KR100188179B1 - Resin compositions for manufacturing extrusion laminate having a low temperature thermosealing - Google Patents

Resin compositions for manufacturing extrusion laminate having a low temperature thermosealing Download PDF

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KR100188179B1
KR100188179B1 KR1019970005234A KR19970005234A KR100188179B1 KR 100188179 B1 KR100188179 B1 KR 100188179B1 KR 1019970005234 A KR1019970005234 A KR 1019970005234A KR 19970005234 A KR19970005234 A KR 19970005234A KR 100188179 B1 KR100188179 B1 KR 100188179B1
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component
melt index
butene
ethylene
weight part
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KR19980068565A (en
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이정규
강경보
이재근
황윤만
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이영일
호남석유화학 주식회사
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

본 발명은 저온 열봉합성 및 이지필성(easy peel)이 우수하며, 별도의 접착제 처리없이 기재에 직접 접착이 가능한 압출 라미네이션용 폴리프로필렌계 수지 조성물을 제공하며, 이 조성물은 하기 (A)성분 40∼60중량부, (B)성분 5∼20중량부, (C)성분 20∼40중량부, (D)성분 3∼15중량부, (E)성분 2∼10중량부 및 (F) 성분 0.001∼0.1중량부를 함유함을 특징으로 한다.:The present invention is excellent in low-temperature heat sealability and easy peel, and provides a polypropylene resin composition for extrusion lamination that can be directly adhered to the substrate without a separate adhesive treatment, the composition (A) component 40 ~ 60 weight part, (B) component 5-20 weight part, (C) component 20-40 weight part, (D) component 3-15 weight part, (E) component 2-10 weight part, and (F) component 0.001- It is characterized by containing 0.1 parts by weight:

(A) 프로필렌과, 에틸렌 또는 1-부텐과의 이원 또는 삼원 공중합체로서 하기 조건 1∼3을 만족하는 것:(A) Binary or terpolymer of propylene and ethylene or 1-butene, satisfying the following conditions 1 to 3:

① 에틸렌 또는 1-부텐 단독 혹은 에틸렌과 1-부텐과의 합이 4∼15몰%① 4 to 15 mol% of ethylene or 1-butene alone or the sum of ethylene and 1-butene

② 용융온도가 135℃ 이하② Melt temperature is below 135 ℃

③ 용융지수가 5∼25g/10min(230℃)③ Melt index of 5 ~ 25g / 10min (230 ℃)

(B) 용융지수가 1∼15g/10min(190℃), 밀도가 0.925g/㎤ 이하인 저밀도 폴리에틸렌(B) low density polyethylene with a melt index of 1 to 15 g / 10 min (190 ° C.) and a density of 0.925 g / cm 3 or less

(C) 용융지수가 0.4∼20g/10min(190℃), 밀도가 0.915g/㎤ 이하인 폴리부텐(C) a polybutene having a melt index of 0.4 to 20 g / 10 min (190 ° C.) and a density of 0.915 g / cm 3 or less

(D) 무정형 또는 저결정성의 에틸렌계α-올레핀 랜덤 공중합체 또는 1-부텐α-올레핀 랜덤 공중합체로서 하기의 조건 1∼3을 만족하는 것 :(D) an amorphous or low crystalline ethylenic α-olefin random copolymer or 1-butene α-olefin random copolymer that satisfies the following conditions 1 to 3:

① α-올레핀의 탄소수가 2∼20① 2 to 20 carbon atoms of α-olefin

② 용융지수가 0.1∼30g/10min(190℃)② Melt Index 0.1 ~ 30g / 10min (190 ℃)

③ 밀도가 0.900g/㎤ 이하③ Density is 0.900g / cm3 or less

(E) 말레산 무수물을 그라프트(graft) 변성시킨 변성 폴리프로필렌 공중합체로서 하기의 조건 1∼2를 만족하는 것 :(E) Modified polypropylene copolymer in which maleic anhydride is graft-modified to satisfy the following conditions 1 to 2:

① 불포화 카르복실산 또는 그 유도체로 그라프트율이 0.1∼10몰%① Graft rate 0.1-10 mol% with unsaturated carboxylic acid or its derivative (s)

② 고유점도가 0.1∼2㎗/g② intrinsic viscosity 0.1∼2㎗ / g

(F) 가교분해제(F) crosslinking agent

상기한 본 발명의 조성물은 저온이면서 넓은 범위의 열봉합 온도를 가지며, 가공성 및 이지필성(Easy Peel)이 우수하고, 별도의 접착제 처리없이 기재에 직접 접착이 가능하다.The composition of the present invention described above has a low temperature and a wide range of heat-sealing temperatures, and is excellent in workability and easy peel, and can be directly adhered to a substrate without a separate adhesive treatment.

Description

직접 접착이 가능하고, 저온 열봉합성 및 이지필성이 우수한 압출 라미네이션용 수지 조성물Resin composition for extrusion lamination that can be directly bonded and has excellent low temperature heat sealing and easy peel

본 발명은 프로필렌계 수지 조성물에 관한 것이고, 보다 상세하게는 저온이면서 넓은 범위의 열봉합 온도를 가지며, 가공성 및 이지필성(Easy Peel)이 우수하고, 별도의 접착제 처리없이 기재에 직접 접착이 가능한 압출 라미네이션용 폴리프로필렌계 수지 조성물을 제공하는 것이다.The present invention relates to a propylene-based resin composition, more specifically, a low temperature and a wide range of heat-sealing temperature, excellent workability and easy peel (Exel Peel), and can be directly bonded to the substrate without a separate adhesive treatment extruded It is to provide a polypropylene resin composition for lamination.

이지필실(Easy Peel Seal)이란 제품의 최종 소비자들의 손의 힘을 이용하여 열봉합된 포장재를 분리하여 내용물을 손쉽게 개봉이 가능하도록 하는 과정을 일컫는 것으로, 열봉합층을 이루고 있는 두면이 박리시키는 강도에 의하여 분리되어지는 인터페이셜 필실(Interfacial Peel Seal)과 공압출 공정에서 여러 다른 고분자간의 접착력 차이를 이용한 디라미네이션 필실(Delamination Peel Seal)이 있다.Easy Peel Seal (Easy Peel Seal) refers to the process of separating the heat-sealed packaging material and opening the contents easily using the power of the hands of the end consumers of the product. The strength of the two sides of the heat-sealing layer is peeled off. There is an interfacial peel seal (Separation Peel Seal) using the adhesive force difference between different polymers in the coextrusion process and the interfacial peel seal (Separated by).

