KR20010050173A - Resin for polyethylene blow molded article and polyethylene blow molded article using the resin - Google Patents
Resin for polyethylene blow molded article and polyethylene blow molded article using the resin Download PDFInfo
- Publication number
- KR20010050173A KR20010050173A KR1020000048952A KR20000048952A KR20010050173A KR 20010050173 A KR20010050173 A KR 20010050173A KR 1020000048952 A KR1020000048952 A KR 1020000048952A KR 20000048952 A KR20000048952 A KR 20000048952A KR 20010050173 A KR20010050173 A KR 20010050173A
- Authority
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- South Korea
- Prior art keywords
- polyethylene
- blow molded
- resin
- low density
- measured
- Prior art date
Links
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 60
- -1 polyethylene Polymers 0.000 title claims abstract description 60
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 60
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 87
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 86
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims abstract description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000005977 Ethylene Substances 0.000 claims abstract description 32
- 239000004711 α-olefin Substances 0.000 claims abstract description 29
- 238000009826 distribution Methods 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 23
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002356 single layer Substances 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims abstract description 14
- 235000013305 food Nutrition 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 20
- 238000000071 blow moulding Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 description 19
- 238000010101 extrusion blow moulding Methods 0.000 description 13
- 230000006835 compression Effects 0.000 description 11
- 238000007906 compression Methods 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920001684 low density polyethylene Polymers 0.000 description 6
- 239000004702 low-density polyethylene Substances 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 235000010746 mayonnaise Nutrition 0.000 description 3
- 239000008268 mayonnaise Substances 0.000 description 3
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- WEPNJTDVIIKRIK-UHFFFAOYSA-N 2-methylhept-2-ene Chemical compound CCCCC=C(C)C WEPNJTDVIIKRIK-UHFFFAOYSA-N 0.000 description 1
- BWEKDYGHDCHWEN-UHFFFAOYSA-N 2-methylhex-2-ene Chemical compound CCCC=C(C)C BWEKDYGHDCHWEN-UHFFFAOYSA-N 0.000 description 1
- UIIMVYYDGLHIAO-UHFFFAOYSA-N 2-methylnon-2-ene Chemical compound CCCCCCC=C(C)C UIIMVYYDGLHIAO-UHFFFAOYSA-N 0.000 description 1
- PKXHXOTZMFCXSH-UHFFFAOYSA-N 3,3-dimethylbut-1-ene Chemical compound CC(C)(C)C=C PKXHXOTZMFCXSH-UHFFFAOYSA-N 0.000 description 1
- AUJLDZJNMXNESO-UHFFFAOYSA-N 3-ethylhex-3-ene Chemical compound CCC=C(CC)CC AUJLDZJNMXNESO-UHFFFAOYSA-N 0.000 description 1
- KNIRLWRQSSLZCZ-UHFFFAOYSA-N 3-ethyloct-3-ene Chemical compound CCCCC=C(CC)CC KNIRLWRQSSLZCZ-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- AAUHUDBDDBJONC-UHFFFAOYSA-N 3-methylhept-3-ene Chemical compound CCCC=C(C)CC AAUHUDBDDBJONC-UHFFFAOYSA-N 0.000 description 1
- RGTDIFHVRPXHFT-UHFFFAOYSA-N 3-methylnon-3-ene Chemical compound CCCCCC=C(C)CC RGTDIFHVRPXHFT-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- YCTDZYMMFQCTEO-UHFFFAOYSA-N 3-octene Chemical compound CCCCC=CCC YCTDZYMMFQCTEO-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- KZJIOVQKSAOPOP-UHFFFAOYSA-N 5,5-dimethylhex-1-ene Chemical compound CC(C)(C)CCC=C KZJIOVQKSAOPOP-UHFFFAOYSA-N 0.000 description 1
- BSJOLASGNWRVEH-UHFFFAOYSA-N 7,7-dimethyloct-1-ene Chemical compound CC(C)(C)CCCCC=C BSJOLASGNWRVEH-UHFFFAOYSA-N 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 244000195452 Wasabia japonica Species 0.000 description 1
- 235000000760 Wasabia japonica Nutrition 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- YKNMBTZOEVIJCM-UHFFFAOYSA-N dec-2-ene Chemical compound CCCCCCCC=CC YKNMBTZOEVIJCM-UHFFFAOYSA-N 0.000 description 1
- GVRWIAHBVAYKIZ-UHFFFAOYSA-N dec-3-ene Chemical compound CCCCCCC=CCC GVRWIAHBVAYKIZ-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- OTTZHAVKAVGASB-UHFFFAOYSA-N hept-2-ene Chemical compound CCCCC=CC OTTZHAVKAVGASB-UHFFFAOYSA-N 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 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
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
- B29C49/04—Extrusion blow-moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0207—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features
- B65D1/0215—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by material, e.g. composition, physical features multilayered
-
- 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
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
Abstract
Description
본 발명은 폴리에틸렌 블로우 성형체용 수지 및 그 수지를 사용한 폴리에틸렌 블로우 성형체에 관한 것이다. 보다 상세하게는, 본 발명은 뛰어난 낙하 내충격성과 샥스킨(sharkskin)이 없는 외관을 가져서 마요네즈용 연질 병과 같은 식품 용기로 바람직한 폴리에틸렌 블로우 성형체용 수지와 그 수지를 사용한 폴리에틸렌 블로우 성형체에 관한 것이다.The present invention relates to a resin for polyethylene blow molded articles and a polyethylene blow molded article using the resin. More specifically, the present invention relates to a resin for polyethylene blow molded articles having an excellent drop impact resistance and an appearance without sharkskin, and which is preferable for a food container such as a soft bottle for mayonnaise, and a polyethylene blow molded article using the resin.
고압 저밀도 폴리에틸렌 또는 지글러-나타 촉매의 존재 하에서 탄소수 3 이상의 α-올레핀과 에틸렌을 일단계로 공중합하여 얻은 선형 저밀도 폴리에틸렌을 사용한 병은, 마요네즈용 병과 같은 식품 용기로써 지금까지 널리 이용되어왔다.Bottles using linear low density polyethylene obtained by copolymerizing ethylene with one or more carbon atoms of α-olefins in one step in the presence of a high pressure low density polyethylene or a Ziegler-Natta catalyst have been widely used as food containers such as mayonnaise bottles.
그러나, 고압 저밀도 폴리에틸렌을 사용한 병는 낙하 내충격성이 결여되어 있으며, 한편 선형 저밀도 폴리에틸렌을 사용한 병는 샥스킨이 있어서 바람직하지 못한 외관을 나타낸다.However, bottles using high pressure low density polyethylene lack drop impact resistance, while bottles using linear low density polyethylene have hot skin and therefore have an undesirable appearance.
