WO2019124817A1 - Film de résine de polyéthylène - Google Patents

Film de résine de polyéthylène Download PDF

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Publication number
WO2019124817A1
WO2019124817A1 PCT/KR2018/015192 KR2018015192W WO2019124817A1 WO 2019124817 A1 WO2019124817 A1 WO 2019124817A1 KR 2018015192 W KR2018015192 W KR 2018015192W WO 2019124817 A1 WO2019124817 A1 WO 2019124817A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyethylene resin
polyethylene
film
resin film
resins
Prior art date
Application number
PCT/KR2018/015192
Other languages
English (en)
Korean (ko)
Inventor
조솔
최이영
장창환
김세영
이승민
임슬기
이진영
이효준
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180152915A external-priority patent/KR102351569B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880013994.7A priority Critical patent/CN110325571B/zh
Priority to US16/487,715 priority patent/US11118040B2/en
Priority to EP18892677.8A priority patent/EP3581611B1/fr
Publication of WO2019124817A1 publication Critical patent/WO2019124817A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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

Definitions

  • the present invention relates to a polyethylene resin film exhibiting excellent transparency while exhibiting excellent processability and mechanical properties.
  • LLDPE linear low-density polyethylene
  • LDPE low-density polyethylene
  • LDPE low-density polyethylene
  • the addition of LDPE to LLDPE improves bubble stability and enables stable formation of a blown film by the meltblown process.
  • the method of adding LDPE to the LLDPE causes a problem of significantly lowering the mechanical properties of the conventional LLDPE even when a very small amount of LDPE is added. Also in this method, it was confirmed that as the thickness of the film becomes larger, the transparency is greatly lowered.
  • the present invention provides a process for producing 2019/124817 1 »(: 1 ⁇ 1 ⁇ 2018/015192
  • the first polyolefin resin has a MFRR (21.6 / 2.16) of 27 to 40
  • the second polyolefin resin has a resin number of 15 to 23 (21.6 / 2.16)
  • Fig. 2 is an optical microscope photograph of a polyethylene resin film of Comparative Example 3
  • Fig. 3 is an optical microscope photograph of a polyethylene resin film of Example 1.
  • the first polyethylene resin and the second polyethylene resin have a weight ratio of the first polyethylene resin to the second polyethylene resin of from 6: 4 to 8: 2, wherein the weight ratio of the first polyethylene resin to the second polyethylene resin is 21.6 / 2.16, wherein the first polyolefin resin has an MFRR (21.6 / 2.16) of 27 to 40, the second polyolefin resin has a MFRR (21.6 / 2.1 phrase is 15 to 23,
  • a polyethylene resin film exhibiting a haze of 10% or less is provided.
  • the conventional LLDPE linear low-density polyethylene
  • LLDPE linear low-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE LLDPE or the like, or a new polyethylene resin having improved bubble stability while exhibiting a better level of mechanical properties.
  • a polyethylene resin is disclosed in Laid-open Patent Publication No. 2017-0099694.
  • the first polyethylene resin obtained by the method disclosed in the above-mentioned Laid-open Patent Publication No. 2017- 0099694 and the first polyethylene resin have MFRR (21.6 / 2.16) Is polyethylene resin which exhibits improved transparency, that is, a haze of 10% or less, while maintaining the excellent mechanical properties, processability and bubble stability of the first polyethylene resin, The film was found to be available and the invention was completed.
  • first and second polyethylene resins whose MFRR (21.6 / 2.16) values are respectively different from each other in the above-described range are mixed in a predetermined weight ratio, for example, from 6: 4 to 8: 2, or from 7: : 2, and the film was formed into a film, 2019/124817 1 »(: 1 ⁇ 1 ⁇ 2018/015192
  • the first and second polyethylene resins are mixed so that a crystalline structure smaller than each of these resins is formed, (1 1 0 ⁇ 11 3 ⁇ 4 ⁇ ) existing in the resin structure of the resin Production can be suppressed, and further, it is predicted that the first and second polyethylene resins physically interact with each other.
  • the polyethylene resin film according to one embodiment can exhibit improved transparency than any previously known polyethylene resin film, and exhibits mechanical properties, workability, and foam stability equal to or higher than that of the previous film, .
  • the polyethylene resin film of one embodiment will be described in more detail for each component.
  • the first and second polyethylene resins included in the film of one embodiment may exhibit equivalent densities, number-average molecular weights, weight-average molecular weights, melt indexes, and the like. As a result, the first and second polyethylene resins can exhibit excellent compatibility with each other, and the film of one embodiment can exhibit various physical properties such as superior transparency and the like.
  • the first and second polyethylene resin has a density of 0.910 to 0.930 3 3 11 ⁇ 0, or 1, 3 to ⁇ 0.915 0.925 3, or 0.918 to 0.923 is ⁇ 3 is / 0! 13 can be seen.
  • the first and second polyethylene resin has a number average molecular weight of from 20,000 to 50,000 11 101, or 30,000 to 48,000 11 101, or 35,000 to 47,000 a, and a weight average molecular weight of from 100,000 to 160,000 ⁇ 0 1, Or 110,000 to 150,000 11101, or 113,000 to 130,000 11101.
