KR101420017B1 - Polyethylene Resine Composition for Plastic Closure and Article Produced with the Same - Google Patents

Polyethylene Resine Composition for Plastic Closure and Article Produced with the Same Download PDF

Info

Publication number
KR101420017B1
KR101420017B1 KR1020120127755A KR20120127755A KR101420017B1 KR 101420017 B1 KR101420017 B1 KR 101420017B1 KR 1020120127755 A KR1020120127755 A KR 1020120127755A KR 20120127755 A KR20120127755 A KR 20120127755A KR 101420017 B1 KR101420017 B1 KR 101420017B1
Authority
KR
South Korea
Prior art keywords
resin composition
polyethylene resin
bottle cap
polyethylene
melt flow
Prior art date
Application number
KR1020120127755A
Other languages
Korean (ko)
Other versions
KR20140060871A (en
Inventor
김동진
Original Assignee
삼성토탈 주식회사
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
Application filed by 삼성토탈 주식회사 filed Critical 삼성토탈 주식회사
Priority to KR1020120127755A priority Critical patent/KR101420017B1/en
Publication of KR20140060871A publication Critical patent/KR20140060871A/en
Application granted granted Critical
Publication of KR101420017B1 publication Critical patent/KR101420017B1/en

Links

Classifications

    • 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
    • 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
    • B65D41/00—Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Abstract

본 발명은 용융흐름지수가 2.16kg의 하중으로 190℃에서 측정했을 때 200g/10분 이상의 에틸렌 단독 중합체(A) 및 에틸렌과 탄소수가 3~20인 α-올레핀의 공중합체(B)를 포함하고, 밀도가 0.965g/cm3 이상이며, 상기 (A)의 비율이 50wt% 이상인 것을 특징으로 하는 병뚜껑용 폴리에틸렌 수지 조성물 및 이로부터 제조된 성형품을 제공한다.
본 발명의 폴리에틸렌 수지 조성물로 제조된 성형품은 온도에 따른 열림 토크의 변화를 최소화하여 개봉성이 일정하다.The present invention includes a copolymer (B) of an ethylene homopolymer (A) having a melt flow index of 200 g / 10 min or more and ethylene and an? -Olefin having 3 to 20 carbon atoms measured at 190 ° C under a load of 2.16 kg , A density of 0.965 g / cm 3 or more, and a ratio of (A) above is 50 wt% or more, and a molded article produced from the same.
The molded article made of the polyethylene resin composition of the present invention minimizes the change of the open torque according to the temperature, and the openability is constant.

Description

플라스틱 병뚜껑용 폴리에틸렌 수지 조성물 및 이로부터 제조된 성형품{Polyethylene Resine Composition for Plastic Closure and Article Produced with the Same}TECHNICAL FIELD [0001] The present invention relates to a polyethylene resin composition for a plastic bottle cover, and a molded article produced from the same.

본 발명은 압축 및 사출 방식으로 성형하는 병뚜껑에 있어서 온도에 따른 열림토크의 변화를 최소화하여 개봉성을 일정하게 하는 플라스틱 병뚜껑용 폴리에틸렌 수지 조성물 및 이로부터 제조된 성형품에 관한 것이다.The present invention relates to a polyethylene resin composition for a plastic bottle lid and to a molded article made therefrom, in which a change in opening torque according to temperature is minimized in a bottle lid molded by a compression and injection method to make the openability constant.

최근 포장용기의 다양화와 환경 측면의 분리수거 확대로 유리병, 폴리에틸렌테레프탈레이트 등의 음료용기에 사용되는 병뚜껑 소재의 플라스틱화가 증가되고 있는 상태이다. 플라스틱 병뚜껑 소재로는 고밀도 폴리에틸렌, 폴리프로필렌 등이 주로 사용되고 있는데 이러한 소재를 기재로 한 병뚜껑은 기존의 알루미늄 소재의 병뚜껑 대비 가볍고 부식성이 없으며, 성형성이 우수할 뿐만 아니라 다양한 디자인의 성형이 가능한 장점으로 그 사용량이 늘어나고 있다. 특히, 고밀도 폴리에틸렌의 경우 폴리프로필렌 대비 유연한 특성을 지니고 있어 음료용기 내용물의 밀봉성 부여를 위해 별도의 라이너가 필요한 폴리프로필렌 소재의 병뚜껑과 달리 라이너를 사용하지 않고도 내용물의 밀봉성 유지할 수 있는 장점을 지니고 있다.In recent years, plasticization of bottle lids used in beverage containers such as glass bottles and polyethylene terephthalate has been increasing due to diversification of packaging containers and separation of environmental aspects. High density polyethylene, polypropylene, etc. are mainly used as plastic bottle lid materials. Bottle lid based on these materials is light and not corrosive compared to conventional aluminum bottle caps, and is excellent in moldability and molding of various designs. Its use is increasing as a possible advantage. Especially, in case of high-density polyethylene, it has flexibility property compared to polypropylene, so that it is possible to maintain the sealing property of the contents without using a liner unlike a polypropylene bottle cap which requires a separate liner for sealing the contents of the beverage container .