상기와 같은 상황에서, 본 발명자는 이러한 문제를 해결하기 위하여 깊이 연구해왔고, 그 결과, 지금까지 알려진 지글러 촉매와 같은 올레핀 중합 촉매의 존재 하에서 탄소수 3~20의 α-올레핀과 에틸렌의 2 단계 중합으로 얻은, 밀도(ASTM D 1505)가 0.930 g/㎤ 이하, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 1.6 dl/g 이상, GPC로 측정한 분자량 분포(Mw/Mn)가 4 이상인 선형 저밀도 폴리에틸렌으로부터 좋은 외관과 뛰어난 낙하 내충격성을 가진 연질 병을 형성할 수 있음을 알았다.In the above situation, the present inventors have studied in depth to solve this problem, and as a result, in the presence of an olefin polymerization catalyst such as the Ziegler catalyst so far, Linear obtained with a density (ASTM D 1505) of 0.930 g / cm 3 or less, intrinsic viscosity [η] measured in 135 ° C. decalin solvent of 1.6 dl / g or more, and molecular weight distribution (Mw / Mn) of 4 or more measured by GPC It has been found that soft bottles with good appearance and excellent drop impact resistance can be formed from low density polyethylene.
본 발명은 상술한 종래 기술에 관한 상기 문제를 해결하고, 연질 병과 같은 단층 또는 다층 용기로써 바람직하며 뛰어난 외관과 낙하 내충격성을 갖는 폴리에틸렌 블로우 성형체를 제조할 수 있는 폴리에틸렌 블로우 성형체용 수지의 제공을 목적으로 한다. 또다른 목적은 상기 수지로부터 제조된 폴리에틸렌 블로우 성형체를 제공하는 것이다.Disclosure of Invention The present invention aims to solve the above-mentioned problems related to the prior art and to provide a resin for a polyethylene blow molded body which can produce a polyethylene blow molded body which is preferable as a single-layer or multi-layer container such as a soft bottle and has excellent appearance and drop impact resistance. It is done. Another object is to provide a polyethylene blow molded body made from the resin.
본 발명에 따른 폴리에틸렌 블로우 성형체용 수지는 밀도(ASTM D 1505)가 0.930 g/㎤ 이하, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 1.6 dl/g 이상, GPC로 측정한 분자량 분포(Mw/Mn)가 4 이상인 선형 저밀도 폴리에틸렌(A)으로 된 것이다.The resin for polyethylene blow molded articles according to the present invention has a density (ASTM D 1505) of 0.930 g / cm 3 or less, an intrinsic viscosity [η] measured in a 135 ° C. decalin solvent of 1.6 dl / g or more, and a molecular weight distribution measured by GPC ( Mw / Mn) is a linear low density polyethylene (A) of 4 or more.
선형 저밀도 폴리에틸렌(A)은 올레핀 중합 촉매의 존재 하에서 탄소수 3~20의 α-올레핀과 에틸렌의 2단계 중합으로 얻은 선형 저밀도 에틸렌/α-올레핀 공중합체라도 좋고; 또는 밀도(ASTM D 1505)가 0.860~0.975 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 0.01~1.80 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 1.0~6.0인 선형 에틸렌/α-올레핀 공중합체(a) 5~95 중량%와, 밀도(ASTM D 1505)가 0.860~0.975g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η] 1.81~10.0 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 1.0~6.0인 선형 에틸렌/α-올레핀 공중합체(b) 5~95 중량%의 블랜드 물이어도 좋다.The linear low density polyethylene (A) may be a linear low density ethylene / α-olefin copolymer obtained by two-step polymerization of α-olefins having 3 to 20 carbon atoms and ethylene in the presence of an olefin polymerization catalyst; Or a molecular weight distribution (Mw / Mn) measured by GPC of 0.01-1.80 dl / g and an inherent viscosity [η] measured in a density (ASTM D 1505) of 0.860 to 0.975 g / cm 3 and 135 ° C decalin solvent. Intrinsic viscosity [η] 1.81-10.0 measured in 5-95 weight% of linear ethylene / alpha-olefin copolymer (a) which is 6.0, and density (ASTM D 1505) in 0.860-0.975g / cm <3>, 135 degreeC decalin solvent 5 to 95 weight% of blend water of linear ethylene / alpha-olefin copolymer (b) whose molecular weight distribution (Mw / Mn) measured by dl / g and GPC is 1.0-6.0 may be sufficient.
본 발명에서 사용되는 선형 저밀도 폴리에틸렌(A)은, -18℃의 분위기에서 5회 반복 낙하 시험 시, 병 내에 채워진 에틸렌 글리콜이 누수되지 않는 낙하 높이가 1.5m 이상인 단층 병(내부 용적:780㎖, 병 무게:25g)를 블로우 성형 할 수 있다.The linear low-density polyethylene (A) used in the present invention is a single-layer bottle (inner volume: 780 ml) having a drop height of 1.5 m or more in which the ethylene glycol filled in the bottle does not leak during five repeated drop tests in an atmosphere of -18 ° C. Bottle weight: 25 g) can be blow molded.
본 발명에 따른 폴리에틸렌 블로우 성형체는 상기 폴리에틸렌 블로우 성형체용 수지로 된 층을 갖는다.The polyethylene blow molded article according to the present invention has a layer made of the resin for the polyethylene blow molded article.
본 발명의 폴리에틸렌 블로우 성형체는 다층 구조를 가져도 좋다.The polyethylene blow molded article of the present invention may have a multilayer structure.
본 발명의 폴리에틸렌 블로우 성형체는 식품 용기로써 적합하게 사용된다.The polyethylene blow molded article of the present invention is suitably used as a food container.
본 발명의 폴리에틸렌 블로우 성형체는 압축 성형에 의해 제조된 두께 2mm의 압축 시트의 인장 항복 응력(ASTM D 638)이 15 MPa 이하인 선형 저밀도 폴리에틸렌(A)으로 된 층을 하나 갖고, 블로우 성형체를 구성하는 모든 층의 총 두께가 0.6mm이하인 한 부분을 가져도 좋다. 이와 같은 폴리에틸렌 블로우 성형체는 일반적으로 연질 병이라 불린다.The polyethylene blow molded body of the present invention has one layer of linear low density polyethylene (A) having a tensile yield stress (ASTM D 638) of 15 mm or less in a compressive sheet having a thickness of 2 mm prepared by compression molding, and constitutes all the blow molded bodies. It may have one part where the total thickness of the layer is 0.6 mm or less. Such polyethylene blow molded bodies are generally called soft bottles.
본 발명에 의한 폴리에틸렌 블로우 성형체용 수지와 그 수지를 사용한 폴리에틸렌 블로우 성형체를 하기에서 상세히 설명한다.The resin for polyethylene blow molded articles and the polyethylene blow molded articles using the resin will be described in detail below.