  • the first and second polyethylene resins may have a melt index measured at 1901: under a temperature of 1901: and a load of 2.16 according to the ASTM 1) 1238 standard of 0.510 1 x 11 ⁇ 10 111 ⁇ 1 to 3, or 0.7 ⁇ 10 111 111 to have 2 ⁇ / 1 0111111, or 0.8 ⁇ 10 ⁇ 111 to 1.5 / 101 11 days.
  • the melt flow rate measured at a temperature of 230 ° C and a load of 21.61 3 ⁇ 4 ,? 11 21.6 ) was measured according to 0 1133 at a temperature of 2301 ° C and a melt 2019/124817 1 »(: 1 ⁇ 1 ⁇ 2018/015192
  • the MFRR (21.6 / 2.16) divided by the flow rate ⁇ 11 2.16 ) and the melt strength can be distinguished from each other by the ratio.
  • the first polyolefin resin may have 27 to 40, or 27 to 35, or 28 to 32
  • the second polyolefin resin may have a resin content of 11.11 (21.6 / 2.16) ) May be from 15 to 23, or from 18 to 23, or from 19 to 22.5
  • the first polyolefin resin may have a melt strength of 6011 or more, or 60 to 100111 or 80 to 9811
  • the second polyolefin resin may have a melt strength of 5011 or less, or 20 to 50111 or 30 to 4011 .
  • the compatibility of these resins can be further improved and the size of the crystal structure in the film of one embodiment is further reduced, Transparency, and more various physical properties.
  • the first and second polyethylene resins deviates from the 1111 (21.6 / 2.16) range or the like and the polyethylene resin is out of the 1111 (21.6 / 2.16) range or the like, It was confirmed that the silver exhibited poor transparency.
  • the above-mentioned first polyethylene resin can be produced and provided with the above-mentioned physical properties according to a method known in, for example, Laid-open Patent Publication No. 2017-0099694,
  • the resin satisfying the above-mentioned properties can be selected from commercially available resins with the product names such as 3, 10201, and so on.
  • the above-mentioned second polyethylene resin may be selected from resin which satisfies the above-mentioned physical properties among commonly known or commercially available LLD? E products.
  • the first and second polyethylene resins may be, for example, a copolymer of ethylene and an alpha olefin.
  • the alpha olefins may be selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-heptene, , 1-tetradecene, 1-nuclear decene, and mixtures thereof.
  • the olefin polymer may be a copolymer of ethylene and 1-nuchene.
  • the film of one embodiment may contain the first and second polyethylene resins described above in a weight ratio of, for example, 6: 4 to 8: 2, or 7: 3 to 8: 2 have. As such, the film of one embodiment has improved transparency, 2019/124817 1 »(: 1 ⁇ 1 ⁇ 2018/015192
  • the haze of the film of one embodiment may increase to deteriorate the transparency or deteriorate various physical properties such as mechanical properties.
  • the film of one embodiment can be produced as a film in a conventional melt blown process after mixing the first and second polyethylene resins in the weight ratio range described above.
  • the manufacturing method of the film is not limited thereto, and a typical film manufacturing process can be applied without any limitations, so that a further description thereof will be omitted.
  • the polyethylene resin film of one embodiment obtained by the above-described method has a haze of 10% or less, more specifically 1 to 10%, or 3 to 9%, for example, in a state of a final film having a thickness of 90 to 110 Can exhibit excellent transparency as defined by haze.
  • the first dolly ethylene resin exhibits a haze of 10 to 30% in the final film state having the same thickness
  • the second polyethylene resin exhibits a haze of more than 30% in the final film state having the same thickness
  • An embodiment of the film in which these are mixed in a predetermined weight ratio can surprisingly exhibit very low haze of less than 10% and greatly improved transparency. This is because, as described above, the first and second polyethylene resins interact with each other to reduce the size of the crystal structure and suppress the occurrence of reclamation.
  • the film may exhibit density, molecular weight, and melt index equivalent to those of the above-described first and second polyethylene resins, in addition to the transparency described above.
  • the film of one embodiment may have a density of 0.910 ⁇ / 011 3 to 0.930 ⁇ Jcgs, or 0.915 ⁇ 3 to 0.925 ⁇ 3 or 0.918 ⁇ 3 to 0.923 nd 3 days .
  • the MFRR (21.6 / 2.16) measured in the final film state of the film of one embodiment may be 23 to 27, or 25 to 26.8.
  • the film of one embodiment has a melt strength of 5 or more, or 50 to 90, 111 to 60,
  • the film of one embodiment can exhibit excellent melt processability, mechanical properties and the like, together with greatly improved transparency (low haze), and thus can be highly preferably applied to various fields / uses.
  • the functions and effects of the present invention will be described in more detail with reference to specific embodiments of the present invention. However, the scope of the present invention is not limited in any way by the present invention. Comparative Example 1: Polyethylene resin film
  • a polyethylene resin film was obtained in the same manner as in Comparative Example 1, except that I polyethylene was used as the polyethylene resin (trade name: 3 312, manufactured by LG Chemical Co., Ltd.).
  • Comparative Example 3 Polyethylene resin film