일반적으로, 바람직한 이지필의 특성은, 많은 견해들이 있으나 가장 지배적인 견해가 600∼1200g/15mm 범위내에서 필이 가능해야 하는 것이다. 또한, 이상적인 필실수지나 필름은 넓은 열접착 온도 범위를 지녀야 하며 그 범위내의 어느 곳에서도 확실한 필실효과를 기대할 수 있어야 하는데, 이러한 특성은 일반적인 열접착의 실시범위내에서 열봉합 강도가 천천히 증가하는 열봉합층에서 기대할 수 있다. 이와 같은 이지필실의 특성을 부여하는 가공 방법으로는 T-다이를 이용한 캐스팅법(Casting)과 압출 라미네이션법이 있는데 주로 압출 라미네이션법을 많이 이용하고 있다. 압출 라미네이션법은 압출 코팅법이라고도 하는데, 예를 들면 원료 수지를 압출기에서 가열용융 및 혼련한 후 압출다이로부터 필름 상태로 압출하고, 이를 피복하고자 하는 기재의 표면에 피복한 후 고무롤과 냉각롤로 압착, 냉각하여 권취하는 방법으로, 이러한 압출 라미네이션 가공은 필름, 쉬트, 종이, 피피크로스, 부직포 등의 박막 기재에 방습성, 가스 배리아성, 내마모성, 내유성, 열봉합성 등의 특성을 부여하기 때문에 널리 사용되어 오고 있다.In general, the desirable characteristics of EZPILL are that there are many views, but the most dominant view should be able to fill within the range of 600-1200g / 15mm. In addition, the ideal film or film should have a wide range of thermal bonding temperatures and be able to expect a certain film effect anywhere within that range, which is characterized by the fact that the heat seal strength increases slowly within the general range of thermal bonding. It can be expected from the suture layer. As a processing method for imparting the characteristics of the easy peel yarn, there are a casting method using an T-die and an extrusion lamination method, and an extrusion lamination method is mainly used. The extrusion lamination method is also called extrusion coating method. For example, the raw material resin is heated and melted and kneaded in an extruder, and then extruded in a film state from an extrusion die, coated on the surface of the substrate to be coated, and then pressed with a rubber roll and a cooling roll, As a method of cooling and winding, such extrusion lamination processing has been widely used because it imparts moisture-proof, gas-barrier resistance, abrasion resistance, oil resistance, heat sealability, etc. to thin film substrates such as films, sheets, paper, pipicross, and nonwoven fabrics. have.

이러한 압출 라미네이션 가공에 사용되는 수지로는 저밀도 폴리에틸렌, 중밀도 폴리에틸렌, 에틸렌-초산비닐 공중합체, 이오노머(ionomer) 수지 등의 폴리올레핀이 대표적으로 사용되고 있으며, 그 중에서도 가공성이 우수하며, 열봉합 온도가 낮은 저밀도 폴리에틸렌이 주로 사용되고 있다. 그러나, 저밀도 폴리에틸렌의 경우에는 이지필성이 우수한 수지 조성물을 제공하고자 할 경우에 적합하지가 않고, 에틸렌-초산비닐 공중합체의 경우에는 넓은 열봉합 온도 범위를 기대할 수 있으나, 가공 온도가 높은 경우 쉽게 열화(Degradation)되어 압출기를 심하게 부식시키는 초산을 방출하는 문제점이 있다.As the resin used in the extrusion lamination, polyolefins such as low density polyethylene, medium density polyethylene, ethylene-vinyl acetate copolymer, and ionomer resin are typically used. Among them, excellent processability and low heat sealing temperature Low density polyethylene is mainly used. However, in the case of low-density polyethylene, it is not suitable to provide a resin composition having excellent easy-filling properties, and in the case of ethylene-vinyl acetate copolymer, a wide heat sealing temperature range can be expected, but it is easily deteriorated when the processing temperature is high. There is a problem of degradation to release acetic acid which severely corrodes the extruder.

한편, 최근에는 폴리프로필렌계, 발포 폴리스티렌계 등을 주로 사용하고, 종종 금속박을 사용하여 다층시트의 포장재를 제조하고 있는데, 이종의 기재로 포장재를 구성하는 데 있어서 직접 접착을 기대하기가 사실상 어려우므로 실제 가공 공정에서는 별도의 접착제(A/C제)를 사용하여 포장재를 제조하고 있다. 그러나, 접착제를 사용하는 경우 잔류 용제로 인하여 식품에 악영향을 끼치는 문제점이 있다.On the other hand, in recent years, polypropylene-based, expanded polystyrene-based, etc. are mainly used, and often the metal foil is used to manufacture the packaging material of the multi-layer sheet, it is difficult to expect direct adhesion in the construction of the packaging material with different substrates In the actual processing process, a packaging material is manufactured using a separate adhesive (manufactured by A / C). However, when using the adhesive there is a problem that adversely affects food due to the residual solvent.

따라서, 이러한 단점을 극복하기 위한 연구가 많이 행하여지고 있으며, 그 내용을 살표보면 다음과 같다.Therefore, a lot of research has been conducted to overcome these disadvantages, and the contents are as follows.

일본 특공소 60-49432에는 올레핀층, 이지필층, 가공성 개선층으로 구성된 필름의 제조 방법이 개시되어 있고, 일본 특공소 61-29377에는 프로필렌 공중합체, 폴리부텐, 에틸렌-프로필렌-1-부텐 삼원공중합체로 이루어진 수지 조성물을 제공하고 있으나 압출 라미네이션시 가공성이 불량하여 압출 라미네이션 수지로 적합하지 않은 문제점이 있다.JP 60-49432 discloses a method for producing a film composed of an olefin layer, an easy peel layer, and a processability improving layer. JP 61-29377 discloses a propylene copolymer, polybutene, and ethylene-propylene-1-butene ternary cavity. There is provided a resin composition consisting of a combination, but there is a problem that is not suitable as an extrusion lamination resin due to poor workability during extrusion lamination.

또한, 일본 특공평 3-4383에는 폴리에틸렌, 에틸렌-프로필렌 랜덤 공중합체, 에틸렌α-올레핀 공중합체로 이루어진 수지 조성물을 제공하고 있으나, 역시 압출라미네이션 수지로 적합하지가 않다. 한편, US 4,189,519에는 에틸렌 중합체와 에틸렌-불포화된 에스테르 공중합체에 이소탁틱폴리부텐(isotactic polybuten) 10∼50중량부로 이루어진 수지 조성물을, US 3,879,492에는 폴리부텐, 스틸렌-부타디엔 공중합체, 저밀도 폴리에틸렌, 고밀도 폴리에틸렌, 폴리이소부텐으로 이루어진 수지 조성물을 제공하고 있으나, 이 조성물들은 고밀도 폴리에틸렌계에는 열접착이 가능하나 폴리프로필렌계에는 접착이 불가능한 문제점이 있다. 또한, US 4,916,190와 US 4,666,778에는 에틸렌 호모폴리머 또는 에틸렌공중합체 10∼30중량부와 1-부텐 호모폴리머 또는 1-부텐 공중합체 55∼60중량부 및 프로필렌 호모폴리머 또는 프로필렌공중합체 25∼45중량부로 이루어진 수지 조성물이 개시되어 있으나, 접착력이 부족하고, 또한 내열성의 부족으로 보일링 및 레토르트 살균에 적합하지 못한 단점이 있다.In addition, Japanese Patent Application Laid-Open No. 3-4383 provides a resin composition composed of polyethylene, an ethylene-propylene random copolymer, and an ethylene? -Olefin copolymer, but is also not suitable as an extrusion lamination resin. On the other hand, US 4,189,519 is a resin composition consisting of 10-50 parts by weight of isotactic polybutene in an ethylene polymer and an ethylene-unsaturated ester copolymer, and US 3,879,492 is a polybutene, styrene-butadiene copolymer, low density polyethylene, high density Although there is provided a resin composition consisting of polyethylene and polyisobutene, these compositions are capable of thermal bonding to high-density polyethylene, but have a problem in that they cannot be bonded to polypropylene. Further, US 4,916,190 and US 4,666,778 include 10 to 30 parts by weight of ethylene homopolymer or ethylene copolymer and 55 to 60 parts by weight of 1-butene homopolymer or 1-butene copolymer and 25 to 45 parts by weight of propylene homopolymer or propylene copolymer. Although a resin composition has been disclosed, there is a disadvantage in that it is not suitable for boiling and retort sterilization due to the lack of adhesion and lack of heat resistance.