본 발명에 따른 폴리에틸렌 블로우 성형체용 수지는 본 발명의 폴리에틸렌 블로우 성형체의 제조에 사용되는 선형 저밀도 폴리에틸렌(A)으로 된다.The resin for polyethylene blow molded articles according to the present invention is a linear low density polyethylene (A) used for producing the polyethylene blow molded articles of the present invention.
본 발명의 폴리에틸렌 블로우 성형체는 각각 특정 범위의 밀도, 고유 점도, 분자량 분포(Mw/Mn)를 갖는 선형 저밀도 폴리에틸렌(A)으로 된 층을 갖는다. 블로우 성형체는 단층 구조 또는 2개 이상의 층을 갖는 다층 구조를 가져도 좋다.The polyethylene blow molded articles of the present invention each have a layer of linear low density polyethylene (A) having a specific range of density, intrinsic viscosity, and molecular weight distribution (Mw / Mn). The blow molded body may have a single layer structure or a multilayer structure having two or more layers.
선형 저밀도 폴리에틸렌(A)Linear Low Density Polyethylene (A)
본 발명에서 사용되는 선형 저밀도 폴리에틸렌(A)은 탄소수 3~20의 α-올레핀과 에틸렌의 공중합체이며, 밀도(ASTM D 1505)가 0.930 g/㎤ 이하, 통상 0.860~0.930 g/㎤, 바람직하게는 0.900~0.930 g/㎤, 더욱 바람직하게는 0.915~0.925 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 1.6 dl/g이상, 통상 1.6~10.0 dl/g, 바람직하게는 1.6~4.0 dl/g, 더욱 바람직하게는 1.8~2.5 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 4.0이상, 통상 4~20, 바람직하게는 4.5~13, 더욱 바람직하게는 5.0~10.0 이다. 상기 범위의 밀도, 고유 점도, 분자량 분포(Mw/Mn)를 갖는 선형 저밀도 폴리에틸렌(A)을 사용하면, 양호한 외관과 뛰어난 낙하 내충격성을 갖는 연질 병 등의 폴리에틸렌 블로우 성형체를 얻을 수 있다.The linear low density polyethylene (A) used in the present invention is a copolymer of α-olefin having 3 to 20 carbon atoms and ethylene, and has a density (ASTM D 1505) of 0.930 g / cm 3 or less, usually 0.860 to 0.930 g / cm 3, preferably Is 0.900 to 0.930 g / cm 3, more preferably 0.915 to 0.925 g / cm 3, intrinsic viscosity [η] measured at 135 ° C. decalin solvent is 1.6 dl / g or more, usually 1.6 to 10.0 dl / g, preferably 1.6-4.0 dl / g, More preferably, 1.8-2.5 dl / g, The molecular weight distribution (Mw / Mn) measured by GPC is 4.0 or more, Usually 4-20, Preferably 4.5-13, More preferably, 5.0 ˜10.0. By using the linear low density polyethylene (A) which has the density, intrinsic viscosity, and molecular weight distribution (Mw / Mn) of the said range, polyethylene blow molded objects, such as soft bottles which have a favorable appearance and excellent drop impact resistance, can be obtained.
분자량 분포(Mw/Mn)는 밀리포어사에서 제조한 GPC-150을 이용하여 다음 방식으로 측정한다.The molecular weight distribution (Mw / Mn) is measured in the following manner using GPC-150 manufactured by Millipore.
직경 72mm, 길이 600mm 사이즈의 칼럼을 갖는 TSK GNH HT의 분리용 칼럼으로, 칼럼 온도 140℃ 조건 하에서 산화 방지제로써 BHT 0.025 중량%, 이동상으로써 o-디클로로벤젠(Wako Junyaku kogoyo K.K로부터 구입 가능)을 사용하여, 시료 500㎕를 주입하여, 속도 1.0㎖/min으로 시료(농도: 0.1 중량%)를 이동시켰다. 검출기로는, 시차 주사열량계를 사용하였다. 표준 폴리스티렌으로, Mw〈1000 및 Mw〉4×106에 대해서는 TOSOH K.K제 폴리스티렌을 사용하였고, 1000≤Mw ≤4×106에 대해서는 Pressure Chemical Co.제 폴리스티렌을 사용하였다.Separation column for TSK GNH HT having a column diameter of 72 mm and a length of 600 mm, using BHT 0.025 wt% as an antioxidant and o-dichlorobenzene (available from Wako Junyaku kogoyo KK) as a mobile phase under a column temperature of 140 ° C. Then, 500 µl of the sample was injected to move the sample (concentration: 0.1 wt%) at a rate of 1.0 ml / min. As a detector, a differential scanning calorimeter was used. As standard polystyrene, polystyrene made of TOSOH KK was used for Mw <1000 and Mw> 4 × 10 6 , and polystyrene made of Pressure Chemical Co. was used for 1000 ≦ Mw ≦ 4 × 10 6 .
탄소수 3~20의 α-올레핀의 예로는 프로필렌, 1-부텐, 1-펜텐, 2-메틸-1-부텐, 3-메틸-1-부텐, 1-헥센, 3-메틸-1-펜텐, 4-메틸-1-펜텐, 3,3-디메틸-1-부텐, 1-헵텐, 메틸-1-헥센, 디메틸-1-펜텐, 트리메틸-1-부텐, 에틸-1-펜텐, 1-옥텐, 메틸-1-펜텐, 디메틸-1-헥센, 트리메틸-1-펜텐, 에틸-1-헥센, 메틸에틸-1-펜텐, 디에틸-1-부텐, 프로필-1-펜텐, 1-데센, 메틸-1-노넨, 디메틸-1-옥텐, 트리메틸-1-헵텐, 에틸-1-옥텐, 메틸에틸-1-헵텐, 디에틸-1-헥센, 1-도데센과 1-헥사도데센을 들 수 있다.Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, 4 -Methyl-1-pentene, 3,3-dimethyl-1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, trimethyl-1-butene, ethyl-1-pentene, 1-octene, methyl -1-pentene, dimethyl-1-hexene, trimethyl-1-pentene, ethyl-1-hexene, methylethyl-1-pentene, diethyl-1-butene, propyl-1-pentene, 1-decene, methyl-1 -Nonene, dimethyl-1-octene, trimethyl-1-heptene, ethyl-1-octene, methylethyl-1-heptene, diethyl-1-hexene, 1-dodecene and 1-hexadodecene.
이러한 α-올레핀은 단독으로 또는 2 종류 이상의 조합으로 사용할 수 있다.These alpha -olefins can be used individually or in combination of 2 or more types.
본 발명에 바람직하게 사용되는 선형 저밀도 폴리에틸렌(A)은 에틸렌/프로필렌 공중합체, 에틸렌/1-부텐 공중합체, 에틸렌/1-펜텐 공중합체, 에틸렌/1-헥센 공중합체, 에틸렌/4-메틸-1-펜텐 공중합체 또는 에틸렌/1-옥텐 공중합체이다.The linear low density polyethylene (A) which is preferably used in the present invention is ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, ethylene / 1-hexene copolymer, ethylene / 4-methyl- 1-pentene copolymer or ethylene / 1-octene copolymer.