  • a polyethylene resin film was obtained in the same manner as in Comparative Example 1 except that the product name: 1 or 912 manufactured by Lotte Chemical Co., Ltd. was used as the polyethylene resin.
  • Example 1 Polyethylene resin film
  • the first polyethylene resin of Comparative Example 1 was used as the first polyethylene resin, and the polyethylene resin of Comparative Example 2 was used as the second polyethylene resin.
  • the first and second polyethylene resins were mixed in a weight ratio of 7: 3.
  • a polyethylene resin film was obtained in the same manner as in Comparative Example 1.
  • Example 2 Polyethylene resin film
  • Example 3 Polyethylene resin film
  • Comparative Example 1 The polyethylene resin of Comparative Example 1 was used as the first polyethylene resin, and the polyethylene resin of Comparative Example 2 was used as the second polyethylene resin.
  • the first and second polyethylene resins were mixed in a weight ratio of 6: 4.
  • a polyethylene resin film was obtained in the same manner as in Comparative Example 1.
  • Comparative Example 5 Polyester resin film
  • the polyethylene resin of Comparative Example 4 was further mixed in addition to the mixture of the first and second polyethylene resins obtained in Example 1 at a weight ratio of 7: 3.
  • the mixture of Example 1 and the polyethylene resin of Comparative Example 4 were mixed at a ratio of 5:
  • the polyethylene resin film was obtained in the same manner as in Comparative Example 1.
  • Comparative Example 6 Polyethylene resin film
  • the polyethylene resin of Comparative Example 1 was used as the first polyethylene resin
  • the polyethylene resin of Comparative Example 2 was used as the second polyethylene resin.
  • These first and second polyethylene resins were mixed in a weight ratio of 5: 5.
  • a polyethylene resin film was obtained in the same manner as in Comparative Example 1.
  • Mw and Mn were derived using a calibration curve formed using polystyrene standards
  • the molecular weight of the polystyrene standards 9,000 kinds were used, 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.
  • MI 2j6 and MFRR (21.6 / 2.16) Melt Index (MI 2 16) was determined according to ASTM D1238 (conditions E,
  • MFRR Melt Flow Rate Ratio
  • the melt strength was measured using Goettfert Rheotens 71.97 with a Model 3211 Instron capillary rheometer.
  • the ethylene resin film melt was discharged through a capillary die (plane die, 180 degree angle) with a ratio of length (L) to diameter (D) of 15 (L / D)
  • the sample was equilibrated at 190 ° C for 10 minutes and then the piston was moved at a rate of 1 inch / minute (2.54 cm / min)
  • the standard test temperature was 190 ° C.
  • the sample was accelerated at an acceleration of 1.2 mm / s 2 Was pulled in unison with a set of accelerating nips located below the die 100 mm.
  • the tension was recorded as a function of the pulling speed of the nip roll.
  • the melt strength was defined as the plasto force (mN) before the strand was broken. The following conditions were used for the melt strength measurement.
  • Shear rate 100 ⁇ 150 average value
  • the films of Examples 1 to 3 exhibit low haze and excellent mechanical properties (such as molecular weight) and processability (melt index, etc.) as the first and second polyethylene resins are mixed / ).
  • Comparative Example 1 prepared only with the first polyethylene resin and Comparative Example 2 made only with the second polyethylene resin, Comparative Example 2 made only with the polyethylene resin different in? 1111 value from the first and second polyethylene resins 4 were all found to exhibit poor transparency (high haze) compared with the examples.
  • Comparative Example 5 in which the composition of Example 1 and the polyethylene resin of Comparative Example 4 were further mixed and the weight ratio of the first and second polyethylene resins was 6: COMPARATIVE EXAMPLE 6 It was also confirmed that it exhibited poor transparency compared with the examples .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un film de résine polyéthylène présentant une transparence plus améliorée tout en présentant une excellente aptitude au traitement et d'excellentes propriétés mécaniques. Le film de résine de polyéthylène possède une densité de 0,910-0,930 g/cm3. Le film de résine de polyéthylène comprend une première et une deuxième résine de polyéthylène, de telle sorte que le rapport en poids de la première résine de polyéthylène et de la deuxième résine de polyéthylène est de 6:4 à 8:3, la première et la deuxième résine de polyéthylène ayant des valeurs différentes de MFRR (21,6/2,16), qui sont obtenues par division de l'indice de fluidité à chaud (MFR21,6) mesuré à une température de 230°C et sous une charge de 21,6 kg selon la norme ISO 1133 par l'indice de fluidité à chaud (MFR2,16) mesuré à une température de 230°C et sous charge de 2,16 kg selon la norme ISO 1133, la première résine de polyoléfine possédant un MFRR (21,6/2,16) de 27-40 et la deuxième résine de polyoléfine possédant un MFRR (21,6/2,16) de 15-23. Le film de résine de polyéthylène présente un voile inférieur ou égal à 10 % à une épaisseur de 90 à 110 µm.
PCT/KR2018/015192 2017-12-18 2018-12-03 Film de résine de polyéthylène WO2019124817A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201880013994.7A CN110325571B (zh) 2017-12-18 2018-12-03 聚乙烯树脂膜
US16/487,715 US11118040B2 (en) 2017-12-18 2018-12-03 Polyethylene resin film
EP18892677.8A EP3581611B1 (fr) 2017-12-18 2018-12-03 Film de résine de polyéthylène

