WO2023234433A1 - Flexible thin film composition for packaging using linear low-density polyethylene containing biomass, and method for preparing same - Google Patents

Flexible thin film composition for packaging using linear low-density polyethylene containing biomass, and method for preparing same Download PDF

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Publication number
WO2023234433A1
WO2023234433A1 PCT/KR2022/007690 KR2022007690W WO2023234433A1 WO 2023234433 A1 WO2023234433 A1 WO 2023234433A1 KR 2022007690 W KR2022007690 W KR 2022007690W WO 2023234433 A1 WO2023234433 A1 WO 2023234433A1
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density polyethylene
linear low
packaging
thin film
flexible thin
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PCT/KR2022/007690
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French (fr)
Korean (ko)
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오수경
김은희
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(주)화진산업
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Priority to PCT/KR2022/007690 priority Critical patent/WO2023234433A1/en
Publication of WO2023234433A1 publication Critical patent/WO2023234433A1/en

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    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins

Definitions

  • the present invention is a result of research conducted under the Regional Specialized Industry Development (R&D) Regional Main Industry Promotion (S3085395) supported by the Ministry of SMEs and Startups, and is a flexible thin film composition for packaging using linear low-density polyethylene containing biomass and a method for manufacturing the same. It's about. More specifically, the present invention is environmentally friendly because polyethylene resin containing biomass derived from corn, potatoes, and sugar cane is used to reduce the amount of synthetic resin used, and it is a bio-based film that exhibits physical properties comparable to those of films made of synthetic resin. It relates to a flexible thin film composition for packaging using mass-containing linear low-density polyethylene and a method for manufacturing the same.
  • R&D Regional Specialized Industry Development
  • S3085395 Regional Main Industry Promotion
  • the purpose of the present invention is to reduce the amount of synthetic resin used by using polyethylene resin containing biomass derived from corn, potatoes, and sugar cane, which is environmentally friendly, and biomass that exhibits physical properties equivalent to films made from synthetic resin.
  • the present invention provides a flexible thin film composition for packaging using linear low-density polyethylene and a method for manufacturing the same.
  • the object of the present invention is to provide a flexible thin film composition for packaging using linear low-density polyethylene containing biomass, characterized in that it consists of linear low-density polyethylene containing biomass, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene. is achieved by
  • the flexible thin film composition for packaging using the biomass-containing linear low-density polyethylene includes 20 to 40% by weight of biomass-containing linear low-density polyethylene, 45 to 78% by weight of linear low-density polyethylene, and propylene-based. It should be composed of 0.5 to 14.5% by weight of elastomer and 0.5 to 1.5% by weight of polyisobutylene.
  • the biomass-containing linear low-density polyethylene has a density of 0.9 to 0.93 g/cm 2 and a melt index of 0.8 to 1.2 g/10 min.
  • the object of the present invention is a melt-kneading step of putting biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene into an extruder and melting and kneading them, and melting and kneading them through the melt-kneading step.
  • a flexible thin film for packaging using linear low-density polyethylene containing biomass characterized in that it consists of an extrusion molding step of extruding the mixture into a film form by extruding it and a cooling step of cooling the molded product extruded through the extrusion molding step. It can also be achieved by providing a method for producing a film composition.
  • the melt kneading step includes 20 to 40% by weight of biomass-containing linear low-density polyethylene, 45 to 78% by weight of linear low-density polyethylene, 0.5 to 14.5% by weight of propylene-based elastomer, and 0.5% by weight of polyisobutylene. It is assumed that 1.5% by weight is added to the extruder.
  • the mixture melted and kneaded through the melt kneading step is extruded through a T-die heated to a temperature of 180 to 250 ° C. to form a film having a thickness of 10 to 150 ⁇ m. It shall be made by molding.
  • the cooling step is performed by passing the molded product extruded through the extrusion molding step through a cooling roller at a temperature of 15 to 40°C.
  • the flexible thin film composition for packaging using linear low-density polyethylene containing biomass according to the present invention and its manufacturing method can reduce the amount of synthetic resin used by using polyethylene resin containing biomass derived from corn, potatoes, and sugarcane. Therefore, it is environmentally friendly and has an excellent effect of providing a flexible thin film composition for packaging with physical properties comparable to those of films made of synthetic resin.
  • Figure 1 is a flowchart showing a method of manufacturing a flexible thin film composition for packaging using linear low-density polyethylene containing biomass according to the present invention.
  • Figures 2 to 5 are graphs showing the evaluation of mechanical properties of flexible thin films for packaging manufactured through Examples 1 to 3 and Comparative Example 1 of the present invention.
  • the flexible thin film composition for packaging using biomass-containing linear low-density polyethylene is composed of biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer and polyisobutylene, and biomass-containing linear low-density polyethylene. It is preferably composed of 20 to 40% by weight of linear low-density polyethylene, 45 to 78% by weight of linear low-density polyethylene, 0.5 to 14.5% by weight of propylene-based elastomer, and 0.5 to 1.5% by weight of polyisobutylene.
  • the biomass-containing linear low-density polyethylene contains 20 to 40% by weight, and is a resin manufactured using biomass as a raw material.
  • the biomass-derived resin is produced by extracting sugars from corn, potatoes, sugar cane, etc. and polymerizing them through alcohol fermentation. It can be manufactured.
  • the bio-linear low-density polyethylene resin may contain biomass derived from sugarcane, and has a fast biodegradation rate, so not only can it replace synthetic resins that cause problems with microplastics, but also has a density of 0.9 to 0.93 g. /cm 2 , and it is preferable to use one having a melt index of 0.8 to 1.2 g/10 min.
  • the above effect is minimal, and if the content of the linear low-density polyethylene exceeds 40% by weight, the above effect is improved, but the mechanical properties of the film produced are reduced. Not only does this decrease, but the biodegradation rate of the film also increases excessively, which is undesirable because its use as a stretch film or silage film may be limited.
  • the linear low-density polyethylene contains 45 to 78% by weight, and polymerized under a Ziegler-Nacha catalyst or a meltalocene catalyst can be used.
  • the ⁇ -olefin comonomer of the linear low density polyethylene resin polymerized under the Ziegler-Natta catalyst is preferably at least one selected from the group consisting of 1-hexene, 1-octene, 1-decene, and 1-dodecene, and more preferably It is best to use one with 6 or more carbon atoms, and most preferably 1-hexene.
  • the Ziegler-Natta catalyst is one of the catalysts for olefin polymerization. It refers to a catalyst system consisting of a combination of a main catalyst mainly composed of a transition metal compound, a cocatalyst made of an organometallic compound, and an electron donor. In the present invention, the Ziegler-Natta catalyst is known as the Ziegler-Natta catalyst. Catalysts known as catalysts may be used without limitation.
  • the ⁇ -olefin comonomer of the linear low-density polyethylene resin polymerized under the metallocene catalyst is preferably at least one selected from the group consisting of 1-hexene, 1-octene, 1-decene, and 1-dodecene, More preferably, it is one with 6 or more carbon atoms, and most preferably, 1-hexene is used.
  • the metallocene catalyst refers to a catalyst with a structure in which a metal is sandwiched between two types of cyclopentadiene, and is a catalyst with a single active site. In the present invention, catalysts known as metallocene catalysts may be used without limitation.
  • the content of the linear low-density polyethylene is less than 45% by weight, the mechanical properties of the produced film are excessively reduced, and biodegradability is excessively improved, which may limit its use as a stretch film or silage film. If it exceeds 78% by weight, the content of linear low-density polyethylene containing biomass is relatively reduced too much, making it impossible to achieve the purpose of the present invention.