선형 저밀도 폴리에틸렌(A)에서, 에틸렌으로부터 유도되는 구성 단위는 통상 65~99 중량%, 바람직하게는 70~98 중량%, 더욱 바람직하게는 75~96 중량%의 양으로 존재하고, 탄소수 3~20의 α-올레핀으로부터 유도되는 구성 단위는 통상 1~35 중량%, 바람직하게는 2~30 중량%, 더욱 바람직하게는 4~25 중량%의 양으로 존재한다.In the linear low density polyethylene (A), the structural unit derived from ethylene is usually present in an amount of 65 to 99% by weight, preferably 70 to 98% by weight, more preferably 75 to 96% by weight, and 3 to 20 carbon atoms. The structural unit derived from the α-olefin of is usually present in an amount of 1 to 35% by weight, preferably 2 to 30% by weight, more preferably 4 to 25% by weight.
에틸렌/α-올레핀 공중합체의 조성은, 통상 10mm 직경의 시료 튜브에서 헥사클로로부타디엔 1㎖에 에틸렌/α-올레핀 공중합체 약 200㎎을 균일하게 용해시켜 얻은 시료의13C-NMR 스펙트럼을, 측정 온도 120℃, 측정 주파수 25.05MHz, 스펙트럼 폭 1500Hz, 펄스 반복 시간 4.2 sec와 펄스 폭 6μsec의 조건 하에서, 측정함으로서 결정할 수 있다.The composition of the ethylene / α-olefin copolymer is a 13 C-NMR spectrum of a sample obtained by uniformly dissolving approximately 200 mg of the ethylene / α-olefin copolymer in 1 ml of hexachlorobutadiene in a 10 mm diameter sample tube. It can determine by measuring under the conditions of temperature 120 degreeC, measurement frequency 25.05MHz, spectrum width 1500Hz, pulse repetition time 4.2 sec, and pulse width 6 microseconds.
상기 특성을 갖는 선형 저밀도 폴리에틸렌(A)은 종래 공지의 지글러 촉매와 같은 올레핀 중합 촉매의 존재 하에서, 탄소수 3~20 α-올레핀과 에틸렌을 공중합 함으로서 제조할 수 있다.The linear low density polyethylene (A) having the above properties can be produced by copolymerizing C3-C20 alpha -olefin and ethylene in the presence of an olefin polymerization catalyst such as a conventionally known Ziegler catalyst.
선형 저밀도 폴리에틸렌(A)은 상기와 같이 얻은 2종류 이상의 에틸렌/α-올레핀을 블랜딩 함으로서 제조될 수 있다.The linear low density polyethylene (A) can be produced by blending two or more kinds of ethylene / α-olefins obtained as described above.
공중합체의 블랜딩은 압출기를 이용하여 실시 할 수 있고, 중합 반응기에서 2 단계 중합으로 2 종류 이상의 에틸렌/α-올레핀 공중합체를 연속적으로 제조함으로서 행할 수 있고, 필요에 따라 그 후 압출기에 의해 과립화하여도 좋다.Blending of the copolymer can be carried out by using an extruder, and can be carried out by continuously producing two or more kinds of ethylene / α-olefin copolymers by two-step polymerization in a polymerization reactor, and then granulated by an extruder if necessary. You may also do it.
본 발명에서 사용되는 선형 저밀도 폴리에틸렌(A)은, 예를 들면, 밀도(ASTM D 1505)가 0.860~0.975g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 0.01~1.80 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 1.0~6.0인 선형 에틸렌/α-올레핀 공중합체(a) 5~95 중량% 와,The linear low density polyethylene (A) used in the present invention has, for example, a density (ASTM D 1505) of 0.860 to 0.975 g / cm 3 and an intrinsic viscosity [η] measured in a 135 ° C decalin solvent of 0.01 to 1.80 dl /. g, 5-95 weight% of linear ethylene / alpha-olefin copolymer (a) whose molecular weight distribution (Mw / Mn) measured by GPC is 1.0-6.0,
밀도(ASTM D 1505)가 0.860~0.975g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 1.81~10.0 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 1.0~6.0인 선형 에틸렌/α-올레핀 공중합체(b)의 5~95 중량%의 블랜드물이 바람직하다.Density (ASTM D 1505) 0.860 to 0.975 g / cm 3, intrinsic viscosity [η] measured in 135 ° C decalin solvent, 1.81 to 10.0 dl / g, molecular weight distribution (Mw / Mn) measured by GPC is 1.0 to 6.0 Preference is given to 5 to 95% by weight of a blend of the phosphorus linear ethylene / α-olefin copolymer (b).
선형 에틸렌/α-올레핀 공중합체(a)는 단독으로 또는 2 종류 이상의 조합으로 사용해도 좋고, 또한 선형 에틸렌/α-올레핀 공중합체(b)는 단독으로 또는 2 종류 이상의 조합으로 사용해도 좋다.The linear ethylene / α-olefin copolymers (a) may be used alone or in combination of two or more kinds, and the linear ethylene / α-olefin copolymers (b) may be used alone or in combination of two or more kinds.
본 발명에서 사용되는 선형 저밀도 폴리에틸렌(A)은, -18℃의 분위기 하에서 5회 반복 낙하 시험 시, 용기 내에 채워진 에틸렌 글리콜이 누수되지 않는 낙하 높이가 1.5m 이상인 단층 병(내부 용적:780㎖, 병 무게; 25g)을 블로우 성형 할 수 있다. 상기 낙하 시험에서, 에틸렌 글리콜을 함유하는 병의 밑을 아래로 하여 동일한 높이에서 바닥으로 5번 반복하여 낙하하여 에틸렌 글리콜이 누수되지 않을 경우, 그 병은 낙하 시험에서 통과된다.The linear low-density polyethylene (A) used in the present invention is a single-layer bottle (inner volume: 780 ml) having a drop height of 1.5 m or more in which the ethylene glycol filled in the container does not leak in five repeated drop tests in an atmosphere of -18 ° C. Bottle weight; 25g) can be blow molded In the drop test, if the bottle containing ethylene glycol falls down from bottom to bottom five times at the same height and no ethylene glycol leaks, the bottle is passed in the drop test.
본 발명에서의 폴리에틸렌 블로우 성형체용 수지는 선형 저밀도 폴리에틸렌(A)에 부가적으로, 본 발명의 목적을 해치지 않는 범위 내에서 다양한 첨가제를 함유해도 좋다.In addition to linear low density polyethylene (A), the resin for polyethylene blow molded objects in this invention may contain various additives within the range which does not impair the objective of this invention.