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2017-0174514 2017-12-18
KR20170174514 2017-12-18
KR10-2018-0152915 2018-11-30
KR1020180152915A KR102351569B1 (ko) 2017-12-18 2018-11-30 폴리에틸렌 수지 필름

Publications (1)

Publication Number Publication Date
WO2019124817A1 true WO2019124817A1 (fr) 2019-06-27

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PCT/KR2018/015192 WO2019124817A1 (fr) 2017-12-18 2018-12-03 Film de résine de polyéthylène

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WO (1) WO2019124817A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014165113A (ja) * 2013-02-27 2014-09-08 Furukawa Electric Co Ltd:The 表面平滑性に優れた樹脂組成物
KR20150132398A (ko) * 2013-03-15 2015-11-25 유니베이션 테크놀로지즈, 엘엘씨 신속한 점착 발생을 갖는 하프노센 촉매화 폴리에틸렌 필름
US20170029542A1 (en) * 2012-03-05 2017-02-02 Univation Technologies, Llc Methods for making catalyst compositions and polymer products produced therefrom
KR20170041727A (ko) * 2014-07-17 2017-04-17 퀘노스 피티와이 엘티디 중합체 수지 조성물 및 상기 조성물로 형성된 물건
KR20170099694A (ko) 2016-02-24 2017-09-01 주식회사 엘지화학 올레핀 중합체 및 이의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170029542A1 (en) * 2012-03-05 2017-02-02 Univation Technologies, Llc Methods for making catalyst compositions and polymer products produced therefrom
JP2014165113A (ja) * 2013-02-27 2014-09-08 Furukawa Electric Co Ltd:The 表面平滑性に優れた樹脂組成物
KR20150132398A (ko) * 2013-03-15 2015-11-25 유니베이션 테크놀로지즈, 엘엘씨 신속한 점착 발생을 갖는 하프노센 촉매화 폴리에틸렌 필름
KR20170041727A (ko) * 2014-07-17 2017-04-17 퀘노스 피티와이 엘티디 중합체 수지 조성물 및 상기 조성물로 형성된 물건
KR20170099694A (ko) 2016-02-24 2017-09-01 주식회사 엘지화학 올레핀 중합체 및 이의 제조 방법

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3581611A4 *

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