  • the propylene-based elastomer contains 0.5 to 14.5% by weight and serves to improve the tensile strength or elongation of the film manufactured through the present invention.
  • the component of the propylene-based elastomer is not particularly limited, but is a propylene-ethylene copolymer. It is desirable to use .
  • any propylene-based elastomer manufactured by a previously known method or manufactured using an existing Ziegler-Natta or metallocene-based catalyst that is already commercialized can be used without any restrictions.
  • the content of the propylene-based elastomer is less than 0.5 parts by weight, the above effect is minimal, and if the content of the propylene-based elastomer exceeds 14.5 weight%, the content of linear low-density polyethylene containing biomass and linear low-density polyethylene are relatively high. If it decreases too much, the biodegradation effect or mechanical properties may be reduced.
  • the polyisobutylene contains 0.5 to 1.5% by weight and plays a role in improving the flexibility and transparency of the film. If the polyisobutylene content is less than 0.5% by weight, the effect is minimal, and the polyisobutylene If the butylene content exceeds 1.5% by weight, the mechanical properties of the film may be excessively reduced without significantly improving the above effects.
  • the method of manufacturing a flexible thin film composition for packaging using biomass-containing linear low-density polyethylene involves adding biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene to an extruder.
  • a melt-kneading step (S101) of melting and kneading an extrusion molding step (S103) of extruding the mixture melted and kneaded through the melt-kneading step (S101) with a T-die and forming it into a film form
  • the extrusion molding step (S103). ) consists of a cooling step (S105) in which the extruded molded product is cooled.
  • the melt-kneading step (S101) is a step of putting biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene into an extruder and melting and kneading them.
  • the bio linear low-density polyethylene resin is located in the middle layer of the film, the linear low-density polyethylene resin is located in the upper surface and anatomical surface of the middle layer, and the propylene-based elastomer component may be located in the inner part of the film when foaming. It is desirable for this to proceed.
  • the extrusion molding step (S103) is a step of extruding the mixture melted and kneaded through the melt and kneading step (S101) into a film form by extruding it into a film form.
  • the mixture melted and kneaded through the melt and kneading step (S101) is molded into a film. It is made by extruding with a T-die heated to a temperature of 180 to 250 °C and molding into a film having a thickness of 10 to 150 ⁇ m.
  • the thickness of the extrusion molded product in the extrusion molding step (S103) is less than 10 ⁇ m
  • the mechanical properties of the manufactured film are excessively reduced, and if the thickness of the molded product exceeds 150 ⁇ m, the mechanical properties of the manufactured film are not significantly improved, but the flexibility of the film is reduced and the weight is excessively increased, which is undesirable.
  • the by-products generated in the extrusion molding step (S103) can be recovered and then reintroduced in the melt kneading step (S101) and recycled.
  • the cooling step (S105) is a step of cooling the molded product extruded through the extrusion molding step (S103), and is achieved by passing the molded product extruded through the extrusion molding step (S103) through a cooling roller at a temperature of 15 to 40 ° C.
  • a cooling roller showing the above temperature the extruded molded product is not only cooled, but also has an even surface, thereby providing a film composition with improved marketability.
  • the kneaded resin is passed through a T-die block heated to a temperature of 200°C to form an 80 ⁇ m thick
  • the manufactured product is passed through a cooling roller (25°C) equipped with a cooling water circulation device to create a flexible thin film for packaging using linear low-density polyethylene containing biomass with a thickness of 25 ⁇ m and a size of 2200mm wide x 2200mm high. was manufactured.
  • Example 2 Proceed in the same manner as Example 1, except that 25% by weight of bio linear low-density polyethylene resin, 72% by weight of linear low-density polyethylene resin, 2% by weight of propylene-based elastomer, and 1% by weight of polyisobutylene were mixed to form a linear polyethylene containing biomass.
  • a flexible thin film for packaging was manufactured using low-density polyethylene.
  • Example 2 Proceed in the same manner as Example 1, except that 35% by weight of bio linear low-density polyethylene resin, 60% by weight of linear low-density polyethylene resin, 4% by weight of propylene-based elastomer, and 1% by weight of polyisobutylene were mixed to form a linear polyethylene containing biomass.
  • a flexible thin film for packaging was manufactured using low-density polyethylene.
  • 99% by weight of petrochemical linear low-density polyethylene resin and 1% by weight of polyisobutylene are melted and kneaded at 190°C, and the kneaded resin is passed through a T-die block heated to a temperature of 200°C to form an 80 ⁇ m thick molded product.
  • the manufactured molded product was passed through a cooling roller (25°C) equipped with a cooling water circulation device to produce a flexible thin film for packaging with a thickness of 25 ⁇ m and a width of 2200mm x a height of 2200mm.
  • Beta analytic's Biobased Testing was measured based on the ASTM D6866 standard.
  • the pMC value according to ASTM D6866 refers to the content of active bio-ingredients.
  • the flexible thin film for packaging manufactured through Examples 1 to 3 of the present invention has a high biomass content.
  • Example 1 the difference in biomass that occurs when comparing Example 1 and Example 2, which have the same content of linear low-density polyethylene containing biomass, is due to the large amount of recovered film by-product administered to the middle layer in Example 1, which is This is because the content of linear low-density polyethylene resin containing biomass is also lowered.
  • Example 2 Example 3 Comparative Example 1 tensile strength (kgf/cm2) longitudinal 451 510 555 537 transverse 353 384 352 405 elongation (%) longitudinal 511 526 610 625 transverse 757 871 906 830
  • the mechanical properties in the longitudinal direction are in the machine direction (MD).
  • MD machine direction
  • the direction in which it is placed and operated in the machine determines the quality of the product.
  • the tensile strength in the machine direction (MD) gradually increases from 451 kgf/cm3 to 555 kgf/cm3, and the elongation increases from 511% to 610%. Comparative Example 1 and Examples 2 to 2 When comparing 3, it can be seen that Examples 2 to 3 show values equivalent to or higher than Comparative Example 1.
  • Example 3 the presence of hazardous ingredients in the flexible thin film for packaging manufactured through Example 3 was evaluated for the content of regulated substances according to the European RoHS Directive by IEC 62321-4, IEC IEC62321-5, IEC 62321-6, 62321-7- 2, As a result of measurement in accordance with IEC 62321-8 by requesting SGS Korea Co., Ltd., located in Anyang-si, a Korean analysis agency, the film manufactured through Example 3 of the present invention was regulated. All hazardous substances were found to be non-detectable, and it was confirmed that it complies with the European RoHS standard.
  • the flexible thin film composition for packaging using linear low-density polyethylene containing biomass according to the present invention and its manufacturing method use polyethylene resin containing biomass derived from corn, potatoes, and sugarcane, thereby reducing the amount of synthetic resin used.
  • This provides a flexible thin film composition for packaging that is environmentally friendly and has properties comparable to those of films made of synthetic resin.

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Abstract

The present invention relates to a flexible thin film composition for packaging using linear low-density polyethylene containing biomass, and a method for preparing same. More specifically, the flexible thin film composition for packaging consists of linear low-density polyethylene containing biomass, linear low-density polyethylene, a propylene-based elastomer, and polyisobutylene, and is prepared by a melt-kneading step of introducing linear low-density polyethylene containing biomass, linear low-density polyethylene, a propylene-based elastomer, and polyisobutylene into an extruder and melting and kneading same, an extrusion molding step of extruding the mixture melted and kneaded through the melt-kneading step with a T-die to form a film, and a cooling step of cooling the molding extruded through the extrusion molding step. As the flexible thin film composition for packaging using linear low-density polyethylene containing biomass manufactured through the above processes uses a polyethylene resin containing biomass derived from corn, potato, sugarcane, and the like, the flexible thin film composition for packaging can reduce the use of a synthetic resin and thus is eco-friendly, and exhibits physical properties equivalent to films made of a synthetic resin.