첨가제의 예로는 충전제, 내후 안정제, 내열 안정제, 대전 방지제, 미끄럼 방지제, 방무제, 윤활제, 색소, 염료, 핵제, 가소제, 난연제, 염산 흡수제를 포함한다.Examples of additives include fillers, weather stabilizers, heat stabilizers, antistatic agents, antiskid agents, antifoam agents, lubricants, pigments, dyes, nucleating agents, plasticizers, flame retardants, hydrochloric acid absorbers.
폴리에틸렌 블로우 성형체Polyethylene Blow Molded Body
본 발명에 있어서 폴리에틸렌 블로우 성형체는 선형 저밀도 폴리에틸렌(A)으로 된 층을 가지며, 단층 구조 또는 다층 구조이어도 좋다. 일반적으로, 단층 구조의 블로우 성형체는 단층 용기로서 사용되고, 다층 구조 블로우 성형체는 다층 용기로서 사용된다.In the present invention, the polyethylene blow molded article has a layer made of linear low density polyethylene (A), and may be a single layer structure or a multilayer structure. Generally, a blow molded body of a single layer structure is used as a single layer container, and a multilayered blow molded body is used as a multilayer container.
본 발명의 다층 용기가, 예를 들어 3층 구조 인 경우, 용기의 내측과 외측의 표층을 선형 저밀도 폴리에틸렌(A)으로 형성하고, 이들 표층사이의 중간층은 에틸렌/비닐 알코올 공중합체와 같은 수지로 형성 할 수 있다.When the multilayer container of the present invention is, for example, a three-layer structure, the inner and outer surface layers of the container are formed of linear low density polyethylene (A), and the middle layer between these surface layers is made of a resin such as ethylene / vinyl alcohol copolymer. Can form.
본 발명의 폴리에틸렌 블로우 성형체는 공지된 블로우 성형법으로 제조된다. 다양한 블로우 성형 방법이 있으며, 그 방법은 압출 블로우 성형법, 2단계 블로우 성형법, 사출 성형법으로 넓게 나누어진다. 본 발명에서는, 압출 블로우 성형법이 특히 바람직하게 채택된다.The polyethylene blow molded article of the present invention is produced by a known blow molding method. There are various blow molding methods, which are broadly divided into extrusion blow molding, two-stage blow molding, and injection molding. In the present invention, the extrusion blow molding method is particularly preferably adopted.
실시예Example
본 발명을 아래 실시예를 참조하여 보다 구체적으로 설명한다. 그러나, 본 발명이 이들 실시예에 한정되는 것은 아니다.The present invention is described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
제조예 1Preparation Example 1
선형 저밀도 폴리에틸렌(LLDPE(1))의 제조Preparation of Linear Low Density Polyethylene (LLDPE (1))
중합반응기에서, 2종류의 폴리에틸렌(a1)과 폴리에틸렌(b1)을 용액 중합에 의해 연속적으로 제조하고, 과립화하여 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 2.1 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 5인 선형 저밀도 폴리에틸렌(LLDPE(1))을 얻었다.In the polymerization reactor, two kinds of polyethylene (a1) and polyethylene (b1) were continuously prepared by solution polymerization, granulated, and inherent in density (ASTM D 1505) measured in 0.920 g / cm 3 and 135 ° C decalin solvent. Linear low-density polyethylene (LLDPE (1)) whose molecular weight distribution (Mw / Mn) measured by 2.1 dl / g and GPC of viscosity [(eta)] was 5 was obtained.
폴리에틸렌(a1)은 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 0.5 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 2.3인 선형 에틸렌/α-올레핀 공중합체였다.Polyethylene (a1) has a density (ASTM D 1505) of 0.920 g / cm 3, intrinsic viscosity [η] measured in 135 ° C decalin solvent, 0.5 dl / g, and molecular weight distribution (Mw / Mn) measured by GPC of 2.3. It was a linear ethylene / α-olefin copolymer.
폴리에틸렌(b1)은 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 3.6 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 2.8인 선형 에틸렌/α-올레핀 공중합체였다.Polyethylene (b1) has a density (ASTM D 1505) of 0.920 g / cm 3, intrinsic viscosity [η] measured in 135 ° C. decalin solvent, 3.6 dl / g, and molecular weight distribution (Mw / Mn) measured by GPC of 2.8. It was a linear ethylene / α-olefin copolymer.
폴리에틸렌(b1)에 대한 폴리에틸렌(a1)의 중량 비((a1)/(b1))는 50/50이다.The weight ratio (a1) / (b1) of polyethylene (a1) to polyethylene (b1) is 50/50.
제조예 2Preparation Example 2
선형 저밀도 폴리에틸렌(LLDPE(2))의 제조Preparation of Linear Low Density Polyethylene (LLDPE (2))
중합반응기에서, 2 종류의 폴리에틸렌(a2)과 폴리에틸렌(b2)을 용액 중합에 의해 연속적으로 제조하고, 과립화하여 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 1.8 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 5인 선형 에틸렌/α-올레핀 공중합체(LLDPE(2))를 얻었다.In the polymerization reactor, two kinds of polyethylene (a2) and polyethylene (b2) were continuously prepared by solution polymerization, granulated, and inherent in density (ASTM D 1505) measured in 0.920 g / cm 3 and 135 ° C decalin solvent. A linear ethylene / α-olefin copolymer (LLDPE (2)) having a viscosity [η] of 1.8 dl / g and a molecular weight distribution (Mw / Mn) measured by GPC of 5 was obtained.
폴리에틸렌(a2)은 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 0.5 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 2.3인 선형 에틸렌/α-올레핀 공중합체였다.Polyethylene (a2) has a density (ASTM D 1505) of 0.920 g / cm 3, intrinsic viscosity [η] measured in 135 ° C decalin solvent, 0.5 dl / g, and molecular weight distribution (Mw / Mn) measured by GPC of 2.3 It was a linear ethylene / α-olefin copolymer.
폴리에틸렌(b2)은 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 3.1 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 2.8인 선형 에틸렌/α-올레핀 공중합체였다.Polyethylene (b2) has a density (ASTM D 1505) of 0.920 g / cm 3, intrinsic viscosity [η] measured in 135 ° C. decalin solvent, 3.1 dl / g, and molecular weight distribution (Mw / Mn) measured by GPC of 2.8. It was a linear ethylene / α-olefin copolymer.
폴리에틸렌(b2)에 대한 폴리에틸렌(a2)의 중량비((a2)/(b2))는 50/50이다.The weight ratio (a2) / (b2) of polyethylene (a2) to polyethylene (b2) is 50/50.