이러한 상황하에서, 본 발명자들은 별도의 접착제 처리없이 기재에 직접 접착이 가능하며, 폴리프로필렌계 수지의 우수한 기계적 및 열적 성질을 살리면서 종래의 단점인 가공성, 높은 열봉합 온도 및 좁은 범위의 열봉합 온도를 개선하여 적절한 이지필성을 부여코자 예의 연구한 결과, 본 발명을 완성하기에 이르렀다.Under these circumstances, the present inventors can directly adhere to the substrate without a separate adhesive treatment, while utilizing the excellent mechanical and thermal properties of the polypropylene-based resin, while the conventional disadvantages are workability, high heat sealing temperature, and narrow heat sealing temperature. As a result of earnestly researching to improve and to provide appropriate easy-filling properties, the present invention has been completed.

따라서, 본 발명의 목적은 하기 성분 (A), (B), (C), (D), (E) 및 (F)를 함유하며, (A)의 함량이 40∼60중량부, (B)의 함량이 5∼20중량부, (C)의 함량이 20∼40중량부, (D)의 함량이 3∼15중량부, (E)의 함량이 2∼10중량부, 그리고 (F)의 함량이 0.001∼0.1중량부임을 특징으로 하는 저온 열봉합성 및 이지필성(easy peel)이 우수하며, 별도의 접착제 처리없이 기재에 직접 접착이 가능한 압출 라미네이션용 폴리프로필렌계 수지 조성물을 제공하는 것이다.Therefore, an object of the present invention contains the following components (A), (B), (C), (D), (E) and (F), and the content of (A) is 40 to 60 parts by weight, (B ) 5 to 20 parts by weight, (C) 20 to 40 parts by weight, (D) 3 to 15 parts by weight, (E) 2 to 10 parts by weight, and (F) It is excellent in low temperature heat sealability and easy peel, characterized in that the content of 0.001 to 0.1 parts by weight, and to provide a polypropylene resin composition for extrusion lamination that can be directly adhered to the substrate without a separate adhesive treatment.

(A) 프로필렌과, 에틸렌 또는 1-부텐과의 이원 또는 삼원 공중합체로서 하기 조건 1∼3을 만족하는 것:(A) Binary or terpolymer of propylene and ethylene or 1-butene, satisfying the following conditions 1 to 3:

① 에틸렌 또는 1-부텐 단독 혹은 에틸렌과 1-부텐과의 합이 4∼15몰%① 4 to 15 mol% of ethylene or 1-butene alone or the sum of ethylene and 1-butene

② 용융온도가 135℃ 이하② Melt temperature is below 135 ℃

③ 용융지수가 5∼25g/10min(230℃)③ Melt index of 5 ~ 25g / 10min (230 ℃)

(B) 용융지수가 1∼15g/10min(190℃), 밀도가 0.925g/㎤ 이하인 저밀도 폴리에틸렌(B) low density polyethylene with a melt index of 1 to 15 g / 10 min (190 ° C.) and a density of 0.925 g / cm 3 or less

(C) 용융지수가 0.4∼20g/10min(190℃), 밀도가 0.915g/㎤ 이하인 폴리부텐(C) a polybutene having a melt index of 0.4 to 20 g / 10 min (190 ° C.) and a density of 0.915 g / cm 3 or less

(D) 무정형 또는 저결정성의 에틸렌계α-올레핀 랜덤 공중합체 또는 1-부텐α-올레핀 랜덤 공중합체로서 하기의 조건 1∼3을 만족하는 것 :(D) an amorphous or low crystalline ethylenic α-olefin random copolymer or 1-butene α-olefin random copolymer that satisfies the following conditions 1 to 3:

① α-올레핀의 탄소수가 2∼20① 2 to 20 carbon atoms of α-olefin

② 용융지수가 0.1∼30g/10min(190℃)② Melt Index 0.1 ~ 30g / 10min (190 ℃)

③ 밀도가 0.900g/㎤ 이하③ Density is 0.900g / cm3 or less

(E) 말레산 무수물을 그라프트(graft) 변성시킨 변성 폴리프로필렌 공중합체로서 하기의 조건 1∼2를 만족하는 것 :(E) Modified polypropylene copolymer in which maleic anhydride is graft-modified to satisfy the following conditions 1 to 2:

① 불포화 카르복실산 또는 그 유도체로 그라프트율이 0.1∼10몰%① Graft rate 0.1-10 mol% with unsaturated carboxylic acid or its derivative (s)

② 고유점도가 0.1∼2㎗/g② intrinsic viscosity 0.1∼2㎗ / g

(F) 가교분해제(F) crosslinking agent

본 발명의 다른 목적 및 적용은 하기 발명의 상세한 설명으로부터 당업자에게 명백해질 것이다.Other objects and applications of the present invention will become apparent to those skilled in the art from the following detailed description of the invention.

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

일반적으로 압출 라미네이션 가공에 적합한 기재로는 페트(PET), 연신 나이론(O-NYLON), 오피피(OPP), 셀로판, 금속박등이 있는데, 압출 라미네이션 가공은 상기한 기재에 저밀도 폴리에틸렌을 1차로 압출 라미네이션한 후, 특정의 수지 조성물을 2차 라미네이션시키는 방법을 주로 사용하고 있다. 또한 특수한 저온 가공용의 앙카코터제(A/C제)를 사용한 기재 위에 직접 특정 수지 조성물을 압출 라미네이션하는 방법도 있다.In general, suitable substrates for extrusion lamination include PET, stretched nylon (O-NYLON), OPP, cellophane, and metal foil. Extrusion lamination is the first extrusion of low density polyethylene onto the substrate. After lamination, the method of secondary laminating a specific resin composition is mainly used. There is also a method of extrusion lamination of a specific resin composition directly on a substrate using an anchor coater (made by A / C) for special low temperature processing.

그러나, 본 발명의 조성물은 저밀도 폴리에틸렌의 압출 라미네이션이나, 특수한 앙카코터제(A/C제)의 사용없이 기재에 직접 압출 라미네이션하여 우수한 막접착 강도를 유지할 수 있는 수지 조성물이다.However, the composition of the present invention is a resin composition capable of maintaining excellent film adhesion strength by extrusion lamination of low density polyethylene or extrusion lamination directly onto a substrate without the use of a special anchor coater (A / C).