Description

바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물 및 그 제조방법Flexible thin film composition for packaging using linear low-density polyethylene containing biomass and its manufacturing method
본 발명은 중소벤처기업부에서 지원하는 지역특화산업육성(R&D) 지역주력산업육성(S3085395)의 연구 수행의 결과로, 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물 및 그 제조방법에 관한 것이다. 보다 구체적으로, 본 발명은 옥수수, 감자 및 사탕수수 등에서 유래된 바이오매스가 함유된 폴리에틸렌 수지가 사용되어 합성수지의 사용량을 절감할 수 있기 때문에 친환경적이며, 합성수지로 제조된 필름과 대등한 물성을 나타내는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물 및 그 제조방법에 관한 것이다.The present invention is a result of research conducted under the Regional Specialized Industry Development (R&D) Regional Main Industry Promotion (S3085395) supported by the Ministry of SMEs and Startups, and is a flexible thin film composition for packaging using linear low-density polyethylene containing biomass and a method for manufacturing the same. It's about. More specifically, the present invention is environmentally friendly because polyethylene resin containing biomass derived from corn, potatoes, and sugar cane is used to reduce the amount of synthetic resin used, and it is a bio-based film that exhibits physical properties comparable to those of films made of synthetic resin. It relates to a flexible thin film composition for packaging using mass-containing linear low-density polyethylene and a method for manufacturing the same.
전 세계적으로 폐플라스틱과 미세플라스틱으로 인한 환경오염이 심화하여 일회용 플라스틱 제품의 사용에 대한 규제에서 나아가 생분해성 플라스틱 및 바이오매스 플라스틱 사용을 추진하고 있으나, 아직은 바이오 플라스틱에 대한 실용화가 미미한 편이다. 하지만, 최근 발표한 한국형(K)-순환경제 이행계획에 따르면 정부는 기존 석유계 플라스틱을 석유계 혼합 바이오 플라스틱으로 전환을 유도하고 있으며, 이에 따라 바이오 플라스틱의 실용화는 시급하게 추진되고 있다.As environmental pollution caused by waste plastics and microplastics is worsening worldwide, regulations on the use of disposable plastic products are being promoted and the use of biodegradable plastics and biomass plastics is being promoted. However, the practical use of bioplastics is still minimal. However, according to the recently announced Korean (K) - Circular Economy Implementation Plan, the government is encouraging the conversion of existing petroleum-based plastics into petroleum-based mixed bioplastics, and accordingly, the commercialization of bioplastics is being promoted urgently.
기존의 플라스틱 포장재는 화석연료로부터 유래한 합성수지만을 이용하여 제품을 제조하기 때문에 화석연료로부터 합성수지의 제조 시 일산화탄소, 질소 산화물 및 기타 오존 형성 오염물 등 온실가스를 유발하며, 사용 후 매립된 경우 분해가 잘 이루어지지 않아 환경오염을 유발하는 문제점이 있었다.Existing plastic packaging materials are manufactured using only synthetic resins derived from fossil fuels. Therefore, when manufacturing synthetic resins from fossil fuels, they cause greenhouse gases such as carbon monoxide, nitrogen oxides, and other ozone-forming pollutants, and are easily decomposed when landfilled after use. As this was not done, there was a problem of causing environmental pollution.
이러한 문제점을 해결하기 위하여 식물성 또는 친환경 제품을 출시하고 있으나, 제품군에 따라 기계적 물성과 내구성이 종래에 합성수지로 이루어진 제품을 대체하지 못하는 경우가 대부분이다.To solve these problems, plant-based or eco-friendly products are being released, but depending on the product group, in most cases, the mechanical properties and durability cannot replace conventional products made of synthetic resin.
특히, 유통 및 물류 산업에서 적용되는 집합 포장용 스트레치 필름과 사료작물을 발효 및 보관하는 농축산업에서 적용되는 사일리지 필름의 경우, 외부 환경에서 장기간 방치되거나 가혹한 운반 조건에서 사용되는데, 종래에 개발된 생분해성 수지로 이루어진 필름은 열에 약하고 지나치게 빠른 생분해 특성으로 인해 적용이 곤란한 문제점이 있었다.In particular, in the case of stretch films for collective packaging applied in the distribution and logistics industry and silage films applied in the agricultural and livestock industries that ferment and store feed crops, they are left in the external environment for long periods of time or used under harsh transport conditions. Films made of resin had the problem of being difficult to apply due to their vulnerability to heat and excessively rapid biodegradation.
따라서, 현재 석유화학계 폴리에틸렌으로 제조된 스트레치 필름 및 사일리지 필름을 대체하기 위해 기존 제품과 동등한 물성을 가지면서도 석유화학계 수지의 사용량을 절감하여 친환경적인 요소를 가미할 수 있는 제품의 개발이 요구되고 있다.Therefore, in order to replace stretch films and silage films currently manufactured from petrochemical polyethylene, there is a need to develop products that have physical properties equivalent to existing products and can add eco-friendly elements by reducing the amount of petrochemical resin used.
본 발명의 목적은 옥수수, 감자 및 사탕수수 등에서 유래된 바이오매스가 함유된 폴리에틸렌 수지가 사용되어 합성수지의 사용량을 절감할 수 있기 때문에 친환경적이며, 합성수지로 제조된 필름과 대등한 물성을 나타내는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물 및 그 제조방법을 제공하는 것이다.The purpose of the present invention is to reduce the amount of synthetic resin used by using polyethylene resin containing biomass derived from corn, potatoes, and sugar cane, which is environmentally friendly, and biomass that exhibits physical properties equivalent to films made from synthetic resin. The present invention provides a flexible thin film composition for packaging using linear low-density polyethylene and a method for manufacturing the same.
본 발명의 목적은 바이오매스를 함유한 선형 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 프로필렌계 엘라스토머 및 폴리이소부틸렌으로 이루어지는 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물을 제공함에 의해 달성된다.The object of the present invention is to provide a flexible thin film composition for packaging using linear low-density polyethylene containing biomass, characterized in that it consists of linear low-density polyethylene containing biomass, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene. is achieved by
본 발명의 바람직한 특징에 따르면, 상기 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물은 바이오매스를 함유한 선형 저밀도 폴리에틸렌 20 내지 40 중량%, 선형 저밀도 폴리에틸렌 45 내지 78 중량%, 프로필렌계 엘라스토머 0.5 내지 14.5 중량% 및 폴리이소부틸렌 0.5 내지 1.5 중량%로 이루어지는 것으로 한다.According to a preferred feature of the present invention, the flexible thin film composition for packaging using the biomass-containing linear low-density polyethylene includes 20 to 40% by weight of biomass-containing linear low-density polyethylene, 45 to 78% by weight of linear low-density polyethylene, and propylene-based. It should be composed of 0.5 to 14.5% by weight of elastomer and 0.5 to 1.5% by weight of polyisobutylene.
본 발명의 더 바람직한 특징에 따르면, 상기 바이오매스를 함유한 선형 저밀도 폴리에틸렌은 밀도가 0.9 내지 0.93g/cm2이며, 용융지수가 0.8 내지 1.2g/10min인 것으로 한다.According to a more preferred feature of the present invention, the biomass-containing linear low-density polyethylene has a density of 0.9 to 0.93 g/cm 2 and a melt index of 0.8 to 1.2 g/10 min.