제조예 3Preparation Example 3
선형 저밀도 폴리에틸렌(LLDPE(3))의 제조Preparation of Linear Low Density Polyethylene (LLDPE (3))
중합반응기에서, 2 종류의 폴리에틸렌(a3)과 폴리에틸렌(b3)을 용액 중합에 의해 연속적으로 제조하고, 과립화하여 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 1.6 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 4인 선형 에틸렌/α-올레핀 공중합체(LLDPE(3))를 얻었다.In the polymerization reactor, two kinds of polyethylene (a3) and polyethylene (b3) were continuously prepared by solution polymerization, granulated, and inherent in density (ASTM D 1505) measured in 0.920 g / cm 3 and 135 ° C decalin solvent. A linear ethylene / α-olefin copolymer (LLDPE (3)) having a viscosity [η] of 1.6 dl / g and a molecular weight distribution (Mw / Mn) measured by GPC of 4 was obtained.
폴리에틸렌(a3)은 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 0.5 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 2.3인 선형 에틸렌/α-올레핀 공중합체였다.Polyethylene (a3) has a density (ASTM D 1505) of 0.920 g / cm 3, intrinsic viscosity [η] measured in 135 ° C decalin solvent, 0.5 dl / g, and molecular weight distribution (Mw / Mn) measured by GPC of 2.3 It was a linear ethylene / α-olefin copolymer.
폴리에틸렌(b3)은 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 2.7 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 2.5인 선형 에틸렌/α-올레핀 공중합체였다.Polyethylene (b3) has a density (ASTM D 1505) of 0.920 g / cm 3, intrinsic viscosity [η] measured in 135 ° C decalin solvent, 2.7 dl / g, and molecular weight distribution (Mw / Mn) measured by GPC of 2.5 It was a linear ethylene / α-olefin copolymer.
폴리에틸렌(b3)에 대한 폴리에틸렌(a3)의 중량비((a3)/(b3))는 50/50이다.The weight ratio (a3) / (b3) of polyethylene (a3) to polyethylene (b3) is 50/50.
제조예 4Preparation Example 4
선형 저밀도 폴리에틸렌(LLDPE(4))의 제조Preparation of Linear Low Density Polyethylene (LLDPE (4))
밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 1.8 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 3인 선형 저밀도 폴리에틸렌(LLDPE(4))을 용액 중합으로 제조하였다.Linear low density polyethylene (LLDPE) having a density (ASTM D 1505) of 0.920 g / cm 3, intrinsic viscosity [η] measured in a decalin solvent of 135 ° C., 1.8 dl / g and a molecular weight distribution (Mw / Mn) of 3 measured by GPC (4)) was prepared by solution polymerization.
제조예 5Preparation Example 5
선형 저밀도 폴리에틸렌(LLDPE(5)) 제조Manufacture of Linear Low Density Polyethylene (LLDPE (5))
밀도(ASTM D 1505)가 0.935 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 2.1 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 5인 선형 저밀도 폴리에틸렌(LLDPE(5))을 용액 중합으로 제조하였다.Linear low density polyethylene (LLDPE) having a density (ASTM D 1505) of 0.935 g / cm 3 and an intrinsic viscosity [η] measured in a decalin solvent of 135 ° C. of 2.1 dl / g and a molecular weight distribution (Mw / Mn) of 5 measured by GPC (5)) was prepared by solution polymerization.
실시예 1Example 1
제조예 1에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(1))을 아래 성형 조건 하에서 압출 블로우 성형기(니폰 세이코 K.K., 모델:JEB-15)를 사용하여 블로우 성형하여 내부 용적 780㎖와 중량 25g을 갖는 병(단층 블로우 성형체)을 얻었다.The linear low density polyethylene (LLDPE (1)) obtained in Preparation Example 1 was blow molded using an extrusion blow molding machine (Nippon Seiko KK, Model: JEB-15) under the following molding conditions to obtain a bottle having an internal volume of 780 ml and a weight of 25 g ( Single layer blow molded body).
블로우 성형 조건Blow molding condition
선형 저밀도 폴리에틸렌(LLDPE(1))의 수지 온도: 200℃Resin temperature of linear low density polyethylene (LLDPE (1)): 200 ° C
수지압력: 320 ㎏/㎡Resin pressure: 320 ㎏ / ㎡
수지 압출 속도: 50 ㎏/hrResin Extrusion Speed: 50 kg / hr
금형 온도: 20℃Mold temperature: 20 ℃
상기에서 얻는 용기를 아래 방법으로 반복 낙하 시험을 하였다. 그 결과는 표 1에 나타낸다.The container obtained above was subjected to the repeated drop test in the following manner. The results are shown in Table 1.
시험 방법Test Methods
내부 용적 780㎖, 중량 25g 인 단층 병을 에틸렌 글리콜로 채웠다. -18℃의 분위기에서, 상기 병의 밑이 아래로 되게 하여, 일정 높이에서 5회 반복하여 낙하시켰다. 5회 반복 낙하 시험에서, 에틸렌 글리콜의 누수가 없는 최고 낙하 높이를 측정하였고, 이 최고 낙하 높이를 상기 병의 낙하 내충격성의 지표로 하였다. 상기 병이 낙하되는 바닥은 두께 2mm 이상인 철판을 콘크리트 바닥에 수평으로 놓은 것이었다.A monolayer bottle with an internal volume of 780 ml, weight 25 g was filled with ethylene glycol. In an atmosphere of −18 ° C., the bottom of the bottle was turned down and dropped five times at a constant height. In the five repeated drop tests, the highest drop height without leakage of ethylene glycol was measured, and the highest drop height was used as an index of drop impact resistance of the bottle. The bottom of the bottle fell was a steel plate 2mm thick or more placed on the concrete floor.
또한, 선형 저밀도 폴리에틸렌(LLDPE(1))으로 ASTM D1928에 따라 2mm 두께의 압축 시트를 압축 성형하였다. 압축 시트의 인장 항복 응력을 ASTM D 638에 따라 측정하였다. 그 결과는 표 1에 나타낸다.In addition, a compression sheet of 2 mm thickness was compression molded into linear low density polyethylene (LLDPE (1)) in accordance with ASTM D1928. The tensile yield stress of the compressed sheet was measured according to ASTM D 638. The results are shown in Table 1.
상기에서 얻은 병는 샥스킨이 없었으며 외관이 좋았다.The bottle obtained above had no skin and had a good appearance.
실시예 2Example 2
제조예 1에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(1)) 대신에 제조예 2에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(2))을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 압출 블로우 성형하여, 내부 용적 780㎖와 중량 25g인 병(단층 블로우 성형체)을 얻었다.Extrusion blow molding in the same manner as in Example 1 except that the linear low density polyethylene (LLDPE (2)) obtained in Preparation Example 2 was used instead of the linear low density polyethylene (LLDPE (1)) obtained in Preparation Example 1 A bottle (single layer blow molded body) having a weight of 780 ml and 25 g was obtained.
압출 블로우 성형 조건은 아래와 같다.Extrusion blow molding conditions are as follows.