본 발명자들은 폴리프로필렌계 압출 라미네이션용 수지 조성물의 제공을 위한 광범위한 실험을 통하여 다음과 같은 사실을 알아내었다. 즉, 적절한 보일링 및 레토르트 살균 및 저온 열봉합성을 가지기 위해서는 특정한 조성을 갖는 프로필렌계 랜덤 공중합체를 사용하고, 우수한 가공성을 위해서는 특정의 저밀도 폴리에틸렌 및 가교분해제를 사용하는 것이 필요하다. 또한 저온이면서 넓은 범위의 열봉합 온도를 갖는 이지필성을 부여하기 위해서는 특정의 폴리부텐과 무정형 또는 저결정성의 에틸렌계α-올레핀 랜덤 공중합체 또는 1-부텐α-올레핀 랜덤 공중합체를 사용하는 것이 필요하며, 단독으로 사용하는 것 보다는 2종을 혼용하여 사용하는 경우 이지필성이 더욱 상승됨을 알았다. 또한, 특수한 A/C제의 사용없이 기재에 직접 압출 라미네이션하여 우수한 막접착 강도를 유지할 수 있도록 하기 위해서는 말레산 무수물을 그라프트 변성시킨 변성 폴리프로필렌 공중합체를 사용해야 함을 알았다.The present inventors found out the following facts through extensive experiments for the provision of the resin composition for polypropylene extrusion lamination. That is, it is necessary to use a propylene random copolymer having a specific composition in order to have proper boiling and retort sterilization and low temperature heat sealing, and to use a specific low density polyethylene and a crosslinking agent for excellent processability. In addition, it is necessary to use a specific polybutene and an amorphous or low crystalline ethylene-α-olefin random copolymer or 1-buteneα-olefin random copolymer in order to impart easy peelability having a low temperature and a wide range of heat-sealing temperatures. In addition, it was found that the easy peel property was further increased when two kinds were used in combination rather than being used alone. In addition, it was found that a modified polypropylene copolymer graft-modified maleic anhydride should be used in order to maintain the excellent film adhesive strength by directly extrusion lamination onto a substrate without using a special A / C agent.

이와 같은 발견에 기초하여 본 발명은 결정성 폴리프로필렌 조성물 중 하기 성분 (A), (B), (C), (D), (E) 및 (F)를 함유하며, (A)의 함량이 40∼60중량부, (B)의 함량이 5∼20중량부, (C)의 함량이 20∼40중량부, (D)의 함량이 3∼15중량부, (E)의 함량이 2∼10중량부, 그리고 (F)의 함량이 0.001∼0.1중량부임을 특징으로 하는 저온 열봉합성 및 이지필성(easy peel)이 우수하며, 별도의 접착제 처리없이 기재에 직접 접착이 가능한 압출 라미네이션용 폴리프로필렌계 수지 조성물을 제공할 수 있다.Based on this finding, the present invention contains the following components (A), (B), (C), (D), (E) and (F) in the crystalline polypropylene composition, wherein the content of (A) 40 to 60 parts by weight, (B) is 5 to 20 parts by weight, (C) is 20 to 40 parts by weight, (D) is 3 to 15 parts by weight, and (E) is 2 to It is excellent in low temperature heat sealability and easy peel, characterized in that the content of 10 parts by weight and (F) of 0.001 to 0.1 parts by weight, and polypropylene for extrusion lamination that can be directly adhered to the substrate without additional adhesive treatment A system resin composition can be provided.

(A) 프로필렌과, 에틸렌 또는 1-부텐과의 이원 또는 삼원 공중합체로서 하기 조건 1∼3을 만족하는 것:(A) Binary or terpolymer of propylene and ethylene or 1-butene, satisfying the following conditions 1 to 3:

① 에틸렌 또는 1-부텐 단독 혹은 에틸렌과 1-부텐과의 합이 4∼15몰%① 4 to 15 mol% of ethylene or 1-butene alone or the sum of ethylene and 1-butene

② 용융온도가 135℃ 이하② Melt temperature is below 135 ℃

③ 용융지수가 5∼25g/10min(230℃)③ Melt index of 5 ~ 25g / 10min (230 ℃)

(B) 용융지수가 1∼15g/10min(190℃), 밀도가 0.925g/㎤ 이하인 저밀도 폴리에틸렌(B) low density polyethylene with a melt index of 1 to 15 g / 10 min (190 ° C.) and a density of 0.925 g / cm 3 or less

(C) 용융지수가 0.4∼20g/10min(190℃), 밀도가 0.915g/㎤ 이하인 폴리부텐(C) a polybutene having a melt index of 0.4 to 20 g / 10 min (190 ° C.) and a density of 0.915 g / cm 3 or less

(D) 무정형 또는 저결정성의 에틸렌계α-올레핀 랜덤 공중합체 또는 1-부텐α-올레핀 랜덤 공중합체로서 하기의 조건 1∼3을 만족하는 것 :(D) an amorphous or low crystalline ethylenic α-olefin random copolymer or 1-butene α-olefin random copolymer that satisfies the following conditions 1 to 3:

① α-올레핀의 탄소수가 2∼20① 2 to 20 carbon atoms of α-olefin

② 용융지수가 0.1∼30g/10min(190℃)② Melt Index 0.1 ~ 30g / 10min (190 ℃)

③ 밀도가 0.900g/㎤ 이하③ Density is 0.900g / cm3 or less

(E) 말레산 무수물을 그라프트(graft) 변성시킨 변성 폴리프로필렌 공중합체로서 하기의 조건 1∼2를 만족하는 것 :(E) Modified polypropylene copolymer in which maleic anhydride is graft-modified to satisfy the following conditions 1 to 2:

① 불포화 카르복실산 또는 그 유도체로 그라프트율이 0.1∼10몰%① Graft rate 0.1-10 mol% with unsaturated carboxylic acid or its derivative (s)

② 고유점도가 0.1∼2㎗/g② intrinsic viscosity 0.1∼2㎗ / g

(F) 가교분해제(F) crosslinking agent

상기 성분 중 결정성 폴리프로필렌 조성물 (A)의 경우는 프로필렌 단독 중합체로는 열봉합 온도를 135℃이하로 낮추는 것이 사실상 어려우므로, 에틸렌, 1-부텐 또는 이들의 혼합물과의 공중합체를 사용한다. 또한, 이들의 함량이 40중량부 미만인 경우에는 내열성이 부족하여 보일링 및 레토르트 살균에 적합하지 않으며, 70중량부 이상인 경우에는 고온이면서 좁은 범위의 열봉합 온도 범위로 인해 우수한 이지필성을 부여할 수 없다.In the case of the crystalline polypropylene composition (A) in the above components, since it is practically difficult to lower the heat-sealing temperature to 135 ° C or lower with the propylene homopolymer, a copolymer with ethylene, 1-butene or a mixture thereof is used. In addition, when the content thereof is less than 40 parts by weight, heat resistance is insufficient, which is not suitable for boiling and retort sterilization, and when it is 70 parts by weight or more, it can be given excellent easy peel property due to the high temperature and narrow heat sealing temperature range. none.

상기 (B)성분인 저밀도 폴리에틸렌 성분은 폴리프로필렌 중합체가 갖는 결점인 가공상의 넥크인(압출기 다이의 폭보다 압출된 필름의 폭이 좁아지는 현상), 위빙(필름의 폭이 일정하지 않은 현상) 및 서징(압출량이 일정하지 않아 인취방향으로 발생하는 두께의 불균일) 현상을 개선하기 위하여 5∼20중량부의 양으로 함유된다. (B)성분의 함량이 5중량부 미만인 경우에는 목적하는 효과를 달성하기 어렵고, 20중량부 이상인 경우에는 가공성은 우수하나, 이지필성이 적합하지 않고, 내열성의 부족으로 보일링 및 레토르트 살균에 적합하지 못하다.The low-density polyethylene component as the component (B) is a processing neck which is a drawback of the polypropylene polymer (a phenomenon in which the width of the extruded film becomes narrower than the width of the extruder die), a weaving (a phenomenon in which the width of the film is not constant), and It is contained in an amount of 5 to 20 parts by weight in order to improve the phenomenon of surging (a nonuniformity in thickness occurring in the take-off direction because the extrusion amount is not constant). When the content of the component (B) is less than 5 parts by weight, it is difficult to achieve the desired effect. When the content of the component (B) is 20 parts by weight or more, the workability is excellent, but the easy peel resistance is not suitable, and it is suitable for boiling and retort sterilization due to lack of heat resistance. I can't.