일반적인 스크루 방식의 병뚜껑에 있어서 중요한 요구물성 중의 하나는 병뚜껑 열림토크로 이는 사람이 음료를 마시기 위해 병뚜껑을 회전하여 열기까지의 힘으로서 열림토크가 과다할 경우 노약자 및 어린이가 음료를 개봉하는 것이 불가능하며, 열림토크가 너무 약할경우 내용물 보관의 문제점이 있기 때문에 통상적으로 병뚜껑 열림토크가 70∼180 N·cm의 힘이 적정한 것으로 규정하고 있다. 열림토크에 대한 규정이 이렇게 넓은 이유는 음료를 저온인 냉장고나 고온인 온장고에 보관할 수 있는데, 고분자 특성상 온도에 따른 수축율에 의해 저온에서의 열림토크는 높고, 고온에서의 열림토크가 낮은 것이 일반적인 특징이기 때문이다. 하지만 열림토크와 관련된 종래의 기술은 첨가제 또는 폴리에틸렌 이외의 성분을 혼합하여 열림토크를 낮추는 것에만 한정되어 있다. One of the most important requirements of the screw cap type bottle cap is the bottle cap opening torque, which is the force that the person rotates the bottle cap to drink, and when the open torque is excessive, the elderly person and the child open the drink And when the opening torque is too weak, there is a problem of storage of contents. Therefore, it is usually prescribed that the bottle lid opening torque is proper to 70-180 N · cm. The reason why the regulation of the opening torque is so wide is that the beverage can be stored in a low-temperature refrigerator or a high-temperature warming oven. Due to the nature of the polymer, the opening torque at low temperature is high and the opening torque at high temperature is low . However, the prior art related to the open torque is limited to lowering the open torque by mixing additives other than the additive or polyethylene.

열림토크는 유리병 또는 폴리에틸렌테레프탈레이트 등의 용기의 병구와 병뚜껑간의 마찰력이 주된 요인으로, 종래의 기술은 열림토크를 낮추기 위한 기술이며 온도에 따른 열림토크의 변화를 최소화하여 개봉성을 일정하게 한 기술은 종래에 없다.Opening torque is mainly caused by frictional force between a bottle of a glass bottle or a container such as polyethylene terephthalate and a bottle lid. The conventional technique is a technique for lowering the open torque, minimizing the change of the open torque according to the temperature, There is no conventional technology.

따라서 본 발명의 목적은 온도에 따른 열림토크의 변화를 최소화하여 개봉성을 일정하게 하는 플라스틱 병뚜껑용 폴리에틸렌 수지 조성물 및 이로부터 제조된 성형품을 제공하는 것이다.SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a polyethylene resin composition for a plastic bottle cap which keeps the openability constant by minimizing the change of the open torque according to the temperature, and a molded article produced therefrom.

상기 목적을 달성하기 위하여, 본 발명은 용융흐름지수가 2.16kg의 하중으로 190℃에서 측정했을 때 200g/10분 이상의 에틸렌 단독 중합체(A); 및 에틸렌과 탄소수가 3~20인 α-올레핀의 공중합체(B);를 포함하고, 밀도가 0.965g/cm3 이상이며, 상기 (A)의 비율이 50중량% 이상인 것을 특징으로 하는 병뚜껑용 폴리에틸렌 수지 조성물을 제공한다. In order to achieve the above object, the present invention relates to an ethylene homopolymer (A) having a melt flow index of 200 g / 10 min or more when measured at 190 DEG C under a load of 2.16 kg; And a copolymer (B) of ethylene and an? -Olefin having 3 to 20 carbon atoms and having a density of 0.965 g / cm 3 or more and a ratio of (A) of 50% There is provided a polyethylene resin composition.

본 발명은 또한 상기 폴리에틸렌 수지 조성물로 제조된 성형품을 제공한다.The present invention also provides a molded article made from the polyethylene resin composition.

본 발명에 따른 플라스틱 병뚜껑용 폴리에틸렌 수지 조성물로부터 제조된 성형품은, 0~50℃ 온도 범위 내 40℃ 온도 차이에서 열림토크의 차이가 10% 미만으로 온도에 따른 열림토크의 변화를 최소화하여 개봉성이 일정하며, 환경응력균열저항성이 우수하고 가공성이 우수하다.The molded article produced from the polyethylene resin composition for a plastic bottle cap according to the present invention has a difference in open torque of less than 10% at a temperature difference of 40 DEG C within a temperature range of 0 to 50 DEG C, minimizing a change in open- And is excellent in environmental stress cracking resistance and workability.

이하, 본 발명을 더욱 상세히 설명한다.Hereinafter, the present invention will be described in more detail.

본 발명은 용융흐름지수가 2.16kg의 하중으로 190℃에서 측정했을 때 200g/10분 이상의 에틸렌 단독 중합체(A); 및 에틸렌과 탄소수가 3~20인 α-올레핀의 공중합체(B);를 포함하고, 밀도가 0.965g/cm3 이상이며, 상기 (A)의 비율이 50wt% 이상인 것을 특징으로 하는 병뚜껑용 폴리에틸렌 수지 조성물에 관한 것이다.The present invention relates to an ethylene homopolymer (A) having a melt flow index of 200 g / 10 min or more as measured at 190 DEG C under a load of 2.16 kg; And a copolymer (B) of ethylene and an? -Olefin having 3 to 20 carbon atoms, wherein the density is 0.965 g / cm 3 or more, and the ratio of (A) is 50 wt% To a polyethylene resin composition.

