxygen index is expressed as a value according to ASTM D2863.
이하, 본 발명을 구체적으로 설명하기 위해 실시예를 들어 설명하기로 한다. 그러나, 본 발명에 따른 실시예들은 여러 가지 다른 형태로 변형될 수 있으며, 본 발명의 범위가 아래에서 상술하는 실시예들에 한정되는 것으로 해석되어지지 않아야 한다. 본 발명의 실시예들은 당 업계에서 평균적인 지식을 가진 자에게 본 발명을 보다 완전하게 설명하기 위해서 제공되어지는 것이다.Hereinafter, the present invention will be described with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. Embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
실시예(1-5) 및 비교예(1-5)의 구분Classification of Example (1-5) and Comparative Example (1-5)
본 발명에 따른 실시예로서 실시예 1 내지 5(하기 표 1 참조)로서 구분 설정하고, 이와 대비하기 위한 목적으로서 비교예 1 내지 5(하기 표 2 참조)를 구분 설정하였다.As examples according to the present invention, the divisions were set as Examples 1 to 5 (see Table 1 below), and Comparative Examples 1 to 5 (see Table 2 below) were set as sections for the purpose of comparison.
전선용 절연피복층 제조Insulation coating layer manufacture for electric wire
상기 하기 표에 따른 실시예 1 내지 5(표 1 참조) 및 비교예 1 내지 5(표 2 참조)에 따른 조성물을 이용한 전선 피복층용 절연재를 제조방법을 단계적으로 설 명하면 다음과 같다.The method of manufacturing an insulation material for an electric wire coating layer using the compositions according to Examples 1 to 5 (see Table 1) and Comparative Examples 1 to 5 (see Table 2) according to the following table will be described as follows.
상기 실시예 1 내지 5에 따른 조성물과 비교예 1 내지 5에 따른 조성물을 각각 준비한다(S1 단계). 상기 준비된 조성물을 120L의 니더기(Kneader)에 투입하여 15분 동안(15 내지 20분이면 바람직함) 혼련시킨다(S2 단계). 상기 혼련된 조성물을 75㎜ 단축 압출기(Single Screw Extruder)를 이용하여 150℃(130 내지 180℃이면 바람직함)의 압출온도 조건하에서 절연재를 압출시킨다(S3 단계). 상기 압출된 난연재에 8Mrad(5 내지 10Mrad이면 바람직함)의 전자빔을 조사하여 가교시킨다(S4 단계).Prepare the composition according to Examples 1 to 5 and the composition according to Comparative Examples 1 to 5, respectively (step S1). The prepared composition is added to a 120 L kneader and kneaded for 15 minutes (preferably 15 to 20 minutes) (step S2). The kneaded composition is extruded under an extrusion temperature of 150 ° C. (preferably 130 to 180 ° C.) using a 75 mm single screw extruder (step S3). The extruded flame retardant is irradiated with 8Mrad (preferably 5-10Mrad) electron beam and crosslinked (step S4).