또한, 본 발명의 목적은 바이오매스를 함유한 선형 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 프로필렌계 엘라스토머 및 폴리이소부틸렌을 압출기에 투입하고 용융 및 혼련하는 용융혼련단계, 상기 용융혼련단계를 통해 용융 및 혼련된 혼합물을 티다이로 압출하여 필름형태로 성형하는 압출성형단계 및 상기 압출성형단계를 통해 압출된 성형물을 냉각하는 냉각단계로 이루어지는 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 제조방법을 제공함에 의해서도 달성될 수 있다.In addition, the object of the present invention is a melt-kneading step of putting biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene into an extruder and melting and kneading them, and melting and kneading them through the melt-kneading step. A flexible thin film for packaging using linear low-density polyethylene containing biomass, characterized in that it consists of an extrusion molding step of extruding the mixture into a film form by extruding it and a cooling step of cooling the molded product extruded through the extrusion molding step. It can also be achieved by providing a method for producing a film composition.
본 발명의 바람직한 특징에 따르면, 상기 용융혼련단계는 바이오매스를 함유한 선형 저밀도 폴리에틸렌 20 내지 40 중량%, 선형 저밀도 폴리에틸렌 45 내지 78 중량%, 프로필렌계 엘라스토머 0.5 내지 14.5 중량% 및 폴리이소부틸렌 0.5 내지 1.5 중량%가 압출기에 투입되어 이루어지는 것으로 한다.According to a preferred feature of the present invention, the melt kneading step includes 20 to 40% by weight of biomass-containing linear low-density polyethylene, 45 to 78% by weight of linear low-density polyethylene, 0.5 to 14.5% by weight of propylene-based elastomer, and 0.5% by weight of polyisobutylene. It is assumed that 1.5% by weight is added to the extruder.
본 발명의 더 바람직한 특징에 따르면, 상기 압출성형단계는 상기 용융혼련단계를 통해 용융 및 혼련된 혼합물을 180 내지 250℃의 온도로 가열된 티다이로 압출하여 10 내지 150㎛의 두께를 나타내는 필름형태로 성형하여 이루어지는 것으로 한다.According to a more preferred feature of the present invention, in the extrusion molding step, the mixture melted and kneaded through the melt kneading step is extruded through a T-die heated to a temperature of 180 to 250 ° C. to form a film having a thickness of 10 to 150 ㎛. It shall be made by molding.
본 발명의 더욱 바람직한 특징에 따르면, 상기 냉각단계는 상기 압출성형단계를 통해 압출된 성형물을 15 내지 40℃의 냉각롤러로 통과시켜 이루어지는 것으로 한다.According to a more preferred feature of the present invention, the cooling step is performed by passing the molded product extruded through the extrusion molding step through a cooling roller at a temperature of 15 to 40°C.
본 발명에 따른 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물 및 그 제조방법은 옥수수, 감자 및 사탕수수 등에서 유래된 바이오매스가 함유된 폴리에틸렌 수지가 사용되어 합성수지의 사용량을 절감할 수 있기 때문에 친환경적이며, 합성수지로 제조된 필름과 대등한 물성의 포장용 연성 박막필름 조성물을 제공하는 탁월한 효과를 나타낸다.The flexible thin film composition for packaging using linear low-density polyethylene containing biomass according to the present invention and its manufacturing method can reduce the amount of synthetic resin used by using polyethylene resin containing biomass derived from corn, potatoes, and sugarcane. Therefore, it is environmentally friendly and has an excellent effect of providing a flexible thin film composition for packaging with physical properties comparable to those of films made of synthetic resin.
도 1은 본 발명에 따른 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 제조방법을 나타낸 순서도이다.Figure 1 is a flowchart showing a method of manufacturing a flexible thin film composition for packaging using linear low-density polyethylene containing biomass according to the present invention.
도 2 내지 5는 본 발명의 실시예 1 내지 3 및 비교예 1을 통해 제조된 포장용 연성 박막필름의 기계적 물성을 평가하여 나타낸 그래프이다.Figures 2 to 5 are graphs showing the evaluation of mechanical properties of flexible thin films for packaging manufactured through Examples 1 to 3 and Comparative Example 1 of the present invention.
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Below, preferred embodiments of the present invention and the physical properties of each component are described in detail, but are intended to be described in detail so that those skilled in the art can easily practice the invention. This does not mean that the technical idea and scope of the present invention are limited.
본 발명에 따른 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물은 바이오매스를 함유한 선형 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 프로필렌계 엘라스토머 및 폴리이소부틸렌으로 이루어지며, 바이오매스를 함유한 선형 저밀도 폴리에틸렌 20 내지 40 중량%, 선형 저밀도 폴리에틸렌 45 내지 78 중량%, 프로필렌계 엘라스토머 0.5 내지 14.5 중량% 및 폴리이소부틸렌 0.5 내지 1.5 중량%로 이루어지는 것이 바람직하다.The flexible thin film composition for packaging using biomass-containing linear low-density polyethylene according to the present invention is composed of biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer and polyisobutylene, and biomass-containing linear low-density polyethylene. It is preferably composed of 20 to 40% by weight of linear low-density polyethylene, 45 to 78% by weight of linear low-density polyethylene, 0.5 to 14.5% by weight of propylene-based elastomer, and 0.5 to 1.5% by weight of polyisobutylene.
상기 바이오매스를 함유한 선형 저밀도 폴리에틸렌은 20 내지 40 중량%가 함유되며, 바이오매스를 원료로 하여 제조된 수지로서 옥수수, 감자, 사탕수수 등에서 당을 추출하여 알코올 발효시켜 중합함으로써 바이오매스 유래 수지를 제조할 수 있다. 바람직하게 상기 바이오 선형 저밀도 폴리에틸렌 수지는 사탕수수에서 유래된 바이오매스를 함유한 것일 수 있으며, 생분해속도가 빠르기 때문에 미세플라스틱의 문제를 유발하는 합성수지를 대체할 수 있을 뿐만 아니라, 밀도가 0.9 내지 0.93g/cm2이며, 용융지수가 0.8 내지 1.2g/10min를 나타내는 것을 사용하는 것이 바람직하다.The biomass-containing linear low-density polyethylene contains 20 to 40% by weight, and is a resin manufactured using biomass as a raw material. The biomass-derived resin is produced by extracting sugars from corn, potatoes, sugar cane, etc. and polymerizing them through alcohol fermentation. It can be manufactured. Preferably, the bio-linear low-density polyethylene resin may contain biomass derived from sugarcane, and has a fast biodegradation rate, so not only can it replace synthetic resins that cause problems with microplastics, but also has a density of 0.9 to 0.93 g. /cm 2 , and it is preferable to use one having a melt index of 0.8 to 1.2 g/10 min.
상기 바이오매스를 함유한 선형 저밀도 폴리에틸렌의 함량이 20 중량% 미만이면 상기의 효과가 미미하며, 상기 선형 저밀도 폴리에틸렌의 함량이 40 중량%를 초과하게 되면 상기의 효과는 향상되지만 제조되는 필름의 기계적 물성이 저하될 뿐만 아니라, 필름의 생분해속도가 지나치게 증가하기 때문에 스트레치 필름이나 사일리지 필름으로는 사용이 제한될 수 있기 때문에 바람직하지 못하다.If the content of the biomass-containing linear low-density polyethylene is less than 20% by weight, the above effect is minimal, and if the content of the linear low-density polyethylene exceeds 40% by weight, the above effect is improved, but the mechanical properties of the film produced are reduced. Not only does this decrease, but the biodegradation rate of the film also increases excessively, which is undesirable because its use as a stretch film or silage film may be limited.