상기 에틸렌 단독 중합체(A)는 용융흐름지수가 2.16kg의 하중으로 190℃에서 측정했을때 200g/10분 이상이고, 바람직하게는 300g/10분 이상이다. 상기 에틸렌 단독 중합체(A)의 2.16kg 용융흐름지수가 200g/10분 미만이면 40℃ 온도 차이에서 열림토크 차이가 20% 이상으로 개봉성이 일정하지 않은 문제점이 있을 수 있다. The ethylene homopolymer (A) has a melt flow rate of 200 g / 10 min or more, preferably 300 g / 10 min or more when measured at 190 DEG C under a load of 2.16 kg. If the 2.16 kg melt flow index of the ethylene homopolymer (A) is less than 200 g / 10 min, there is a problem that the open torque difference is not more than 20% and the openability is not constant at a temperature difference of 40 ° C.

본 발명의 폴리에틸렌 수지 조성물은 에틸렌과 탄소수가 3 내지 20, 바람직하게는 3 내지 8인 α-올레핀의 공중합체(B)을 포함한다. 공중합체(B)의 α-올레핀의 탄소수가 20을 초과하면 반응성이 저하되고 수지 생산비용이 크게 증가하는 문제점이 있을 수 있다.The polyethylene resin composition of the present invention comprises a copolymer (B) of ethylene and an? -Olefin having 3 to 20 carbon atoms, preferably 3 to 8 carbon atoms. If the? -Olefin of the copolymer (B) has more than 20 carbon atoms, the reactivity may be lowered and the resin production cost may increase.

또한 상기 에틸렌 단독 중합체(A)의 비율은 50wt% 이상, 바람직하게는 55wt% 이상이다. 상기 범위보다 낮을 경우 개봉성이 일정하지 않은 문제가 발생할 수 있다.The proportion of the ethylene homopolymer (A) is 50 wt% or more, preferably 55 wt% or more. If it is lower than the above range, there is a problem that the openability is not constant.

본 발명에 따른 폴리에틸렌 수지 조성물에 있어 밀도는 0.965g/cm3 이상인 것이 바람직하다. 상기 범위보다 낮을 경우 개봉성이 일정하지 않은 문제가 발생할 수 있다. The density of the polyethylene resin composition according to the present invention is 0.965 g / cm < 3 > Or more. If it is lower than the above range, there is a problem that the openability is not constant.

본 발명의 폴리에틸렌 수지 조성물의 용융흐름지수는 2.16kg의 하중으로 190℃에서 측정했을때 1.0~4.0g/10분, 더욱 바람직하게는 1.0~3.0g/10분이다. 1.0g/10분 미만인 경우 Spiral Flow Length가 낮아져 가공성 문제가 발생할 수 있고, 4.0g/10분을 초과할 경우, ESCR성이 나빠질 수 있다.The melt flow index of the polyethylene resin composition of the present invention is 1.0 to 4.0 g / 10 min, more preferably 1.0 to 3.0 g / 10 min when measured at 190 DEG C under a load of 2.16 kg. If it is less than 1.0 g / 10 min, the spiral flow length may be lowered to cause processability problems, and if it exceeds 4.0 g / 10 min, the ESCR property may deteriorate.

본 발명에 따른 폴리에틸렌 수지 조성물은 폴리에틸렌 수지 조성물 100중량부에 대하여 산화방지제 0.01~0.5 중량부, 바람직하게는 0.05~0.2 중량부 및 중화제 0.01~0.3 중량부, 바람직하게는 0.05~0.2 중량부를 더 포함할 수 있다. The polyethylene resin composition according to the present invention further contains 0.01 to 0.5 parts by weight, preferably 0.05 to 0.2 parts by weight, and 0.01 to 0.3 parts by weight, preferably 0.05 to 0.2 parts by weight, of an antioxidant per 100 parts by weight of the polyethylene resin composition can do.

상기 산화방지제 함량이 0.01 중량부 미만이면 보관시 변색, 가공 중 점도 변화 등의 문제가 있고, 0.5중량부를 초과하면 맛이나 냄새가 변질되는 문제가 있을 수 있다. 상기 중화제의 함량이 0.01 중량부 미만이면 가공 중 변색 및 점도변화가 생기고, 0.3중량부를 초과하면 장기보관시 색상, 강도 등의 물성 변화가 발생할 수 있다.If the content of the antioxidant is less than 0.01 parts by weight, discoloration during storage and viscosity change during processing may occur. If the content of the antioxidant is more than 0.5 parts by weight, there may be a problem that the taste and odor are deteriorated. If the content of the neutralizing agent is less than 0.01 parts by weight, discoloration and viscosity change during processing may occur. If the amount of the neutralizing agent is more than 0.3 parts by weight, changes in physical properties such as color and strength may occur.