물성측정 및 평가Property measurement and evaluation
한편, 하기 표 1에서는 실시예 1 내지 5에 나타낸 조성에 따른 수지조성물을 이용하여 제조된 절연재료에 대한 기계적 물성인 인장강도와 신장율을 측정하고, 내열성 평가를 위해 노화인장잔율 및 노화신장잔율을 측정하였으며, 난연성 평가를 위해 산소지수를 측정하였으며, 내한성 평가를 위해 -30℃의 저온에서 내한타격시험을 진행하였으며, 그 결과를 하기 표 1에 나타내었다. 상기 인장강도 및 신장율은 두께 1㎜의 프레스 시트로부터 IEC 60811-1-1에 의한 덤벨형 시험편을 제작하고, 250㎚/min의 속도로 진행하면서 측정하였다. 상기 내열성 평가와 관련된 노화인장잔율 및 노화신장잔율은 100℃의 공기 조건에서 7일간 노화시킨 후, 인장강도 및 신장율을 측정하여 잔율로 평가하였다. 상기 난연성은 두께 3㎜의 프레스 시트로부터 ASTM D2863에 의한 산소지수 측정법으로 측정하였다. 상기 내한성은 두께 2㎜의 프레스 시트로부터 ASTM D746-04의 내한타격시험법으로부터 5개의 시편 모두 에서 크랙이 발생되지 않는 경우를 합격으로 판정하였다.Meanwhile, in Table 1 below, tensile strength and elongation, which are mechanical properties, of the insulating material prepared by using the resin compositions according to the compositions shown in Examples 1 to 5 were measured, and aging tensile and residual aging elongation rates were evaluated for heat resistance evaluation. The oxygen index was measured for flame retardancy evaluation, and the cold resistance test was performed at a low temperature of -30 ° C. for evaluation of cold resistance, and the results are shown in Table 1 below. The tensile strength and the elongation rate were measured while producing a dumbbell-type test piece according to IEC 60811-1-1 from a press sheet having a thickness of 1 mm and proceeding at a speed of 250 nm / min. The aging tensile elongation and aging elongation residual rate associated with the heat resistance evaluation were evaluated by the residual strength by measuring the tensile strength and elongation after aging for 7 days under air condition of 100 ℃. The flame retardancy was measured by an oxygen index measuring method according to ASTM D2863 from a press sheet having a thickness of 3 mm. The cold resistance was determined to be a pass when no crack was generated in all five specimens from the cold-breaking test method of ASTM D746-04 from a press sheet having a thickness of 2 mm.
상기 표 1에서, EVA는 비닐아세테이트 함량이 17%인 에틸렌 비닐 아세테이트이며, LDPE 가교된 저밀도폴리에틸렌이며, 변성 PE는 말레인산 무수물이 도입된 폴리에틸렌이며, 난연제는 수산화마그네슘이고, 난연조제는 실리카계 화합물이며, 산화방지제는 힌더드 페놀계 화합물이며, 활제로는 스테아린산이다.In Table 1, EVA is ethylene vinyl acetate having a vinyl acetate content of 17%, LDPE crosslinked low density polyethylene, modified PE is polyethylene introduced with maleic anhydride, flame retardant is magnesium hydroxide, flame retardant aid is a silica-based compound The antioxidant is a hindered phenol compound, and the lubricant is stearic acid.
상기 표 1에 나타낸 바와 같은 각 실시예들에서의 물성 평가항목과 동일한 평가항목에 관하여 비교예 1 내지 5에 대해서도 동일한 방법으로 진행하였으며, 그 결과를 하기 표 2에 나타내었다.About the same evaluation item as the physical property evaluation item in each embodiment as shown in Table 1, and proceeded in the same manner for Comparative Examples 1 to 5, the results are shown in Table 2 below.
상기 표 2에서, EVA-1은 비닐아세테이트 함량이 17%인 에틸렌 비닐 아세테이트이며, EVA-2는 비닐아세테이트 함량이 33%인 에틸렌 비닐 아세테이트이며, LDPE는 가교된 저밀도 폴리에틸렌이며, 변성 PE는 말레인산 무수물이 도입된 폴리에틸렌이며, 난연제는 수산화마그네슘이며, 난연조제는 실리카계 화합물이며, 산화방지제는 티오화합물이고, 활제는 스테아린산이다.In Table 2, EVA-1 is ethylene vinyl acetate having a vinyl acetate content of 17%, EVA-2 is ethylene vinyl acetate having a vinyl acetate content of 33%, LDPE is a crosslinked low density polyethylene, and modified PE is maleic anhydride. This polyethylene is introduced, the flame retardant is magnesium hydroxide, the flame retardant aid is a silica-based compound, the antioxidant is a thio compound, and the lubricant is stearic acid.
상기 표 1 및 2에 따른 실시예들과 비교예들의 물성 비교를 통해 확인할 수 있는 바와 같이, 본 발명에 따른 실시예에서 각종 기계적 특성, 내열성, 난연성 및 내한성에 보다 우수한 결과가 나타났음을 확인할 수 있다.As can be confirmed by comparing the physical properties of the Examples and Comparative Examples according to the Tables 1 and 2, it can be confirmed that the results according to the embodiment according to the present invention showed better results in various mechanical properties, heat resistance, flame resistance and cold resistance. .