상기 선형 저밀도 폴리에틸렌은 45 내지 78 중량%가 함유되는데, 지글러-나차 촉매나 멜탈로센 촉매 하에서 중합된 것을 사용할 수 있는데, 본 발명을 통해 제조되는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 주재료가 되는 성분으로 기계적 물성을 부여하는 역할을 한다.The linear low-density polyethylene contains 45 to 78% by weight, and polymerized under a Ziegler-Nacha catalyst or a meltalocene catalyst can be used. A flexible thin film for packaging using linear low-density polyethylene containing biomass produced through the present invention. It is the main ingredient of the film composition and plays a role in providing mechanical properties.
상기 지글러-나타 촉매 하에 중합된 선형 저밀도 폴리에틸렌 수지의 α-올레핀 공단량체는 1-헥센, 1-옥텐, 1-데센 및 1-도데센으로 이루어진 군에서 선택되는 1종 이상인 것이 바람직하며, 더욱 바람직하게는 탄소 원자수 6 이상의 것으로, 가장 바람직하게는 1-헥센을 사용하는 것이 좋다. 상기 지글러-나타 촉매는 올레핀 중합용 촉매의 하나로, 전이금속화합물이 주성분인 주촉매, 유기금속 화합물인 조촉매, 및 전자공여체의 조합으로 이루어지는 촉매계를 의미하는 것으로, 본 발명에서는 공지의 지글러-나타 촉매로 알려진 촉매는 제한없이 사용될 수 있다.The α-olefin comonomer of the linear low density polyethylene resin polymerized under the Ziegler-Natta catalyst is preferably at least one selected from the group consisting of 1-hexene, 1-octene, 1-decene, and 1-dodecene, and more preferably It is best to use one with 6 or more carbon atoms, and most preferably 1-hexene. The Ziegler-Natta catalyst is one of the catalysts for olefin polymerization. It refers to a catalyst system consisting of a combination of a main catalyst mainly composed of a transition metal compound, a cocatalyst made of an organometallic compound, and an electron donor. In the present invention, the Ziegler-Natta catalyst is known as the Ziegler-Natta catalyst. Catalysts known as catalysts may be used without limitation.
또한, 상기 메탈로센 촉매 하에 중합된 선형 저밀도 폴리에틸렌 수지의 α-올레핀 공단량체는 1-헥센, 1-옥텐, 1-데센 및 1-도데센으로 이루어진 군에서 선택되는 1종 이상인 것이 바람직하며, 더욱 바람직하게는 탄소 원자수 6 이상의 것으로, 가장 바람직하게는 1-헥센을 사용하는 것이 좋다. 상기 메탈로센 촉매는 2종의 사이클로펜타디엔 사이에 금속이 끼어있는 구조의 촉매를 말하며, 단일 활성점을 갖는 촉매이다. 본 발명에서는 본 발명에서는 공지의 메탈로센 촉매로 알려진 촉매는 제한없이 사용될 수 있다.In addition, the α-olefin comonomer of the linear low-density polyethylene resin polymerized under the metallocene catalyst is preferably at least one selected from the group consisting of 1-hexene, 1-octene, 1-decene, and 1-dodecene, More preferably, it is one with 6 or more carbon atoms, and most preferably, 1-hexene is used. The metallocene catalyst refers to a catalyst with a structure in which a metal is sandwiched between two types of cyclopentadiene, and is a catalyst with a single active site. In the present invention, catalysts known as metallocene catalysts may be used without limitation.
상기 선형 저밀도 폴리에틸렌의 함량이 45 중량% 미만이면 제조되는 필름의 기계적 물성이 지나치게 저하되며, 생분해성이 지나치게 향상되어 스트레치 필름이나 사일리지 필름으로는 사용이 제한될 수 있으며, 상기 선형 저밀도 폴리에틸렌의 함량이 78 중량%를 초과하게 되면 상대적으로 바이오매스를 함유한 선형 저밀도 폴리에틸렌의 함량이 지나치게 줄어들어 본 발명의 목적을 달성할 수 없다.If the content of the linear low-density polyethylene is less than 45% by weight, the mechanical properties of the produced film are excessively reduced, and biodegradability is excessively improved, which may limit its use as a stretch film or silage film. If it exceeds 78% by weight, the content of linear low-density polyethylene containing biomass is relatively reduced too much, making it impossible to achieve the purpose of the present invention.
상기 프로필렌계 엘라스토머는 0.5 내지 14.5 중량%가 함유되며, 본 발명을 통해 제조되는 필름의 인장강도나 연신율을 향상시키는 역할을 하는데, 플로필렌계 엘라스토머의 성분은 특별히 한정되지는 않지만 프로필렌-에틸렌 공중합체를 사용하는 것이 바람직하다.The propylene-based elastomer contains 0.5 to 14.5% by weight and serves to improve the tensile strength or elongation of the film manufactured through the present invention. The component of the propylene-based elastomer is not particularly limited, but is a propylene-ethylene copolymer. It is desirable to use .
또한, 상기 프로필렌계 엘라스토머로는 이전부터 알려진 공지된 방법으로 제조되거나, 이미 상용화되어 있는 기존의 지글러-나타 또는 메탈로센계 촉매로 제조된 프로필렌계 엘라스토머를 별다른 제한 없이 모두 사용할 수 있다.In addition, as the propylene-based elastomer, any propylene-based elastomer manufactured by a previously known method or manufactured using an existing Ziegler-Natta or metallocene-based catalyst that is already commercialized can be used without any restrictions.
상기 프로필렌계 엘라스토머의 함량이 0.5 중량부 미만이면 상기의 효과가 미미하며, 상기 프로필렌계 엘라스토머의 함량이 14.5 중량%를 초과하게 되면 상대적으로 바이오매스를 함유한 선형 저밀도 폴리에틸렌과 선형 저밀도 폴리에틸렌의 함량이 지나치게 줄어들어 생분해 효과나 기계적 물성이 저하될 수 있다.If the content of the propylene-based elastomer is less than 0.5 parts by weight, the above effect is minimal, and if the content of the propylene-based elastomer exceeds 14.5 weight%, the content of linear low-density polyethylene containing biomass and linear low-density polyethylene are relatively high. If it decreases too much, the biodegradation effect or mechanical properties may be reduced.
상기 폴리이소부틸렌은 0.5 내지 1.5 중량%가 함유되며, 필름의 유연성과 투명을 향상시키는 역할을 하는데, 상기 폴리이소부틸렌의 함량이 0.5 중량% 미만이면 상기의 효과가 미미하며, 상기 폴리이소부틸렌의 함량이 1.5 중량%를 초과하게 되면 상기의 효과는 크게 향상되지 않으면서 필름의 기계적 물성을 지나치게 저하시킬 수 있다.The polyisobutylene contains 0.5 to 1.5% by weight and plays a role in improving the flexibility and transparency of the film. If the polyisobutylene content is less than 0.5% by weight, the effect is minimal, and the polyisobutylene If the butylene content exceeds 1.5% by weight, the mechanical properties of the film may be excessively reduced without significantly improving the above effects.
또한, 본 발명에 따른 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 제조방법은 바이오매스를 함유한 선형 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 프로필렌계 엘라스토머 및 폴리이소부틸렌을 압출기에 투입하고 용융 및 혼련하는 용융혼련단계(S101), 상기 용융혼련단계(S101)를 통해 용융 및 혼련된 혼합물을 티다이로 압출하여 필름형태로 성형하는 압출성형단계(S103) 및 상기 압출성형단계(S103)를 통해 압출된 성형물을 냉각하는 냉각단계(S105)로 이루어진다.In addition, the method of manufacturing a flexible thin film composition for packaging using biomass-containing linear low-density polyethylene according to the present invention involves adding biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene to an extruder. a melt-kneading step (S101) of melting and kneading, an extrusion molding step (S103) of extruding the mixture melted and kneaded through the melt-kneading step (S101) with a T-die and forming it into a film form, and the extrusion molding step (S103). ) consists of a cooling step (S105) in which the extruded molded product is cooled.