상기 산화방지제의 대표적인 예로는 1,3,5-트리메틸-2,4,6-트리스(3,5-디-tert-부틸-4-히드록시벤질)벤젠(1,3,5-Trimethyl-2,4,6-tris(3,5-di- tert-butyl-4-hydroxybenzyl)benzene), 1,6-비스[3-(3,5-디-tert-부틸-4-하이드록시페닐)프로피온아미도]헥산(1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propion amido]hexane), 1,6-비스[3-(3,5-디-tert-부틸-4-히드록시페닐)프로피온아미도]프로판(1,6-Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamido]propane), 테트라키스[메틸렌(3,5-디-tert-부틸-4-히드록시히드로시나메이트)]메탄(tetrakis[methyl ene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]methane), 비스(2,6-디-tert-부틸-4-메틸페닐)펜타에리트리톨-디-포스파이트(Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol-di-phosphite), 비스 (2,4-디-tert-부틸페닐)펜타에리트리톨-디-포스파이트(Bis(2,4-di-tert-butylphenyl)Pentraerythritol-di-phosphite) 등을 예시할 수 있다.Representative examples of the antioxidant include 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (1,3,5- , 4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 1,6-bis [3- (3,5- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamido] hexane), 1,6-bis [3- Propylamido] propane), tetrakis [methylene (3, 5-di-tert-butyl-4-hydroxyphenyl) Butyl-4-hydroxyhydrocinnamate)] methane), bis (2,6-di-tert-butyl-4-hydroxyhydrocinnamate) di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite), bis (2,4-di- Bis (2,4-di-tert-butylphenyl) pentraerythritol-di-phosphite) and the like.

상기 중화제의 대표적인 예로는 칼슘 스테아르산, 아연 스테아르산, 마그네슘 알루미늄 하이드록시 카보네이트, 산화아연, 마그네슘 하이드록시 스테아르산 또는 이들의 혼합물 등을 포함할 수 있다.Representative examples of the neutralizing agent may include calcium stearate, zinc stearate, magnesium aluminum hydroxycarbonate, zinc oxide, magnesium hydroxystearic acid, or a mixture thereof.

본 발명의 병뚜껑용 폴리에틸렌 수지 조성물은 스파이럴 플로우 길이(Spiral Flow Length)가 70cm 이상인 것이 바람직하다. 상기 스파이럴 플로우 길이가 70cm 미만이면 병뚜껑을 성형하는데 시간이 많이 걸려 공정비용이 올라가는 문제가 있을 수 있다.The polyethylene resin composition for a bottle cap of the present invention preferably has a spiral flow length of 70 cm or more. If the spiral flow length is less than 70 cm, it takes a lot of time to form the bottle cap, which may raise the process cost.

상기 폴리에틸렌 수지 조성물은 환경응력균열저항성(ESCR)이 20시간 이상인 것이 바람직하다. 상기 환경응력균열저항성이 20시간 미만이면 병뚜껑으로 병을 밀봉 후 보관시 뚜껑이 깨져서 음료의 변질을 초래할 수 있다. The polyethylene resin composition preferably has an environmental stress cracking resistance (ESCR) of 20 hours or more. If the environmental stress cracking resistance is less than 20 hours, the lid may be broken when the bottle is sealed after being sealed with the bottle lid, resulting in deterioration of the beverage.

본 발명은 상기 폴리에틸렌 수지 조성물로 제조된 성형품을 제공한다. The present invention provides a molded article made of the polyethylene resin composition.

상기 폴리에틸렌 수지 조성물을 압축 또는 사출 성형하여 제조된 성형품은 0~50℃ 온도 범위 내 40℃ 온도 차이에서 열림토크 차이가 10% 미만으로 온도에 따른 열림토크의 변화를 최소화하여 개봉성이 일정하다.
The molded product manufactured by compression molding or injection molding of the polyethylene resin composition has an open torque difference of less than 10% at a temperature difference of 40 ° C within the temperature range of 0 to 50 ° C, and the openability is kept constant by minimizing the change of the open torque according to the temperature.

이하, 실시예를 통하여 본 발명을 상세하게 설명한다. 그러나 이들 실시예는 예시적인 목적일 뿐, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of examples. However, these embodiments are for illustrative purposes only, and the present invention is not limited thereto.

각 실시예 및 비교예에 있어서의 제반 물성의 측정법은 다음과 같다.The measurement methods of physical properties in each of the examples and comparative examples are as follows.

용융흐름지수Melt flow index

ASTM D1238에 따라서 190℃에서 2.16kg과 21.6kg 하중으로 측정하였다.Lt; RTI ID = 0.0 > 190 C < / RTI > according to ASTM D1238.

MFRRMFRR

MI21.6(21.66kg 하중, 190℃에서의 용융흐름지수)/MI2.16(2.16kg 하중, 190℃에서의 용융흐름지수)MI21.6 (21.66 kg load, melt flow index at 190 DEG C) /MI2.16 (2.16 kg load, melt flow index at 190 DEG C)

밀도density

ASTM D1505에 준하여 측정하였다.Measured according to ASTM D1505.

ESCR(ESCR ( 환경응력균열저항성Environmental Stress Crack Resistance ))

ASTM D1693에 준하여 측정하였다. 시험액으로는 Rhodia사의 Igepal 10wt% 수용액을 사용하였고, 환경 응력에 의한 균열이 발생하는 확률이 50%(이하 F50으로 기재)가 되는 시간을 계산한 값이다.Measured according to ASTM D1693. The test solution used was a 10 wt% aqueous solution of Igepal manufactured by Rhodia, and the time at which the probability of cracking due to environmental stress was 50% (hereinafter referred to as F50) was calculated.