이상에서 설명된 본 발명의 최적 실시예들이 개시되었다. 여기서 특정한 용어들이 사용되었으나, 이는 단지 당업자에게 본 발명을 상세히 설명하기 위한 목적에서 사용된 것이지 의미한정이나 특허청구범위에 기재된 본 발명의 범위를 제한하기 위해 사용된 것이 아니다.Optimal embodiments of the present invention described above have been disclosed. Although specific terms have been used herein, they are used only for the purpose of describing the present invention in detail to those skilled in the art and are not intended to limit the scope of the present invention as defined in the claims or the claims.
본 발명에 따르면, 사용된 조성물 성분 내에 할로겐 원소가 포함되어 있지 않아 연소시 종래의 할로겐계 제품에 비해 친환경적이라 할 수 있으며, 난연성, 가공유연성, 기계적 특성이 요구되는 조건을 충분하게 만족시킴은 물론, 저온 지역이나 선박 등에 사용되는 전선(cable)용 절연피복층에 요구되는 내한성까지 충분하게 확보됨으로 인해, 저온에서 절연재가 깨짐으로써 발생되는 제품이나 설비의 고장, 불량 등을 방지할 수 있으므로, 전선용 절연피복층과 같은 절연재가 사용되는 장소의 기후나, 온도 조건에 최적화된 물성을 구비한 절연제품을 생산할 수 있어 바람직하다.According to the present invention, since it does not contain a halogen element in the composition composition used, it can be said to be environmentally friendly compared to the conventional halogen-based products when burning, satisfies the requirements that the flame retardancy, process flexibility, mechanical properties are required as well as By securing sufficient cold resistance required for the insulation coating layer for cables used in low-temperature areas or ships, it is possible to prevent breakdowns or defects in products or facilities caused by breakdown of insulation materials at low temperatures. It is preferable to produce an insulation product having properties optimized for the climate and temperature conditions where an insulation material such as an insulation coating layer is used.
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| KR100947169B1 (en) * | 2008-03-28 | 2010-03-12 | 엘에스전선 주식회사 | Composition for manufacturing non-halogen flame retardant and insulated wire manufactured using the same |
| CN101792544A (en) * | 2010-03-30 | 2010-08-04 | 上海工程技术大学 | Environment-friendly flame retardant rubber material and preparation method thereof |
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| US9085678B2 (en) | 2010-01-08 | 2015-07-21 | King Abdulaziz City For Science And Technology | Clean flame retardant compositions with carbon nano tube for enhancing mechanical properties for insulation of wire and cable |
| KR101237741B1 (en) * | 2010-06-30 | 2013-02-26 | 주식회사 투에이취켐 | Highly flowalbe and flame-retardant modified polyethylene resin composition for metal coating, modified polyethylene powder for metal coating, and mehtod of manufacturing the same |
| US8871019B2 (en) | 2011-11-01 | 2014-10-28 | King Abdulaziz City Science And Technology | Composition for construction materials manufacturing and the method of its production |
| CN102888048B (en) * | 2012-10-18 | 2014-01-01 | 苏州希普拉斯新材料有限公司 | Low-smoke halogen-free and flame-retardant cable sheath material based on glass transition mechanism |
| CN117567807A (en) * | 2023-11-27 | 2024-02-20 | 宝胜科技创新股份有限公司 | An ultra-low smoke density cold-resistant halogen-free flame-retardant cable material and its preparation method |
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| JP2004010811A (en) | 2002-06-10 | 2004-01-15 | Sumitomo Electric Ind Ltd | Flame retardant resin composition and insulated wire using the same |
| KR20040098415A (en) * | 2003-05-15 | 2004-11-20 | 엘지전선 주식회사 | Halogen free burning resist composition and automotive wire using thereit |
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| JPH08138451A (en) * | 1994-11-04 | 1996-05-31 | Fujikura Ltd | Insulated electric wire |
| JP2004010811A (en) | 2002-06-10 | 2004-01-15 | Sumitomo Electric Ind Ltd | Flame retardant resin composition and insulated wire using the same |
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| KR100947169B1 (en) * | 2008-03-28 | 2010-03-12 | 엘에스전선 주식회사 | Composition for manufacturing non-halogen flame retardant and insulated wire manufactured using the same |
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