또한, 본 발명의 폴리프로필렌계 수지 조성물은 저온이면서 넓은 범위의 열봉합 온도를 갖기 위해서 (C) 성분인 폴리부텐을 20∼40중량부의 양으로 함유하는데, 함유량이 20중량부 미만인 경우 목적하는 효과를 달성하기 어렵고, 40중량부 이상인 경우에는 이지필성은 적합하나 가공성의 저하로 압출 라미네이션 수지 조성물로 적합하지 않다. 이때 사용되는 (C) 성분의 경우 밀도가 0.915g/㎤이하인 것이 좋으며, 바람직하게는 0.911g/㎤이하인 것이 좋다.In addition, the polypropylene resin composition of the present invention contains a polybutene (C) component in an amount of 20 to 40 parts by weight in order to have a low temperature and a wide range of heat-sealing temperature, the desired effect when the content is less than 20 parts by weight. It is difficult to achieve, and when it is 40 parts by weight or more, easy peelability is suitable, but it is not suitable as an extruded lamination resin composition due to deterioration of workability. In the case of the component (C) used at this time, the density is preferably 0.915 g / cm 3 or less, and preferably 0.911 g / cm 3 or less.

또한, 본 발명의 조성물은 상기 (A), (B) 및 (C)성분 이외에 (D)성분을 3∼15중량부로 함유하여, 가공성의 저하없이 이지필성에 적합한 수지 조성물을 제공할 수 있다. (D) 성분의 함량은 3중량부 이하인 경우 가공성의 개선 및 혼련효과를 기대할 수 없고, 15중량부 이상인 경우에는 내열성의 부족으로 보일링 및 레토르트 살균에 적합치 않으므로 3∼15중량부가 바람직하다.In addition, the composition of the present invention contains 3 to 15 parts by weight of component (D) in addition to the components (A), (B) and (C), and can provide a resin composition suitable for easy peelability without degrading workability. When the content of the component (D) is 3 parts by weight or less, improvement in workability and kneading effect cannot be expected. When the content of component (D) is 15 parts by weight or more, 3 to 15 parts by weight is preferable because it is not suitable for boiling and retort sterilization due to lack of heat resistance.

그러나, 상기 (A), (B) (C) 및 (D) 성분들로서는 접착제없이 기재에 직접 접착하는 것이 불가능하므로, 본 발명의 조성물은 (E)성분을 2∼10중량부의 양으로 함유한다. 함유량이 2중량부 미만인 경우에는 접착강도가 불량하고, 10중량부 이상인 경우에는 접착강도가 너무 우수하여 이지필성에 적합하지 않으므로 2∼10중량부의 양으로 함유하는 것이 바람직하다.However, since the above-mentioned (A), (B) (C) and (D) components cannot be directly adhered to the substrate without an adhesive, the composition of the present invention contains the (E) component in an amount of 2 to 10 parts by weight. . When the content is less than 2 parts by weight, the adhesive strength is poor, and when the content is 10 parts by weight or more, the adhesive strength is so excellent that it is not suitable for easy peelability, and therefore it is preferably contained in an amount of 2 to 10 parts by weight.

한편, 본 발명의 폴리프로필렌계 수지 조성물을 압출 라미네이션용으로 사용하기 위해서는 용융 흐름성이 중요한데, 이는 다음의 2가지 방법에 의해 달성될 수 있다. 첫째는 중합에 의해 용융지수가 10g/10min 이상되는 수지를 중합하는 방법이고, 둘째는 가교분해제에 의해 용융지수를 올리는 방법으로, 본 발명에서는 후자의 방법을 채택하였다. 그러나 본 발명의 특징인 특정 용융지수를 갖는 폴리프로필렌의 제공이 상기 방법에만 제한되는 것은 아니다.On the other hand, in order to use the polypropylene resin composition of the present invention for extrusion lamination, melt flowability is important, which can be achieved by the following two methods. The first method is to polymerize a resin having a melt index of 10 g / 10 min or more by polymerization, and the second method is to raise a melt index by a crosslinking agent. However, the provision of polypropylene with a particular melt index, which is a feature of the invention, is not limited to this method.

본 발명에서 특정 용융지수를 갖는 폴리프로필렌계 수지를 제공하기 위해 사용할 수 있는 가교분해제(F)로는 특별히 한정되지는 않지만, 예를들면, 메틸에틸케톤퍼옥사이드, 메틸이소부틸케톤퍼옥사이드 등의 케톤퍼옥사이드류; 2,4,4-트리메틸펜틸-2-하이드로퍼옥사이드, 디이소프로필벤젠하이드로퍼옥사이드 등의 하이드로퍼옥사이드류; 이소부틸퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드, 벤조일퍼옥사이드, 1,3-비스(터셔리-부틸퍼옥시이소프로필렌)벤젠, 2,5-디메틸-2,5-디(터셔리부틸퍼옥시)헥산 등의 디아실퍼옥사이드류; 1,1-디-터셔리-부틸퍼옥시-3,3,5-트리메틸사이클헥산, 2,2-디-(터셔리부틸퍼옥시)부탄 등의 퍼옥시케탈류; 2,2,4-트리메틸펜틸퍼옥시네오데칸노에이트, 터셔리-부틸퍼옥시-네오데칸노에이트 등의 알킬퍼에스테르류; 및 디-3-메톡시부틸퍼옥시디카보네이트, 터셔리퍼옥시부틸퍼옥시이소프로필카보네이트 등의 퍼카보네이트류가 있다. 그러나 본 발명은 이들 예에만 한정되는 것은 아니다.Although it does not specifically limit as a crosslinking | decomposing agent (F) which can be used in order to provide the polypropylene resin which has a specific melt | dissolution index in this invention, For example, methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, etc. Ketone peroxides; Hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide and diisopropylbenzenehydroperoxide; Isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,3-bis (tert-butylperoxyisopropylene) benzene, 2,5-dimethyl-2,5-di (tert-butyl Diacyl peroxides such as peroxy) hexane; Peroxy ketals such as 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclehexane and 2,2-di- (tertarybutylperoxy) butane; Alkyl peresters such as 2,2,4-trimethylpentyl peroxy neodecannoate and tertiary-butyl peroxy-neodecannoate; And percarbonates such as di-3-methoxybutyl peroxydicarbonate and tertiary oxybutyl peroxy isopropyl carbonate. However, the present invention is not limited only to these examples.