스파이럴Spiral 플로우Flow 길이 Length

사출기는 Toyo사 SI180III-F200모델을 사용하였으며, 금형의 wall thickness는 2mm, 사출압력 1000kgf/cm2, 사출온도 235℃, 사출속도 30mm/초, 금형온도 50℃, 냉각시간 10초의 조건으로 성형하였다.Molding was performed under the conditions of mold wall thickness of 2 mm, injection pressure of 1000 kgf / cm 2, injection temperature of 235 ° C, injection speed of 30 mm / sec, mold temperature of 50 ° C, and cooling time of 10 seconds using Toyo's SI180III-F200 model.

병뚜껑 성형Bottle cap molding

병뚜껑 성형품의 제조는 28mm 규격으로 48개 캐비티를 가진 사출기를 사용하였으며, 사출온도 250℃, 사출압력 175바, 사출속도 160mm/초, 사출보압 45바의 조건으로 성형하였다.The moldings of the bottle lid were molded using an injection machine having 48 cavities of 28 mm size and molding conditions of an injection temperature of 250 ° C, an injection pressure of 175 bar, an injection speed of 160 mm / sec and an injection pressure of 45 bar.

열림토크Open Talk

성형된 병뚜껑을 48시간 상온에서 어닐링 후, 350ml의 폴리에틸렌테레프탈레이트 용기 기재의 용기에 물을 90% 채우고 18lb-in의 힘으로 병뚜껑을 잠근 후, 5, 25, 45℃의 냉장고, 항온오븐에 넣고 7일 후 토크메타를 이용해서 열림토크를 측정하였다.
After the molded bottle lid was annealed at room temperature for 48 hours, a container of 350 ml of polyethylene terephthalate container was filled with 90% of water and the bottle lid was closed with a force of 18 lb-in. Then, the container was put in a refrigerator at 5, And after 7 days, the open torque was measured using a torque meter.

실시예 1Example 1

연속 슬러리 중합법으로, 직렬에 접속한 2개의 중합조에 의한 2단 중합을 실시하였다. 이용한 코모노머는 1-부텐이다. 첫번째 중합조에는 모노머로 에틸렌만을 공급하고, 두번째 중합조에는 에틸렌과 1-부텐을 공급하여 중합하였다. Two-stage polymerization was carried out in two polymerization tanks connected in series by continuous slurry polymerization. The comonomer used is 1-butene. In the first polymerization reactor, only ethylene was fed as the monomer, and in the second polymerization reactor, ethylene and 1-butene were fed to polymerize.

첫번째 중합조에서 얻어지는 에틸렌 단독 중합체(A)의 2.16kg 하중, 190℃에서의 용융흐름지수(1단 MI)는 700g/10분, (A)의 비율(Blend ratio, B/R)은 55wt%, 두번째 중합조에서 얻어지는 에틸렌과 1-부텐의 공중합체(B)의 비율(100-B/R)은 45wt%이며, A와 B가 혼합된 수지 조성물의 용융흐름지수(MI)는 2.1, MFRR은 85, 밀도는 0.969이다. 실시예 1에서 얻어진 수지 조성물로 성형된 병뚜껑은 표 1에 기재한 것과 같이 5℃, 45℃의 열림토크의 차이가 5.8%로 매우 낮고, ESCR성 32hr로 병뚜껑용으로 장기간 보관에 적합하며 Spiral Flow Length(SFL)도 84cm로 가공성 또한 우수한 결과를 나타내었다.
The ethylene homopolymer (A) obtained in the first polymerization reactor had a load of 2.16 kg, a melt flow index (1-stage MI) at 190 ° C of 700 g / 10 min, a blend ratio (B / R) of 55% (100-B / R) of the copolymer (B) of ethylene and 1-butene obtained in the second polymerization reactor is 45 wt%, the melt flow index (MI) of the resin composition in which A and B are mixed is 2.1, MFRR Is 85, and the density is 0.969. As shown in Table 1, the bottle lid molded with the resin composition obtained in Example 1 had a very low difference in open torque at 5.degree. C. and 45.degree. C. of 5.8% and was suitable for long-term storage for bottle caps with ESCR The spiral flow length (SFL) was also 84 cm.

실시예 2Example 2

1단 MI를 300g/10분으로 변경하고 다른 조건은 실시예 1과 동일하게 중합하여 표 1과 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 5.8%로 매우 낮고, ESCR성 28hr로 병뚜껑용으로 장기관 보관에 적합하며 Spiral Flow Length(SFL)도 84cm로 가공성 또한 우수한 결과를 나타내었다.
The first stage MI was changed to 300 g / 10 min and other conditions were polymerized in the same manner as in Example 1 to obtain the results shown in Table 1. The difference of opening torque at 5 ℃ and 45 ℃ was very low as 5.8% and ESCR was 28hr. It was suitable for storage of the organ for the bottle cap and the spiral flow length (SFL) of 84cm also showed excellent processability.