블로우 성형 조건Blow molding condition
선형 저밀도 폴리에틸렌(LLDPE(2))의 수지 온도:200℃Resin temperature of linear low density polyethylene (LLDPE (2)): 200 degrees Celsius
수지압력: 280 ㎏/㎡Resin pressure: 280 ㎏ / ㎡
수지 압출 속도: 50 ㎏/hrResin Extrusion Speed: 50 kg / hr
금형 온도: 20℃Mold temperature: 20 ℃
상기에서 얻은 병을 상술한 방법대로 반복 낙하 시험을 하였다. 그 결과는 표1에 나타낸다.The bottle obtained above was subjected to the repeated drop test in the manner described above. The results are shown in Table 1.
또한, 선형 저밀도 폴리에틸렌(LLDPE(2))으로 ASTM D1928에 따라 두께 2mm인 압축 시트를 압축 성형하였다. 압축 시트의 인장 항복 응력을 ASTM D 638에 따라 측정하였다. 그 결과는 표 1에 나타낸다.In addition, a compression sheet having a thickness of 2 mm was compression molded into linear low density polyethylene (LLDPE (2)) according to ASTM D1928. The tensile yield stress of the compressed sheet was measured according to ASTM D 638. The results are shown in Table 1.
상기에서 얻은 병은 샥스킨이 없었으며 외관이 좋았다.The bottle obtained above had no skin and had a good appearance.
실시예 3Example 3
제조예 1에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(1)) 대신에 제조예 3에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(3))을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 압출 블로우 성형하여, 내부 용적 780㎖와 중량 25g인 병(다층 블로우 성형체)을 얻었다.Extrusion blow molding in the same manner as in Example 1 except that the linear low density polyethylene (LLDPE (3)) obtained in Preparation Example 3 was used instead of the linear low density polyethylene (LLDPE (1)) obtained in Preparation Example 1 A bottle (multilayer blow molded article) having a weight of 780 ml and 25 g was obtained.
압출 블로우 성형 조건은 아래와 같다.Extrusion blow molding conditions are as follows.
블로우 성형 조건Blow molding condition
선형 저밀도 폴리에틸렌(LLDPE(3))의 수지 온도:200℃Resin temperature of linear low density polyethylene (LLDPE (3)): 200 degrees Celsius
수지압력: 250 ㎏/㎡Resin pressure: 250 ㎏ / ㎡
수지 압출 속도: 50 ㎏/hrResin Extrusion Speed: 50 kg / hr
금형 온도: 20℃Mold temperature: 20 ℃
상기에서 얻은 병을 상술한 방법으로 반복 낙하 시험을 하였다. 그 결과는 표1에 나타낸다.The bottle obtained above was subjected to the repeated drop test by the method described above. The results are shown in Table 1.
또한, 선형 저밀도 폴리에틸렌(LLDPE(3))으로 ASTM D1928에 따라 두께 2mm인 압축 시트를 압축 성형하였다. 압축 시트의 인장 항복 응력을 ASTM D 638에 따라 측정하였다. 그 결과는 표 1에 나타낸다.In addition, a compression sheet 2 mm thick in accordance with ASTM D1928 was compression molded from linear low density polyethylene (LLDPE (3)). The tensile yield stress of the compressed sheet was measured according to ASTM D 638. The results are shown in Table 1.
상기에서 얻은 병은 샥스킨이 없었으며 외관이 좋았다.The bottle obtained above had no skin and had a good appearance.
비교예 1Comparative Example 1
제조예 1에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(1)) 대신에 밀도(ASTM D 1505)가 0.920 g/㎤, 135℃ 데카린 용매 중에서 측정한 고유 점도[η]가 1.3 dl/g, GPC로 측정한 분자량 분포(Mw/Mn)가 5인 고압 저밀도 폴리에틸렌(HPLDPE)을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 압출 블로우 성형하여, 내부 용적 780㎖와 중량 25g을 갖는 병(단층 블로우 성형체)을 얻었다.Instead of the linear low density polyethylene (LLDPE (1)) obtained in Preparation Example 1, the density (ASTM D 1505) was measured at 0.920 g / cm 3 and 135 ° C decalin solvent, intrinsic viscosity [η] at 1.3 dl / g, measured by GPC. Extrusion blow molding in the same manner as in Example 1, except that one high molecular weight distribution (Mw / Mn) of 5 was used (HPLDPE), and a bottle (single layer blow molded body) having an internal volume of 780 ml and a weight of 25 g. Got.
압출 블로우 성형 조건은 아래와 같다.Extrusion blow molding conditions are as follows.
블로우 성형 조건Blow molding condition
고압 저밀도 폴리에틸렌(HPLDPE)의 수지 온도:200℃Resin temperature of high pressure low density polyethylene (HPLDPE): 200 degrees Celsius
수지압력: 300 ㎏/㎡Resin pressure: 300 ㎏ / ㎡
수지 압출 속도: 50 ㎏/hrResin Extrusion Speed: 50 kg / hr
금형 온도: 20℃Mold temperature: 20 ℃
상기에서 얻은 병을 상술한 방법으로 반복 낙하 시험을 하였다. 그 결과는 표 1에 나타낸다.The bottle obtained above was subjected to the repeated drop test by the method described above. The results are shown in Table 1.
또한, 고압 저밀도 폴리에틸렌(HPLDPE)은 ASTM D1928에 따라 2mm 두께의 압축 시트를 압축 성형하였다. 이 압축 시트의 인장 항복 응력을 ASTM D 638에 따라 측정하였다. 그 결과는 표 1에 나타낸다.In addition, high pressure low density polyethylene (HPLDPE) compression molded a 2 mm thick compressed sheet according to ASTM D1928. The tensile yield stress of this compressed sheet was measured according to ASTM D 638. The results are shown in Table 1.
상기에서 얻은 용기는 샥스킨이 없었으며 외관이 좋았다.The vessel obtained above had no skin and had a good appearance.
비교예 2Comparative Example 2
제조예 1에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(1)) 대신에 제조예 4에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(4))을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 압출 블로우 성형하여, 내부 용적 780㎖와 중량 25g을 갖는 병(단층 블로우 성형체)을 얻었다.Extrusion blow molding in the same manner as in Example 1 except that the linear low density polyethylene (LLDPE (4)) obtained in Preparation Example 4 was used instead of the linear low density polyethylene (LLDPE (1)) obtained in Preparation Example 1 A bottle (single layer blow molded body) having 780 ml and a weight of 25 g was obtained.
압출 블로우 성형 조건은 아래와 같다.Extrusion blow molding conditions are as follows.
블로우 성형 조건Blow molding condition
선형 저밀도 폴리에틸렌(LLDPE(4))의 수지 온도:210℃Resin temperature of linear low density polyethylene (LLDPE (4)): 210 degreeC
수지압력: 400 ㎏/㎡Resin pressure: 400 ㎏ / ㎡
수지 압출 속도: 50 ㎏/hrResin Extrusion Speed: 50 kg / hr
금형 온도: 20℃Mold temperature: 20 ℃
상기에서 얻은 병을 상술한 방법으로 반복 낙하 시험을 하였다. 그 결과는 표 1에 나타낸다.The bottle obtained above was subjected to the repeated drop test by the method described above. The results are shown in Table 1.