상기 (F)성분인 가교분해제는 전체 수지 조성물의 0.001∼0.1중량부의 양으로 사용할 수 있으며, 0.001중량부 미만인 경우에는 용융지수를 15g/10min이상 올리기 어려우며, 가공성의 저하와 서징현상이 발생한다. 또한 0.1중량부 이상인 경우에는 폴리프로필렌 중합체의 과다분해로 폴리프로필렌 중합체의 기본 특성을 저해하는 동시에 (B), (C), (D)성분들의 용융 흐름성 저하로 인하여 압출 가공시 서징, 넥크인 현상이 발생한다.The cross-linking agent as the component (F) may be used in an amount of 0.001 to 0.1 parts by weight of the entire resin composition, and when it is less than 0.001 parts by weight, it is difficult to raise the melt index by 15 g / 10 min or more, and workability decreases and surging occurs. . In addition, when the content is 0.1 parts by weight or more, the polypropylene polymer may be excessively decomposed to inhibit the basic properties of the polypropylene polymer, and at the same time, the surging and the neck may be reduced during extrusion due to the reduced melt flowability of the components (B), (C) and (D). Phenomenon occurs.

이하 실시예를 통하여 본 발명을 구체화시키고자 한다.The present invention will be embodied through the following examples.

하기의 실시예 및 비교예에서 채택한 각종 물성의 평가 방법은 다음의 시험법에 의해 행하였다.The evaluation method of the various physical properties adopted by the following example and the comparative example was performed by the following test method.

1) 용융지수는 ASTM D-1238법으로 측정하였다.1) Melt index was measured by ASTM D-1238.

2) 가공성은 네크인을 측정하였으며, 그 방법으로는 용융지수가 압출되는 다이스폭과 압출 라미네이션 가공후의 라미네이팅 폭과의 차이를 측정하였다.2) The machinability was measured by the neck-in, and the method measured the difference between the die width where the melt index is extruded and the lamination width after extrusion lamination processing.

3) 열봉합 온도는 20㎛ 두께의 연신나이론 필름 위에 저밀도 폴리에틸렌을 20㎛ 두께로 라미네이션한 후, 본 발명의 수지 조성물들을 20㎛ 두께로 2차 압출 라미네이션하여 23±1℃ 온도 및 50±5% 습도의 항온항습실에 24시간 방치한 후, 열봉합 온도 측정기를 사용하여 두 개의 시편을 압력 3㎏/㎤, 시간 1초에서 온도가 경사진 5개의 금속 표면에 의해 접착시킨 후 인장 시험기로 인장 실험속도 300mm/min으로 실시하였을때 600g의 힘이 걸리는 온도를 측정하였다.3) The heat-sealing temperature is a low-density polyethylene of 20㎛ thickness on a 20㎛ thick stretched nylon film, and then the resin composition of the present invention to 20㎛ thickness secondary extrusion lamination to 23 ± 1 ℃ temperature and 50 ± 5% After standing in a constant temperature and humidity room for 24 hours, two specimens were bonded to each other by using a heat-sealing temperature meter at a pressure of 3 kg / cm 3 and 5 seconds at a temperature of 1 second. When the speed was performed at 300 mm / min, the temperature at which a force of 600 g was applied was measured.

4) 내열성은 한미 HI-TECH사 제품인 가압식 증기 살균기를 사용하여 110℃에서 20분간 가압 살균을 행하는 레토르트 살균방법을 택하였으며, 필름의 외관, 열봉합 부위의 변형 유무를 관찰하였다.4) The heat resistance was selected by the retort sterilization method, which was autoclaved at 110 ° C. for 20 minutes using a pressurized steam sterilizer manufactured by Hanmi HI-TECH. The appearance of the film and deformation of the heat seal were observed.

5) 이지필후 계면 외관의 양호 정도 및 이지필시 관능적인 힘의 정도를 측정하였다.5) After the easy peel, the degree of good interface appearance and the sensory force during easy peel were measured.

6) 막접착 강도는 20㎛ 두께의 연신나이론 필름 위에 본 발명의 수지 조성물들을 20㎛ 두께로 압출 라미네이션시킨 다음, 23±1℃ 온도 및 50±5% 습도의 항온항습실에 24시간 방치한 후, 20mm 폭으로 만든 시편을 인장 시험기로 인장 실험속도 300mm/min으로 실시하였을때 걸리는 강도를 측정하였다.6) The film adhesion strength is extruded lamination of the resin compositions of the present invention to 20㎛ thickness on a stretched nylon film of 20㎛ thickness, then left in a constant temperature and humidity chamber of 23 ± 1 ℃ temperature and 50 ± 5% humidity for 24 hours, 20 mm width specimen was measured using a tensile tester at a tensile test rate of 300 mm / min.

[실시예 1]Example 1

(A)성분으로서 용융지수가 16g/10min(230℃), 용융온도가 132℃, 비카트 연화점이 124℃, 에틸렌 함유량이 3.0몰%, 1-부텐 함유량이 5.0몰%인 프로필렌-에틸렌-1-부텐 삼원공중합체 분말 50중량부, (B)성분으로서 용융지수가 8g/10min(190℃), 그리고 밀도가 0.920g/㎤인 저밀도 폴리에틸렌 15중량부, (C)성분으로서 용융지수가 2g/10min(190℃), 그리고 밀도가 0.911g/㎤인 폴리부텐 25중량부, (D)성분으로서 에틸렌 함량 70몰%인 에틸렌-프로필렌 공중합체 10중량부, (E)성분으로서 고유점도가 0.4㎗/g이고 말레산 무수물 그라프트율이 3%로 변성시킨 말레산 무수물 변성 폴리프로필렌 공중합체 5중량부, 그리고 (F)성분으로서 1,3-비스-(터셔리-부틸퍼옥시-이소프로필렌)벤젠 0.01중량부, 페놀계 산화방지제 0.1중량부 및 칼슘스테아레이트 0.1중량부의 양으로 첨가하고 헨셀 믹서로 약 5분간 믹싱한후 압출기로 200∼210℃에서 압출하여 펠렛상의 조성물을 얻었다. 얻어진 조성물의 각종 물성을 상기 서술한 방법에 따라 측정하고, 그 결과를 표 1에 나타내었다.(A) As the component, propylene-ethylene-1 having a melt index of 16 g / 10 min (230 ° C.), a melting temperature of 132 ° C., a vicat softening point of 124 ° C., an ethylene content of 3.0 mol% and a 1-butene content of 5.0 mol%. 50 parts by weight of butene terpolymer powder, (B) component having a melt index of 8 g / 10 min (190 DEG C), 15 parts by weight of low density polyethylene having a density of 0.920 g / cm 3, and a component of (C) having a melt index of 2 g / 10 parts by weight (190 ° C.), 25 parts by weight of polybutene having a density of 0.911 g / cm 3, 10 parts by weight of an ethylene-propylene copolymer having an ethylene content of 70 mol% as the component (D), and an intrinsic viscosity of 0.4 kPa as the component (E). 5 parts by weight of a maleic anhydride-modified polypropylene copolymer modified with a maleic anhydride graft ratio of 3 g / g and (F) component 1,3-bis- (tertary-butylperoxy-isopropylene) benzene 0.01 Add 5 parts by weight, 0.1 part by weight of phenolic antioxidant and 0.1 part by weight of calcium stearate, and use the Henschel mixer for about 5 minutes. After mixing with each other, it extruded at 200-210 degreeC with the extruder, and obtained the composition of a pellet form. Various physical properties of the obtained composition were measured in accordance with the method described above, and the results are shown in Table 1.