실시예 3Example 3

1단 MI를 500g/10분, B/R을 60wt%으로 변경하고 다른 조건은 실시예 1과 동일하게 중합하여 표 1과 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 6.1%로 매우 낮고, ESCR성 41hr로 병뚜껑용으로 장기관 보관에 적합하며 Spiral Flow Length(SFL)도 87cm로 가공성 또한 우수한 결과를 나타내었다.
The first stage MI was changed to 500 g / 10 min and the B / R was changed to 60 wt%. The other conditions were the same as in Example 1, and the results were as shown in Table 1. The difference in opening torque between 5 ℃ and 45 ℃ was very low as 6.1% and 41hr ESCR was suitable for storage of the organ for the bottle cap and the spiral flow length (SFL) was also 87cm.

실시예 4Example 4

B/R을 50wt%으로 변경하고 다른 조건은 실시예 3과 동일하게 중합하여 표 1과 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 5.6%로 매우 낮고, ESCR성 21hr로 병뚜껑용으로 장기관 보관에 적합하며 Spiral Flow Length(SFL)도 80cm로 가공성 또한 우수한 결과를 나타내었다.
B / R was changed to 50 wt% and other conditions were polymerized in the same manner as in Example 3, and the same results as in Table 1 were obtained. The difference in opening torque between 5 ℃ and 45 ℃ was very low as 5.6% and the ESCR was 21hr. It was suitable for storing the organ for the bottle cap and the Spiral Flow Length (SFL) was also 80cm.

실시예 5Example 5

B/R을 55wt% 변경하고 최종 수지조성물의 용융흐름지수가 1.1이 되도록 중합하고 다른 조건은 실시예 3과 동일하게 중합하여 표 1과 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 7.2%로 매우 낮고, ESCR성 98hr로 병뚜껑용으로 장기관 보관에 적합하며 Spiral Flow Length(SFL)도 72cm로 가공성 또한 우수한 결과를 나타내었다.
B / R was changed to 55 wt% and polymerization was carried out so that the melt flow index of the final resin composition was 1.1. The other conditions were the same as in Example 3, and the results were as shown in Table 1. The difference in opening torque between 5 ℃ and 45 ℃ was very low at 7.2% and the ESCR 98hr was suitable for storage of the organ for the bottle cap and the spiral flow length (SFL) was also good at 72cm.

실시예 6Example 6

B/R을 55wt% 변경하고 최종 수지조성물의 용융흐름지수가 3.8이 되도록 중합하고 다른 조건은 실시예 3과 동일하게 중합하여 표 1과 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 6.8%로 매우 낮고, ESCR성 21hr로 병뚜껑용으로 장기관 보관에 적합하며 Spiral Flow Length(SFL)도 92cm로 가공성 또한 우수한 결과를 나타내었다.
B / R was changed to 55 wt% and polymerization was carried out so that the melt flow index of the final resin composition was 3.8. The other conditions were the same as in Example 3, and the results are shown in Table 1. The difference in opening torque between 5 ℃ and 45 ℃ was very low at 6.8% and ESCR was 21hr. It was suitable for storage of long - term storage for bottle cap and the spiral flow length (SFL) was 92cm.

실시예 7Example 7

B/R을 55wt% 변경하고 최종 수지조성물의 밀도가 0.965이 되도록 중합하고 다른 조건은 실시예 3과 동일하게 중합하여 표 1과 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 8.9%로 매우 낮고, ESCR성 85hr로 병뚜껑용으로 장기관 보관에 적합하며 Spiral Flow Length(SFL)도 82cm로 가공성 또한 우수한 결과를 나타내었다.
B / R was changed to 55% by weight and polymerization was carried out so that the density of the final resin composition was 0.965. The other conditions were the same as in Example 3, and the results as shown in Table 1 were obtained. The difference in opening torque between 5 ℃ and 45 ℃ was very low at 8.9% and the ESCR was 85hr. It was suitable for storage of the organ for the bottle cap and the spiral flow length (SFL) was 82cm.

실시예 8Example 8

B/R을 55wt% 변경하고 최종 수지조성물의 밀도가 0.971이 되도록 중합하고 다른 조건은 실시예 3과 동일하게 중합하여 표 1과 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 4.5%로 매우 낮고, ESCR성 21hr로 병뚜껑용으로 장기관 보관에 적합하며 Spiral Flow Length(SFL)도 83cm로 가공성 또한 우수한 결과를 나타내었다.
B / R was changed to 55 wt% and the final resin composition was polymerized to have a density of 0.971. The other conditions were the same as in Example 3, and the results were as shown in Table 1. The difference in opening torque between 5 ℃ and 45 ℃ was very low as 4.5% and ESCR was 21hr. It was suitable for storage of long - term storage for bottle cap and also showed excellent processability with Spiral Flow Length (SFL) of 83cm.

실시예 9Example 9

최종 수지조성물의 MI가 0.6이 되도록 중합하고 다른 조건은 실시예 1과 동일하게 중합하여 표 2와 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 7.6%로 우수하나 SFL이 62cm로 가공성이 떨어짐을 확인하였다.
The polymerization was carried out so that the MI of the final resin composition was 0.6, and the other conditions were the same as in Example 1, and the results as shown in Table 2 were obtained. It was confirmed that the difference in opening torque between 5 ° C and 45 ° C was excellent at 7.6%, but the workability was lowered with SFL of 62cm.