상기 용융혼련단계(S101)는 바이오매스를 함유한 선형 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 프로필렌계 엘라스토머 및 폴리이소부틸렌을 압출기에 투입하고 용융 및 혼련하는 단계로, 바이오매스를 함유한 선형 저밀도 폴리에틸렌 20 내지 40 중량%, 선형 저밀도 폴리에틸렌 45 내지 78 중량%, 프로필렌계 엘라스토머 0.5 내지 14.5 중량% 및 폴리이소부틸렌 0.5 내지 1.5 중량%를 압출기에 투입하고 160 내지 240℃의 온도에서 용융 및 혼련하는 과정으로 이루어진다.The melt-kneading step (S101) is a step of putting biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene into an extruder and melting and kneading them. Linear low-density polyethylene containing biomass 20 to 40% by weight, 45 to 78% by weight of linear low-density polyethylene, 0.5 to 14.5% by weight of propylene-based elastomer, and 0.5 to 1.5% by weight of polyisobutylene, into an extruder and melted and kneaded at a temperature of 160 to 240°C. It comes true.
이때, 상기 용융혼련은 필름의 중간층에 바이오 선형 저밀도 폴리에틸렌 수지가 위치하고, 중간층의 상부면 및 해부면에 선형 저밀도 폴리에틸렌 수지가 위치하고, 포상시 필름의 내부가 되는 부분에는 프로필렌계 엘라스토머 성분이 위치할 수 있도록 진행되는 것이 바람직하다.At this time, in the melt kneading, the bio linear low-density polyethylene resin is located in the middle layer of the film, the linear low-density polyethylene resin is located in the upper surface and anatomical surface of the middle layer, and the propylene-based elastomer component may be located in the inner part of the film when foaming. It is desirable for this to proceed.
또한, 상기 바이오매스를 함유한 선형 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 프로필렌계 엘라스토머 및 폴리이소부틸렌의 성분 및 함량에 따른 임계적 의의에 대한 설명은 상기 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물에 기재된 내용과 동일하므로, 이에 대한 설명은 생략하기로 한다.In addition, a description of the critical significance of the components and contents of the biomass-containing linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene is given in the section on packaging ductility using the biomass-containing linear low-density polyethylene. Since the contents are the same as those described in the thin film composition, description thereof will be omitted.
상기 압출성형단계(S103)는 상기 용융혼련단계(S101)를 통해 용융 및 혼련된 혼합물을 티다이로 압출하여 필름형태로 성형하는 단계로, 상기 용융혼련단계(S101)를 통해 용융 및 혼련된 혼합물을 180 내지 250℃의 온도로 가열된 티다이로 압출하여 10 내지 150㎛의 두께를 나타내는 필름형태로 성형하여 이루어지는데, 상기 압출성형단계(S103)에서 압출성형된 성형물의 두께가 10㎛ 미만이면 제조되는 필름의 기계적 물성이 지나치게 저하되며, 상기 성형물의 두께가 150㎛를 초과하게 되면 제조되는 필름의 기계적 물성은 크게 향상되지 않으면서 필름의 유연성이 저하되며 중량이 지나치게 증가하기 때문에 바람직하지 못하다.The extrusion molding step (S103) is a step of extruding the mixture melted and kneaded through the melt and kneading step (S101) into a film form by extruding it into a film form. The mixture melted and kneaded through the melt and kneading step (S101) is molded into a film. It is made by extruding with a T-die heated to a temperature of 180 to 250 ℃ and molding into a film having a thickness of 10 to 150 ㎛. If the thickness of the extrusion molded product in the extrusion molding step (S103) is less than 10 ㎛ The mechanical properties of the manufactured film are excessively reduced, and if the thickness of the molded product exceeds 150㎛, the mechanical properties of the manufactured film are not significantly improved, but the flexibility of the film is reduced and the weight is excessively increased, which is undesirable.
이때, 상기 압출성형단계(S103)에서 발생하는 부산물은 회수된 후에 상기 용융혼련단계(S101)에서 재투입되어 재활용될 수 있다.At this time, the by-products generated in the extrusion molding step (S103) can be recovered and then reintroduced in the melt kneading step (S101) and recycled.
상기 냉각단계(S105)는 상기 압출성형단계(S103)를 통해 압출된 성형물을 냉각하는 단계로, 상기 압출성형단계(S103)를 통해 압출된 성형물을 15 내지 40℃의 냉각롤러로 통과시켜 이루어지는데, 상기의 온도를 나타내는 냉각롤러를 통과하게 되면 압출된 성형물의 냉각이 진행될 뿐만 아니라, 고른 표면을 나타내어 상품성이 향상된 필름 조성물을 제공할 수 있다.The cooling step (S105) is a step of cooling the molded product extruded through the extrusion molding step (S103), and is achieved by passing the molded product extruded through the extrusion molding step (S103) through a cooling roller at a temperature of 15 to 40 ° C. When passing through a cooling roller showing the above temperature, the extruded molded product is not only cooled, but also has an even surface, thereby providing a film composition with improved marketability.
이하에서는, 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 제조방법 및 그 제조방법으로 제조된 포장용 연성 박막피름의 물성을 실시예를 들어 설명하기로 한다.Hereinafter, a method for manufacturing a flexible thin film composition for packaging using linear low-density polyethylene containing biomass and the physical properties of a flexible thin film for packaging manufactured using the manufacturing method will be described using examples.
<실시예 1><Example 1>
필름의 중간층 부위에 바이오 선형 저밀도 폴리에틸렌 수지(밀도: 0.916g/㎤, 용융지수:1.0g/10min) 25 중량%, 상기 중간층의 상부면 및 하부면에 선형 저밀도 폴리에틸렌 수지 60 중량% 및 필름의 내측에 프로필렌계 엘라스토머 4 중량%, 폴리이소부틸렌 1 중량%가 위치하도록 190℃의 온도에서 용융 및 혼련한 후에, 혼련된 수지를 200℃의 온도로 가열된 티다이 블록으로 통과시켜 80㎛ 두께의 성형물을 제조한 후에, 제조된 성형물을 냉각수 순환장치가 구비된 냉각롤러(25℃)로 통과시켜 두께가 25㎛이며 가로 2200mm×세로 2200mm인 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름을 제조하였다.25% by weight of bio linear low-density polyethylene resin (density: 0.916g/cm3, melt index: 1.0g/10min) on the middle layer of the film, 60% by weight of linear low-density polyethylene resin on the upper and lower surfaces of the middle layer, and the inside of the film. After melting and kneading at a temperature of 190℃ so that 4% by weight of propylene-based elastomer and 1% by weight of polyisobutylene are placed, the kneaded resin is passed through a T-die block heated to a temperature of 200℃ to form an 80㎛ thick After manufacturing the molded product, the manufactured product is passed through a cooling roller (25°C) equipped with a cooling water circulation device to create a flexible thin film for packaging using linear low-density polyethylene containing biomass with a thickness of 25㎛ and a size of 2200mm wide x 2200mm high. was manufactured.
<실시예 2><Example 2>
상기 실시예 1과 동일하게 진행하되, 바이오 선형 저밀도 폴리에틸렌 수지 25 중량%, 선형 저밀도 폴리에틸렌 수지 72 중량%, 프로필렌계 엘라스토머 2 중량%, 폴리이소부틸렌 1 중량%를 혼합하여 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름을 제조하였다.Proceed in the same manner as Example 1, except that 25% by weight of bio linear low-density polyethylene resin, 72% by weight of linear low-density polyethylene resin, 2% by weight of propylene-based elastomer, and 1% by weight of polyisobutylene were mixed to form a linear polyethylene containing biomass. A flexible thin film for packaging was manufactured using low-density polyethylene.