[실시예 2∼6]EXAMPLES 2-6

실시예 1에 있어서, (A), (B), (C), (D), (E) 및 (F)의 함량을 하기 표 1에 기재된 바와 같이 변화시키는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, the same as in Example 1 except that the content of (A), (B), (C), (D), (E) and (F) was changed as described in Table 1 below. To obtain a composition, and to measure the physical properties thereof are shown in Table 1.

[실시예 7]Example 7

실시예 1에 있어서, (A)성분으로서 용융지수가 16g/10min(230℃), 용융온도가 135℃, 비카트 연화점이 126℃, 1-부텐 함유량이 12몰%인 프로필렌-1-부텐의 랜덤 이원공중합체 분말 50중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, propylene-1-butene having a melt index of 16 g / 10 min (230 ° C.), a melting temperature of 135 ° C., a vicat softening point of 126 ° C., and a 1-butene content of 12 mol% as (A) component. Except for using 50 parts by weight of random binary copolymer powder was carried out in the same manner as in Example 1 to obtain a composition, the results of measuring the physical properties are shown in Table 1.

[실시예 8]Example 8

실시예 1에 있어서, (A)성분으로서 용융지수가 16g/10min(230℃), 용융온도가 132℃, 비카트 연화점이 123℃, 에틸렌 함유량이 7몰%인 프로필렌-에틸렌의 랜덤 이원공중합체 분말 50중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, as the component (A), a random copolymer of propylene-ethylene having a melt index of 16 g / 10 min (230 ° C.), a melting temperature of 132 ° C., a vicat softening point of 123 ° C., and an ethylene content of 7 mol%. Except that 50 parts by weight of powder was used in the same manner as in Example 1 to obtain a composition, the physical properties of the results are shown in Table 1.

[실시예 9]Example 9

실시예 1에 있어서, (B)성분으로서 용융지수가 14g/10min(190℃), 밀도가 0.920g/㎤인 저밀도 폴리에틸렌을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, the composition was obtained in the same manner as in Example 1 except that a low density polyethylene having a melt index of 14 g / 10 min (190 ° C.) and a density of 0.920 g / cm 3 was used as the component (B). The results of measuring their physical properties are shown in Table 1.

[실시예 10]Example 10

실시예 1에 있어서, (C)성분으로서 용융지수가 18g/10min(190℃), 밀도가 0.911g/㎤인 폴리부텐을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고. 그의 물성을 측정한 결과를 표 1에 나타내었다.The composition was obtained in the same manner as in Example 1, except that polybutene having a melt index of 18 g / 10 min (190 ° C.) and a density of 0.911 g / cm 3 was used as component (C). The results of measuring their physical properties are shown in Table 1.

[실시예 11]Example 11

실시예 1에 있어서, (D)성분으로서 에틸렌 함량이 70몰%인 에틸렌-1-부텐 공중합체를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, the composition was obtained in the same manner as in Example 1 except that the ethylene-1-butene copolymer having an ethylene content of 70 mol% was used as the component (D), and the physical properties thereof were measured. Is shown in Table 1.

[비교예 1∼10]Comparative Examples 1 to 10

실시예 1에 있어서, (A), (B), (C), (D), (E) 및 (F)의 함량을 하기 표 1에 기재된 바와 같이 변화시키는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성 측정한 결과를 표 1에 나타내었다.In Example 1, the same as in Example 1 except that the content of (A), (B), (C), (D), (E) and (F) was changed as described in Table 1 below. To obtain a composition, and the results of measuring physical properties thereof are shown in Table 1.

[비교예 11]Comparative Example 11

실시예 1에 있어서, (A)성분으로서 용융지수가 4g/10min(230℃), 용융온도가 135℃, 비카트 연화점이 126℃, 1-부텐 함유량이 12몰%인 프로필렌-1-부텐의 랜덤 이원공중합체 분말 50중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, propylene-1-butene having a melt index of 4 g / 10 min (230 ° C.), a melting temperature of 135 ° C., a vicat softening point of 126 ° C., and a 1-butene content of 12 mol% as (A) component. Except for using 50 parts by weight of random binary copolymer powder was carried out in the same manner as in Example 1 to obtain a composition, the results of measuring the physical properties are shown in Table 1.

[비교예 12]Comparative Example 12

실시예 1에 있어서, (A)성분으로서 용융지수가 30g/10min(230℃), 용융온도가 135℃, 비카트 연화점이 126℃, 1-부텐 함유량이 12몰%인 프로필렌-1-부텐의 랜덤 이원공중합체 분말 50중량부를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, as the component (A), propylene-1-butene having a melt index of 30 g / 10 min (230 ° C.), a melting temperature of 135 ° C., a vicat softening point of 126 ° C., and a 1-butene content of 12 mol%. Except for using 50 parts by weight of random binary copolymer powder was carried out in the same manner as in Example 1 to obtain a composition, the results of measuring the physical properties are shown in Table 1.

[비교예 13]Comparative Example 13

실시예 1에 있어서, (B)성분으로서 용융지수가 25g/10min(190℃), 밀도가 0.920g/㎤인 저밀도 폴리에틸렌을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, the composition was obtained in the same manner as in Example 1 except that a low density polyethylene having a melt index of 25 g / 10 min (190 ° C.) and a density of 0.920 g / cm 3 was used as the component (B). The results of measuring their physical properties are shown in Table 1.

[비교예 14]Comparative Example 14

실시예 1에 있어서, (C)성분으로서 용융지수가 0.2g/10min(190℃), 밀도가 0.911g/㎤인 폴리부텐을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, the composition was obtained in the same manner as in Example 1 except that polybutene having a melt index of 0.2 g / 10 min (190 ° C.) and a density of 0.911 g / cm 3 was used as the component (C). And the results of measuring their physical properties are shown in Table 1.

[비교예 15]Comparative Example 15

실시예 1에 있어서, (C)성분으로서 용융지수가 25g/10 min(190℃), 밀도가 0.911g/㎤인 폴리부텐을 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, the composition was obtained in the same manner as in Example 1 except that polybutene having a melt index of 25 g / 10 min (190 ° C) and a density of 0.911 g / cm 3 was used as the component (C). And the results of measuring their physical properties are shown in Table 1.

[비교예 16][Comparative Example 16]

실시예 1에 있어서, (D)성분으로서 용융지수가 35g/10 min(190℃), 에틸렌 함량이 70몰%인 에틸렌-프로필렌 공중합체를 사용하는 것을 제외하고는 실시예 1과 동일하게 실시하여 조성물을 얻고, 그의 물성을 측정한 결과를 표 1에 나타내었다.In Example 1, (D) was carried out in the same manner as in Example 1 except for using the ethylene-propylene copolymer having a melt index of 35g / 10 min (190 ℃), ethylene content of 70 mol% as (D) The composition was obtained, and the result of having measured the physical property is shown in Table 1.