실시예 10Example 10

최종 수지조성물의 MI가 5.0이 되도록 중합하고 다른 조건은 실시예 1과 동일하게 중합하여 표 2와 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 5.9%로 우수하나 ESCR이 15hr로 떨어짐을 확인하였다.
The polymerization was carried out so that the MI of the final resin composition was 5.0, and the other conditions were the same as in Example 1, and the results as shown in Table 2 were obtained. It was confirmed that the difference of the open torque at 5 ° C and 45 ° C was excellent at 5.9% but the ESCR dropped to 15 hr.

비교예 1Comparative Example 1

1단 MI를 100g/10분으로 변경하고 다른 조건은 실시예 1과 동일하게 중합하여 표 2와 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 11.3%로 온도에 따른 개봉성이 실시예보다 나쁨을 확인하였다.
The first stage MI was changed to 100 g / 10 min and the other conditions were polymerized in the same manner as in Example 1, and the results shown in Table 2 were obtained. It was confirmed that the difference in opening torque between 5 ° C and 45 ° C was 11.3%, which is worse than that of the example.

비교예 2Comparative Example 2

B/R을 45wt%로 변경하고 다른 조건은 실시예 1과 동일하게 중합하여 표 2와 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 17.6%로 온도에 따른 개봉성이 실시예보다 나쁨을 확인하였다.
B / R was changed to 45 wt% and other conditions were polymerized in the same manner as in Example 1, and the results shown in Table 2 were obtained. It was confirmed that the difference in opening torque between 5 占 폚 and 45 占 폚 was 17.6% and that the openability according to the temperature was worse than the example.

비교예 3Comparative Example 3

최종 수지 조성물의 밀도가 0.963이 되도록 중합하고 다른 조건은 실시예 1과 동일하게 중합하여 표 2와 같은 결과를 얻었다. 5℃, 45℃의 열림토크의 차이가 24.3%로 온도에 따른 개봉성이 나쁨을 확인하였다.The polymerization was carried out so that the density of the final resin composition was 0.963, and other conditions were polymerized in the same manner as in Example 1, and the results shown in Table 2 were obtained. The difference in open torque between 5 ° C and 45 ° C was 24.3%, indicating poor openability with temperature.

Figure 112012092950877-pat00001
Figure 112012092950877-pat00001

Figure 112012092950877-pat00002
Figure 112012092950877-pat00002

Claims (7)

용융흐름지수가 2.16kg의 하중으로 190℃에서 측정했을 때 200g/10분 이상의 에틸렌 단독 중합체(A); 및 에틸렌과 탄소수가 3~20인 α-올레핀의 공중합체(B);를 포함하고, 밀도가 0.965g/cm3 이상이며, 상기 (A)의 비율이 50wt% 이상인 병뚜껑용 폴리에틸렌 수지 조성물이며,
상기 폴리에틸렌 수지 조성물로 제조된 성형품은 0~50℃ 온도 범위 내 40℃ 온도 차이에서 열림 토크(open torque) 차이가 10% 미만인 것을 특징으로 하는 병뚜껑용 폴리에틸렌 수지 조성물.An ethylene homopolymer (A) having a melt flow index of 200 g / 10 min or more when measured at 190 DEG C under a load of 2.16 kg; And a copolymer (B) of ethylene and an? -Olefin having 3 to 20 carbon atoms, wherein the density is 0.965 g / cm 3 or more and the ratio of (A) is 50 wt% or more ,
Wherein the molded article made of the polyethylene resin composition has an open torque difference of less than 10% at a temperature difference of 40 ° C within a temperature range of 0 to 50 ° C. 제1항에 있어서, 상기 폴리에틸렌 수지 조성물은 용융흐름지수가 2.16kg의 하중으로 190℃에서 측정했을 때 1.0~4.0g/10분인 것을 특징으로 하는 병뚜껑용 폴리에틸렌 수지 조성물.The polyethylene resin composition for a bottle cap according to claim 1, wherein the polyethylene resin composition has a melt flow rate of 1.0 to 4.0 g / 10 min when measured at 190 DEG C under a load of 2.16 kg. 제1항에 있어서, 폴리에틸렌 수지 조성물 100중량부에 대하여 산화방지제 0.01~0.5 중량부, 및 중화제 0.01~0.3 중량부를 더 포함하는 것을 특징으로 하는 병뚜껑용 폴리에틸렌 수지 조성물. The polyethylene resin composition for a bottle cap according to claim 1, further comprising 0.01 to 0.5 parts by weight of an antioxidant and 0.01 to 0.3 parts by weight of a neutralizing agent based on 100 parts by weight of the polyethylene resin composition. 제1항에 있어서, 상기 폴리에틸렌 수지 조성물은 스파이럴 플로우 길이(Spiral Flow Length)가 70cm 이상인 것을 특징으로 하는 병뚜껑용 폴리에틸렌 수지 조성물.The polyethylene resin composition for a bottle cap according to claim 1, wherein the polyethylene resin composition has a spiral flow length of 70 cm or more. 제1항에 있어서, 상기 폴리에틸렌 수지 조성물은 환경응력균열저항성(ESCR)이 20시간 이상인 것을 특징으로 하는 병뚜껑용 폴리에틸렌 수지 조성물.The polyethylene resin composition for a bottle cap according to claim 1, wherein the polyethylene resin composition has an environmental stress cracking resistance (ESCR) of 20 hours or more. 제1항 내지 제5항 중 어느 한 항에 기재된 폴리에틸렌 수지 조성물로 제조된 성형품. A molded article produced from the polyethylene resin composition according to any one of claims 1 to 5. 삭제delete
KR1020120127755A 2012-11-12 2012-11-12 Polyethylene Resine Composition for Plastic Closure and Article Produced with the Same KR101420017B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020120127755A KR101420017B1 (en) 2012-11-12 2012-11-12 Polyethylene Resine Composition for Plastic Closure and Article Produced with the Same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020120127755A KR101420017B1 (en) 2012-11-12 2012-11-12 Polyethylene Resine Composition for Plastic Closure and Article Produced with the Same