<실시예 3><Example 3>
상기 실시예 1과 동일하게 진행하되, 바이오 선형 저밀도 폴리에틸렌 수지 35 중량%, 선형 저밀도 폴리에틸렌 수지 60 중량%, 프로필렌계 엘라스토머 4 중량%, 폴리이소부틸렌 1 중량%를 혼합하여 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름을 제조하였다.Proceed in the same manner as Example 1, except that 35% by weight of bio linear low-density polyethylene resin, 60% by weight of linear low-density polyethylene resin, 4% by weight of propylene-based elastomer, and 1% by weight of polyisobutylene were mixed to form a linear polyethylene containing biomass. A flexible thin film for packaging was manufactured using low-density polyethylene.
<비교예 1><Comparative Example 1>
석유화학계 선형 저밀도 폴리에틸렌 수지 99 중량%, 폴리이소부틸렌 1 중량%를 190℃에서 수지를 용융 및 혼련시키며, 혼련된 수지를 200℃의 온도로 가열된 티다이 블록으로 통과시켜 80㎛ 두께의 성형물을 제조한 후에, 제조된 성형물을 냉각수 순환장치가 구비된 냉각롤러(25℃)로 통과시켜 두께가 25㎛이며 가로 2200mm×세로 2200mm인 포장용 연성 박막필름을 제조하였다.99% by weight of petrochemical linear low-density polyethylene resin and 1% by weight of polyisobutylene are melted and kneaded at 190°C, and the kneaded resin is passed through a T-die block heated to a temperature of 200°C to form an 80㎛ thick molded product. After manufacturing, the manufactured molded product was passed through a cooling roller (25°C) equipped with a cooling water circulation device to produce a flexible thin film for packaging with a thickness of 25㎛ and a width of 2200mm x a height of 2200mm.
상기 실시예 1 내지 3 및 비교예 1을 통해 제조된 포장용 연성 박막필름의 바이오매스 C14의 농도값을 측정하여 아래 표 1에 나타내었다.The concentration values of biomass C 14 in the flexible thin film for packaging manufactured through Examples 1 to 3 and Comparative Example 1 were measured and shown in Table 1 below.
{단, 바이오매스 C14의 농도값을 측정하기 위하여 Beta analytic의 Biobased Testing을 ASTM D6866 규격을 기준으로 측정하였다. 상기 ASTM D6866에 의한 pMC 값은 유효 바이오 성분의 함량을 의미한다.}{However, in order to measure the concentration value of biomass C 14 , Beta analytic's Biobased Testing was measured based on the ASTM D6866 standard. The pMC value according to ASTM D6866 refers to the content of active bio-ingredients.}
구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 1Comparative Example 1
Percent
Modern
Carbon(pMC)Percent
Modern
Carbon(pMC) 		11.23 (±0.07)11.23 (±0.07) 21.62 (±0.09)21.62 (±0.09) 28.86 (±0.11)28.86 (±0.11) 1.62
(±0.04)1.62
(±0.04)
Atmospheric
Adjustment
Factor(REF) Atmospheric
Adjustment
Factor(REF) 		100.0 ;
= pMC/1.000100.0 ;
=pMC/1.000 		100.0 ;
= pMC/1.000100.0 ;
=pMC/1.000 		100.0 ;
= pMC/1.000100.0 ;
=pMC/1.000 		101.0 ;
= pMC/1.010101.0 ;
=pMC/1.010
상기 표 1에 나타낸 것처럼, 본 발명의 실시예 1 내지 3을 통해 제조된 포장용 연성 박막필름은 바이오매스의 함량이 높은 것을 알 수 있다.As shown in Table 1, it can be seen that the flexible thin film for packaging manufactured through Examples 1 to 3 of the present invention has a high biomass content.
다만, 바이오매스를 함유한 선형 저밀도 폴리에틸렌의 함량이 같은 실시예 1과 실시예 2를 비교했을 때 발생하는 바이오매스의 차이는 실시예 1의 경우 중간층으로 투여되는 필름 부산물의 회수량이 많아, 그게 따른 바이오매스가 함유된 선형 저밀도 폴리에틸렌 수지의 함량도 낮아지기 때문이다.However, the difference in biomass that occurs when comparing Example 1 and Example 2, which have the same content of linear low-density polyethylene containing biomass, is due to the large amount of recovered film by-product administered to the middle layer in Example 1, which is This is because the content of linear low-density polyethylene resin containing biomass is also lowered.
또한, 상기 실시예 1 내지 3 및 비교예 1을 통해 제조된 포장용 연성 박막필름의 기계적 물성을 평가하여 아래 표 2 및 도 2 내지 5에 나타내었다.In addition, the mechanical properties of the flexible thin films for packaging prepared through Examples 1 to 3 and Comparative Example 1 were evaluated and are shown in Table 2 and Figures 2 to 5 below.
{단, 기계적 물성은 KS M 3001 및 ASTM D882의 시험 규격에 의해 측정하였으며, 일정 면적에 대한 최대 하중 및 연신율을 종방향(MD)과 횡방향(TD)에 따라 측정하였다.}{However, mechanical properties were measured according to the test standards of KS M 3001 and ASTM D882, and the maximum load and elongation for a certain area were measured in the longitudinal direction (MD) and transverse direction (TD).}
구분division 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 1Comparative Example 1
인장강도
(kgf/㎠)tensile strength
(kgf/㎠) 		종방향longitudinal 451451 510510 555555 537537
횡방향transverse 353353 384384 352352 405405
연신율
(%)elongation
(%) 		종방향longitudinal 511511 526526 610610 625625
횡방향transverse 757757 871871 906906 830830
상기 표 2와 아래 도 2 내지 5에 나타낸 것처럼, 종방향의 기계적 물성은 기계방향(Machine Direction, MD)으로 실제 스트레치 필름 또는 사일리지 필름을 사용할 때 기계에 거치되어 작동하는 방향으로 제품의 품질을 좌우하는데, 바이오매스 함량이 늘어남에 따라 종방향(MD)의 인장강도가 451kgf/㎤에서 555kgf/㎤까지 점차 증가하며, 연신율은 511%에서 610%로 높아지는 것을 보이며, 비교예 1과 실시예 2 내지 3을 비교했을 때 실시예 2 내지 3이 비교예 1과 동등 또는 그 이상의 수치를 나타내는 것을 알 수 있다.As shown in Table 2 above and Figures 2 to 5 below, the mechanical properties in the longitudinal direction are in the machine direction (MD). When using an actual stretch film or silage film, the direction in which it is placed and operated in the machine determines the quality of the product. However, as the biomass content increases, the tensile strength in the machine direction (MD) gradually increases from 451 kgf/cm3 to 555 kgf/cm3, and the elongation increases from 511% to 610%. Comparative Example 1 and Examples 2 to 2 When comparing 3, it can be seen that Examples 2 to 3 show values equivalent to or higher than Comparative Example 1.
또한, 상기 실시예 3을 통해 제조된 포장용 연성 박막필름의 유해성분 함유여부를 유럽 RoHS 지침에 따라 규제물질의 함유 평가를 IEC 62321-4, IEC IEC62321-5, IEC 62321-6, 62321-7-2, IEC 62321-8에 의거하여 한국의 분석기관인 안양시 소재 에스지에스 코리아(주) (SGS Korea Co., Ltd.)에 의뢰하여 측정한 결과, 본 발명의 실시예 3을 통해 제조된 필름은 규제물질인 유해성분이 모두 불검출로 나타났으며, 이에 따라 유럽 RoHS 기준에 적합한 것을 알 수 있었다.In addition, the presence of hazardous ingredients in the flexible thin film for packaging manufactured through Example 3 was evaluated for the content of regulated substances according to the European RoHS Directive by IEC 62321-4, IEC IEC62321-5, IEC 62321-6, 62321-7- 2, As a result of measurement in accordance with IEC 62321-8 by requesting SGS Korea Co., Ltd., located in Anyang-si, a Korean analysis agency, the film manufactured through Example 3 of the present invention was regulated. All hazardous substances were found to be non-detectable, and it was confirmed that it complies with the European RoHS standard.