[표1]Table 1

구분division AA BB CC DD EE FF 용융지수Melt index 열봉합온도Heat seal temperature 막접착강도Membrane adhesion strength 가공성Machinability 내열성Heat resistance 이지필성Ji Pil Sung 중량부Parts by weight g/10ming / 10min g/15mmg / 15mm ◎ 매우 양호,○ 양호, × 불량◎ Very good, ○ Good, × Bad 실시예 1Example 1 5050 1010 2525 1010 55 0.010.01 2020 116116 25002500 실시예 2Example 2 5050 1010 3030 55 55 0.010.01 1919 118118 22002200 실시예 3Example 3 4545 2020 2020 1010 55 0.010.01 2020 115115 27002700 실시예 4Example 4 5050 2020 2020 55 55 0.010.01 1818 120120 22002200 실시예 5Example 5 5050 1010 2525 1010 55 0.0030.003 1616 116116 22002200 실시예 6Example 6 5050 1010 2525 1010 55 0.080.08 3232 116116 21002100 실시예 7Example 7 5050 1010 2525 1010 55 0.010.01 2020 116116 26002600 실시예 8Example 8 5050 1010 2525 1010 55 0.010.01 2020 115115 24002400 실시예 9Example 9 5050 1010 2525 1010 55 0.010.01 2222 116116 25002500 실시예10Example 10 5050 1010 2525 1010 55 0.010.01 2323 116116 26002600 실시예11Example 11 5050 1010 2525 1010 55 0.010.01 2020 116116 27002700 비교예 1Comparative Example 1 5050 1010 2525 1010 55 ­­ 1212 116116 25002500 ×× 비교예 2Comparative Example 2 5555 1010 2525 1010 ­­ 0.010.01 1818 120120 150150 ×× 비교예 3Comparative Example 3 5050 1010 2525 1010 55 0.00080.0008 1313 120120 25002500 ×× 비교예 4Comparative Example 4 5050 1010 2525 1010 55 0.150.15 4747 120120 23002300 ×× 비교예 5Comparative Example 5 54.254.2 1010 2525 1010 0.80.8 0.010.01 1818 119119 220220 ×× 비교예 6Comparative Example 6 4040 1010 2525 1010 1515 0.010.01 2222 114114 30003000 ×× ×× 비교예 7Comparative Example 7 6868 1010 1515 22 55 0.010.01 2020 124124 23002300 ×× ×× 비교예 8Comparative Example 8 3030 1515 4040 1010 55 0.010.01 1414 112112 22002200 ×× ×× 비교예 9Comparative Example 9 5050 33 3232 1010 55 0.010.01 1616 118118 20002000 ×× 비교예10Comparative Example 10 5050 1515 1010 2020 55 0.010.01 1515 116116 24002400 ×× ×× 비교예11Comparative Example 11 5050 1010 2525 1010 55 0.010.01 1010 118118 24002400 ×× 비교예12Comparative Example 12 5050 1010 2525 1010 55 0.010.01 2626 116116 22002200 ×× 비교예13Comparative Example 13 5050 1010 2525 1010 55 0.010.01 2222 116116 22002200 ×× ×× 비교예14Comparative Example 14 5050 1010 2525 1010 55 0.010.01 1818 116116 24002400 ×× ×× 비교예15Comparative Example 15 5050 1010 2525 1010 55 0.010.01 2626 116116 24002400 ×× ×× 비교예16Comparative Example 16 5050 1010 2525 1010 55 0.010.01 2626 116116 24002400 ×× ××

이상에서 설명한 바와 같이, 본 발명의 압출 라미네이션용 수지 조성물은 저온 열봉합성 및 이지필성이 우수하고, 또한 별도의 접착제 처리없이 기재에 직접 접착이 가능하다.As described above, the resin composition for extrusion lamination of the present invention is excellent in low-temperature heat sealability and easy peelability, and can be directly adhered to a substrate without additional adhesive treatment.

Claims (1)

압출 라미네이션용 수지 조성물에 있어서,In the resin composition for extrusion lamination, 하기 (A)성분 40∼60중량부, (B)성분 5∼20중량부, (C)성분 20∼40중량부, (D)성분 3∼15중량부, (E)성분 2∼10중량부 및 (F)성분 0.001∼0.1중량부를 함유함을 특징으로 하는 압출 라미네이션용 폴리프로필렌계 수지 조성물.The following (A) component 40-60 weight part, (B) component 5-20 weight part, (C) component 20-40 weight part, (D) component 3-15 weight part, (E) component 2-10 weight part And 0.001 to 0.1 parts by weight of component (F). (A) 프로필렌과, 에틸렌 또는 1-부텐과의 이원 또는 삼원 공중합체로서 하기 조건 1∼3을 만족하는 것:(A) Binary or terpolymer of propylene and ethylene or 1-butene, satisfying the following conditions 1 to 3: ① 에틸렌 또는 1-부텐 단독 혹은 에틸렌과 1-부텐과의 합이 4∼15몰%① 4 to 15 mol% of ethylene or 1-butene alone or the sum of ethylene and 1-butene ② 용융온도가 135℃ 이하② Melt temperature is below 135 ℃ ③ 용융지수가 5∼25g/10min(230℃)③ Melt index of 5 ~ 25g / 10min (230 ℃) (B) 용융지수가 1∼15g/10min(190℃), 밀도가 0.925g/㎤ 이하인 저밀도 폴리에틸렌(B) low density polyethylene with a melt index of 1 to 15 g / 10 min (190 ° C.) and a density of 0.925 g / cm 3 or less (C) 용융지수가 0.4∼20g/10min(190℃), 밀도가 0.915g/㎤ 이하인 폴리부텐(C) a polybutene having a melt index of 0.4 to 20 g / 10 min (190 ° C.) and a density of 0.915 g / cm 3 or less (D) 무정형 또는 저결정성의 에틸렌계α-올레핀 랜덤 공중합체 또는 1-부텐α-올레핀 랜덤 공중합체로서 하기의 조건 1∼3을 만족하는 것 :(D) an amorphous or low crystalline ethylenic α-olefin random copolymer or 1-butene α-olefin random copolymer that satisfies the following conditions 1 to 3: ① α-올레핀의 탄소수가 2∼20① 2 to 20 carbon atoms of α-olefin ② 용융지수가 0.1∼30g/10min(190℃)② Melt Index 0.1 ~ 30g / 10min (190 ℃) ③ 밀도가 0.900g/㎤ 이하③ Density is 0.900g / cm3 or less (E) 말레산 무수물을 그라프트(graft) 변성시킨 변성 폴리프로필렌 공중합체로서 하기의 조건 1∼2를 만족하는 것 :(E) Modified polypropylene copolymer in which maleic anhydride is graft-modified to satisfy the following conditions 1 to 2: ① 불포화 카르복실산 또는 그 유도체로 그라프트율이 0.1∼10몰%① Graft rate 0.1-10 mol% with unsaturated carboxylic acid or its derivative (s) ② 고유점도가 0.1∼2㎗/g② intrinsic viscosity 0.1∼2㎗ / g (F) 가교분해제(F) crosslinking agent
KR1019970005234A 1997-02-21 1997-02-21 Resin compositions for manufacturing extrusion laminate having a low temperature thermosealing KR100188179B1 (en)

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KR101738723B1 (en) * 2013-11-29 2017-05-22 롯데케미칼 주식회사 Low temperature heat-sealing properties of atactic-polypropylene resin composition

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HUE050157T2 (en) * 2017-10-26 2020-11-30 Amcor Flexibles Singen Gmbh Composite film
KR102106711B1 (en) * 2018-10-19 2020-05-04 한화토탈 주식회사 Polyolefin Resin Composition for a Sealant Layer of a Peelable Film and Peelable Film Comprising a Sealant Layer Prepared Therefrom

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