또한, 선형 저밀도 폴리에틸렌(LLDPE(4))으로 ASTM D1928에 따라 2mm 두께의 압축 시트를 압축 성형하였다. 이 압축 시트의 인장 항복 응력을 ASTM D 638에 따라 측정하였다. 그 결과는 표 1에 나타낸다.In addition, 2 mm thick compression sheets were compression molded into linear low density polyethylene (LLDPE (4)). The tensile yield stress of this compressed sheet was measured according to ASTM D 638. The results are shown in Table 1.
상기에서 얻은 병은 샥스킨이 있었다.The bottle obtained above had heatskin.
비교예 3Comparative Example 3
제조예 1에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(1)) 대신에 제조예 5에서 얻은 선형 저밀도 폴리에틸렌(LLDPE(5))을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 압출 블로우 성형하여, 내부 용적 780㎖와 중량 25g을 갖는 병(단층 블로우 성형체)을 얻었다.Extrusion blow molding in the same manner as in Example 1 except that the linear low density polyethylene (LLDPE (5)) obtained in Preparation Example 5 was used instead of the linear low density polyethylene (LLDPE (1)) obtained in Preparation Example 1 A bottle (single layer blow molded body) having 780 ml and a weight of 25 g was obtained.
압출 블로우 성형 조건은 아래와 같다.Extrusion blow molding conditions are as follows.
블로우 성형 조건Blow molding condition
선형 저밀도 폴리에틸렌(LLDPE(5))의 수지 온도:210℃Resin temperature of linear low density polyethylene (LLDPE (5)): 210 degreeC
수지압력: 400 ㎏/㎡Resin pressure: 400 ㎏ / ㎡
수지 압출 속도: 50 ㎏/hrResin Extrusion Speed: 50 kg / hr
금형 온도: 20℃Mold temperature: 20 ℃
상기에서 얻은 병을 상술한 방법으로 반복 낙하 시험을 하였다. 그 결과는 표 1에 나타낸다.The bottle obtained above was subjected to the repeated drop test by the method described above. The results are shown in Table 1.
또한, 선형 저밀도 폴리에틸렌(LLDPE(5))으로 ASTM D1928에 따라 2mm 두께의 압축 시트를 압축 성형하였다. 이 압축 시트의 인장 항복 응력을 ASTM D 638에 다라 측정하였다. 그 결과는 표 1에 나타낸다.In addition, 2 mm thick compression sheets were compression molded into linear low density polyethylene (LLDPE (5)). The tensile yield stress of this compressed sheet was measured according to ASTM D 638. The results are shown in Table 1.
상기에서 얻은 용기는 샥스킨이 없었으며 외관이 좋았다.The vessel obtained above had no skin and had a good appearance.
본 발명의 폴리에틸렌 블로우 성형체용 수지에 의하면, 샥스킨이 없어 외관이 양호하고 뛰어난 낙하 내충격성을 갖는 단층 또는 다층 구조의 폴리에틸렌 블로우 성형체(예, 연질 병)가 제공될 수 있다.According to the resin for polyethylene blow molded articles of the present invention, a polyethylene blow molded article (eg, soft bottle) having a single skin or a multilayer structure having no heat skin and having a good appearance and excellent drop impact resistance can be provided.
본 발명의 폴리에틸렌 블로우 성형체는 본 발명의 상기 수지로 된 층을 갖기 때문에 샥스킨이 없어 외관이 좋고, 뛰어난 낙하 내충격성을 갖는다.Since the polyethylene blow molded article of the present invention has the layer of the above-mentioned resin of the present invention, there is no heat skin and the appearance is good, and it has excellent drop impact resistance.
따라서, 본 발명의 폴리에틸렌 블로우 성형체는 마요네즈, 케찹, 와사비 페이스트 또는 머스타드 페이스트와 같은 식품의 용기로 적합하게 사용할 수 있다.Therefore, the polyethylene blow molded article of the present invention can be suitably used as a container for food, such as mayonnaise, ketchup, wasabi paste or mustard paste.
Claims (7)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP99-247323 | 1999-09-01 | ||
| JP24732399 | 1999-09-01 | ||
| JP2000-234146 | 2000-08-02 | ||
| JP2000234146A JP4430799B2 (en) | 1999-09-01 | 2000-08-02 | Polyethylene hollow molded body resin and polyethylene hollow molded body using the resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20010050173A true KR20010050173A (en) | 2001-06-15 |
| KR100610171B1 KR100610171B1 (en) | 2006-08-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020000048952A KR100610171B1 (en) | 1999-09-01 | 2000-08-23 | Resin for polyethylene blow molded article and polyethylene blow molded article using the resin |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4430799B2 (en) |
| KR (1) | KR100610171B1 (en) |
| CN (1) | CN1300233C (en) |
| ID (1) | ID29316A (en) |
| TW (1) | TW553952B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BR112012028877A2 (en) * | 2010-05-13 | 2016-07-26 | Unilever Nv | pipe and process for manufacturing a pipe |
| CN106633325B (en) * | 2015-10-28 | 2019-04-16 | 中国石油化工股份有限公司 | A kind of polyethylene composition and durable membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6016880A (en) * | 1983-07-08 | 1985-01-28 | 今野 富夫 | Manufacture of heat insulating concrete board |
| JPH07116251B2 (en) * | 1985-03-11 | 1995-12-13 | 東ソー株式会社 | Method for producing modified polyethylene |
| JP3355534B2 (en) * | 1992-09-10 | 2002-12-09 | 住友化学工業株式会社 | Ethylene-α-olefin copolymer and molded article molded using the copolymer |
| JPH1180259A (en) * | 1997-09-10 | 1999-03-26 | Tosoh Corp | Polyethylene resin for large blow-molded product, its production and large blow-molded container |
-
2000
- 2000-08-02 JP JP2000234146A patent/JP4430799B2/en not_active Expired - Lifetime
- 2000-08-23 KR KR1020000048952A patent/KR100610171B1/en not_active IP Right Cessation
- 2000-08-31 TW TW089117751A patent/TW553952B/en not_active IP Right Cessation
- 2000-08-31 ID IDP20000736D patent/ID29316A/en unknown
- 2000-09-01 CN CNB001264907A patent/CN1300233C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1288910A (en) | 2001-03-28 |
| JP4430799B2 (en) | 2010-03-10 |
| CN1300233C (en) | 2007-02-14 |
| KR100610171B1 (en) | 2006-08-09 |
| TW553952B (en) | 2003-09-21 |
| ID29316A (en) | 2001-08-16 |
| JP2001139630A (en) | 2001-05-22 |
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