따라서, 본 발명에 따른 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물 및 그 제조방법은 옥수수, 감자 및 사탕수수 등에서 유래된 바이오매스가 함유된 폴리에틸렌 수지가 사용되어 합성수지의 사용량을 절감할 수 있기 때문에 친환경적이며, 합성수지로 제조된 필름과 대등한 물성의 포장용 연성 박막필름 조성물을 제공한다.Therefore, the flexible thin film composition for packaging using linear low-density polyethylene containing biomass according to the present invention and its manufacturing method use polyethylene resin containing biomass derived from corn, potatoes, and sugarcane, thereby reducing the amount of synthetic resin used. This provides a flexible thin film composition for packaging that is environmentally friendly and has properties comparable to those of films made of synthetic resin.

Claims (7)

  1. 바이오매스를 함유한 선형 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 프로필렌계 엘라스토머 및 폴리이소부틸렌으로 이루어지는 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물.A flexible thin film composition for packaging using linear low-density polyethylene containing biomass, characterized in that it consists of linear low-density polyethylene containing biomass, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene.
  2. 청구항 1에 있어서,In claim 1,
    상기 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물은 바이오매스를 함유한 선형 저밀도 폴리에틸렌 20 내지 40 중량%, 선형 저밀도 폴리에틸렌 45 내지 78 중량%, 프로필렌계 엘라스토머 0.5 내지 14.5 중량% 및 폴리이소부틸렌 0.5 내지 1.5 중량%로 이루어지는 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물.The flexible thin film composition for packaging using biomass-containing linear low-density polyethylene includes 20 to 40% by weight of biomass-containing linear low-density polyethylene, 45 to 78% by weight of linear low-density polyethylene, 0.5 to 14.5% by weight of propylene-based elastomer, and poly A flexible thin film composition for packaging using linear low-density polyethylene containing biomass, characterized in that it consists of 0.5 to 1.5% by weight of isobutylene.
  3. 청구항 1 또는 2에 있어서,In claim 1 or 2,
    상기 바이오매스를 함유한 선형 저밀도 폴리에틸렌은 밀도가 0.9 내지 0.93g/cm2이며, 용융지수가 0.8 내지 1.2g/10min인 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물.The linear low-density polyethylene containing biomass has a density of 0.9 to 0.93 g/cm 2 and a melt index of 0.8 to 1.2 g/10 min. A flexible thin film composition for packaging using linear low-density polyethylene containing biomass. .
  4. 바이오매스를 함유한 선형 저밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 프로필렌계 엘라스토머 및 폴리이소부틸렌을 압출기에 투입하고 용융 및 혼련하는 용융혼련단계;A melt-kneading step in which linear low-density polyethylene, linear low-density polyethylene, propylene-based elastomer, and polyisobutylene containing biomass are put into an extruder and melted and kneaded;
    상기 용융혼련단계를 통해 용융 및 혼련된 혼합물을 티다이로 압출하여 필름형태로 성형하는 압출성형단계; 및An extrusion molding step of extruding the melted and kneaded mixture through a T-die and forming it into a film form through the melt-kneading step; and
    상기 압출성형단계를 통해 압출된 성형물을 냉각하는 냉각단계;로 이루어지는 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 제조방법.A method of producing a flexible thin film composition for packaging using linear low-density polyethylene containing biomass, comprising a cooling step of cooling the molded product extruded through the extrusion molding step.
  5. 청구항 4에 있어서,In claim 4,
    상기 용융혼련단계는 바이오매스를 함유한 선형 저밀도 폴리에틸렌 20 내지 40 중량%, 선형 저밀도 폴리에틸렌 45 내지 78 중량%, 프로필렌계 엘라스토머 0.5 내지 14.5 중량% 및 폴리이소부틸렌 0.5 내지 1.5 중량%가 압출기에 투입되어 이루어지는 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 제조방법.In the melt-kneading step, 20 to 40% by weight of linear low-density polyethylene containing biomass, 45 to 78% by weight of linear low-density polyethylene, 0.5 to 14.5% by weight of propylene-based elastomer, and 0.5 to 1.5% by weight of polyisobutylene are added to the extruder. A method for producing a flexible thin film composition for packaging using linear low-density polyethylene containing biomass, characterized in that it is made of.
  6. 청구항 4에 있어서,In claim 4,
    상기 압출성형단계는 상기 용융혼련단계를 통해 용융 및 혼련된 혼합물을 180 내지 250℃의 온도로 가열된 티다이로 압출하여 10 내지 150㎛의 두께를 나타내는 필름형태로 성형하여 이루어지는 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 제조방법.The extrusion molding step is a bio product characterized in that the mixture melted and kneaded through the melt kneading step is extruded through a T-die heated to a temperature of 180 to 250 ° C. and molded into a film having a thickness of 10 to 150 ㎛. Method for producing a flexible thin film composition for packaging using mass-containing linear low-density polyethylene.
  7. 청구항 4에 있어서,In claim 4,
    상기 냉각단계는 상기 압출성형단계를 통해 압출된 성형물을 15 내지 40℃의 냉각롤러로 통과시켜 이루어지는 것을 특징으로 하는 바이오매스가 함유된 선형 저밀도 폴리에틸렌을 이용한 포장용 연성 박막필름 조성물의 제조방법.The cooling step is a method of producing a flexible thin film composition for packaging using linear low-density polyethylene containing biomass, characterized in that the molded product extruded through the extrusion molding step is passed through a cooling roller at 15 to 40 ° C.
PCT/KR2022/007690 2022-05-30 2022-05-30 Flexible thin film composition for packaging using linear low-density polyethylene containing biomass, and method for preparing same WO2023234433A1 (en)

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Publication number Priority date Publication date Assignee Title
KR101986123B1 (en) * 2017-11-28 2019-06-05 (주) 화진산업 Composition for stretch film comprising low carbon-type biomass polyethylene and method for preparing the same
KR20200044529A (en) * 2018-10-19 2020-04-29 주식회사 에이유 Biomass plastic composition with carbon dioxide absorption performance, biomass plastic sheet using the same and method of manufacturing thereof
KR102129605B1 (en) * 2019-08-16 2020-07-03 (주)죽암엠앤씨 multi layer stretch film for use in frozen conditions
JP6818245B2 (en) * 2016-04-26 2021-01-20 大日本印刷株式会社 Laminates with a polyolefin resin layer and packaging products with them
JP2021049784A (en) * 2020-12-15 2021-04-01 大日本印刷株式会社 Laminate having resin layer derived from biomass
JP6863483B2 (en) * 2017-12-26 2021-04-21 Dic株式会社 Laminated film and food packaging bag

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JP6818245B2 (en) * 2016-04-26 2021-01-20 大日本印刷株式会社 Laminates with a polyolefin resin layer and packaging products with them
KR101986123B1 (en) * 2017-11-28 2019-06-05 (주) 화진산업 Composition for stretch film comprising low carbon-type biomass polyethylene and method for preparing the same
JP6863483B2 (en) * 2017-12-26 2021-04-21 Dic株式会社 Laminated film and food packaging bag
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