Publications (2)

Publication Number Publication Date
KR20140060871A KR20140060871A (en) 2014-05-21
KR101420017B1 true KR101420017B1 (en) 2014-07-15

Family

ID=50890056

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020120127755A KR101420017B1 (en) 2012-11-12 2012-11-12 Polyethylene Resine Composition for Plastic Closure and Article Produced with the Same

Country Status (1)

Country Link
KR (1) KR101420017B1 (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101625753B1 (en) * 2014-11-05 2016-05-30 한화토탈 주식회사 Polyethylene resin composition and product produced by the composition
KR101675641B1 (en) * 2014-11-07 2016-11-11 한화토탈 주식회사 Polyethylene Resin Composition for Plastic Closure and Article Produced with the Same
KR101699869B1 (en) 2014-11-27 2017-01-25 롯데케미칼 주식회사 Preparation method of food container
KR102440779B1 (en) * 2020-10-20 2022-09-06 한화토탈에너지스 주식회사 Polyethylene resin composition and product produced by the composition for beverage cap
KR102621528B1 (en) * 2020-11-18 2024-01-04 롯데케미칼 주식회사 Polyethylene resin composition with reduced deformation due to temperature change

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002060559A (en) * 2000-08-23 2002-02-26 Japan Polyolefins Co Ltd Polyethylene resin for container
KR100901632B1 (en) * 2008-04-01 2009-06-08 호남석유화학 주식회사 Polyethlene resin composition for preparing container closure
KR20100050105A (en) * 2008-11-05 2010-05-13 삼성토탈 주식회사 Polyethylene resin composition for aseptic caps and the article manufactured by using the composition
JP2011231316A (en) * 2010-04-06 2011-11-17 Japan Polyethylene Corp Polyethylene-based resin molding material for use in container cap

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002060559A (en) * 2000-08-23 2002-02-26 Japan Polyolefins Co Ltd Polyethylene resin for container
KR100901632B1 (en) * 2008-04-01 2009-06-08 호남석유화학 주식회사 Polyethlene resin composition for preparing container closure
KR20100050105A (en) * 2008-11-05 2010-05-13 삼성토탈 주식회사 Polyethylene resin composition for aseptic caps and the article manufactured by using the composition
JP2011231316A (en) * 2010-04-06 2011-11-17 Japan Polyethylene Corp Polyethylene-based resin molding material for use in container cap

Also Published As

Publication number Publication date
KR20140060871A (en) 2014-05-21

Similar Documents

Publication Publication Date Title
KR101420017B1 (en) Polyethylene Resine Composition for Plastic Closure and Article Produced with the Same
CA2629576C (en) Closures for bottles
JP5835439B2 (en) Polyethylene resin molding material for container lid
KR101517662B1 (en) Bimodal polyethylene composition for injection moulded articles
EP2451851B1 (en) Caps and closures
CA2465964C (en) Screw cap composition
WO2009077142A1 (en) Pe moulding composition for producing injection-molded screw cap closures and high-strenght screw cap closure for carbonated beverages produced therewith
CN106543547A (en) A kind of little hollow blow molding modification high-density polyethylene resin and preparation method thereof of easy processing food-grade
KR101768337B1 (en) Polyethylene Resin Composition for Plastic Closure and Article Produced with the Same
KR101625753B1 (en) Polyethylene resin composition and product produced by the composition
EP2360192A1 (en) Caps and closures
KR101675641B1 (en) Polyethylene Resin Composition for Plastic Closure and Article Produced with the Same
JP2005074711A (en) Molded product made of high density polyethylenic resin
KR102440779B1 (en) Polyethylene resin composition and product produced by the composition for beverage cap
KR100601146B1 (en) Polyethylene resin composition for plastic closure and its article
JP6167930B2 (en) Polyethylene resin molding material for container lid
KR101825613B1 (en) Method for preparing low-odor polyethylene resin composition for plastic closure and Article Produced with the Same
KR100922179B1 (en) Polyethylene Composition for Plastic Bottle Cap and the Molded Article
JP6500463B2 (en) Polyethylene cap
KR102614436B1 (en) Polyethylene resin composition for closure, method of manufacturing the same and molded article including the same
JP2023149991A (en) Polyolefin resin molding material and pet bottle cap for non-carbonic acid beverage
KR20040089205A (en) Polyethylene Resin Composition for Plastic Closure
KR20140038730A (en) Polypropylene resin composition and process for their manufacture
KR20210059910A (en) Polyethylene resin composition for closure to minimize the influence on the taste of beverages

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right
GRNT Written decision to grant
FPAY Annual fee payment

Payment date: 20180626

Year of fee payment: 5

FPAY Annual fee payment

Payment date: 20190624

Year of fee payment: 6