KR20020006982A - Polyolefin resin composition for a blown film having a matt property, and a matt film using it - Google Patents

Polyolefin resin composition for a blown film having a matt property, and a matt film using it Download PDF

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KR20020006982A
KR20020006982A KR1020000040613A KR20000040613A KR20020006982A KR 20020006982 A KR20020006982 A KR 20020006982A KR 1020000040613 A KR1020000040613 A KR 1020000040613A KR 20000040613 A KR20000040613 A KR 20000040613A KR 20020006982 A KR20020006982 A KR 20020006982A
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film
resin
ethylene
matte
melt index
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Korean (ko)
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이규종
이장원
임용수
이태근
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유승렬
에스케이 주식회사
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    • 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
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/14Peroxides
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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
    • C08L23/06Polyethene
    • 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
    • C08L23/16Elastomeric 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
    • C08L2203/00Applications
    • C08L2203/16Applications used for films
    • CCHEMISTRY; METALLURGY
    • 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
    • CCHEMISTRY; METALLURGY
    • 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

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

PURPOSE: A polyolefin resin composition for a flat blown film and a flat film prepared by using the composition are provided, to reduce the gloss of the surface of a film, thereby improving the value and merchantability of products. CONSTITUTION: The polyolefin resin composition comprises 30-70 wt% of a copolymer resin of an α-olefin of C1-C10 and ethylene or an ethylene homopolymer resin which has a melt index of 0.01-0.4 g/10 min and a density of 0.930-0.970 g/cm¬3; 30-70 wt% of an impact polypropylene resin which comprises an ethylene-propylene copolymer and has a melt index of 0.1-10 g/10 min, or random polypropylene resin which comprises ethylene and/or 1-butene and has a melt index of 0.1-10 g/10 min; and optionally 10-300 ppm of peroxides. The flat film is prepared by blow molding the composition to form a surface layer of a product. Preferably the extrusion temperature is 180-250 deg.C.

Description

무광특성을 갖는 블로운 필름용 폴리올레핀 수지 조성물 및 이를 이용하여 제조된 무광택 필름 {Polyolefin resin composition for a blown film having a matt property, and a matt film using it}Polyolefin resin composition for a blown film having a matte property and a matte film manufactured using the same {Polyolefin resin composition for a blown film having a matt property, and a matt film using it}

본 발명은 무광특성을 갖는 블로운 필름용 폴리올레핀 수지 조성물 및 이를 이용하여 제조된 무광택 필름에 관한 것으로, 좀 더 상세하게는 블로운 필름 성형방법으로 필름제조가 가능하며 무광특성이 우수한 폴리올레핀 수지 조성물 및 이를 블로운 필름 성형방법을 이용하여 제조하는 무광택 필름에 관한 것이다.The present invention relates to a polyolefin resin composition for a blown film having a matte property and a matte film prepared using the same, and more particularly, to a polyolefin resin composition capable of producing a film by a blown film forming method and having excellent matte properties. It relates to a matte film produced using a blown film forming method.

폴리올레핀 수지는 경제적인 면과 기능적인 면에서 균형을 이루는 수지로서, 이러한 폴리올레핀 수지로 제조된 필름은 기계적, 열적, 전기적 특성이 우수하고, 내약품성 및 성형성이 뛰어나 식품포장, 상품포장 및 종이 등의 다른 소재의 코팅재료로서 전세계적으로 광범위하게 사용되고 있다. 그 중에서도 근래에는 표면 광택이 적고 필름에 부드러운 감촉을 부여하여 포장된 소재의 상품성을 높여주는 무광택 필름(matt film)이 고부가가치 상품으로 널리 사용되고 있는데, 이러한 무광택 필름은 통상적으로 폴리올레핀 수지를 캐스팅 방법을 이용하여 제조하고 있다.Polyolefin resin is a resin that balances economic and functional aspects. Films made of such polyolefin resin have excellent mechanical, thermal, and electrical properties, and are excellent in chemical resistance and formability, such as food packaging, product packaging, and paper. It is widely used worldwide as a coating material for other materials. In particular, matte films, which have a low surface gloss and impart a soft touch to the film to enhance the merchandise of the packaged material, are widely used as high value-added commodities. It manufactures using.

무광택 현상은 반사 표면의 요철에 의한 난반사 현상에 기인하는 것으로, 필름의 표면에 무광특성을 부여하기 위해서는 하기 기재된 방법을 사용할 수 있다.Matte development is caused by the diffuse reflection phenomenon by the unevenness | corrugation of a reflective surface, and the method described below can be used in order to provide a matte characteristic to the surface of a film.

첫째, 일반 필름의 표면을 코팅 및 에칭 등의 방법으로 표면처리하는 방법,First, the surface treatment of the surface of the general film by a method such as coating and etching,

둘째, 비상용성을 갖는 수지 혼합물의 특징인, 혼합된 수지간의 흐름성, 수축율 및 굴절율 차이를 이용하는 방법,Secondly, a method using the flowability, shrinkage and refractive index difference between the mixed resins, which is characteristic of the resin mixture having incompatibility;

셋째, 무기물을 활용하여 표면에 요철을 부여하는 방법, 및Third, a method of applying unevenness to the surface by using inorganic materials, and

넷째, 냉각롤에 요철을 주어 엠보싱 처리하는 방법.Fourth, the embossing process by giving unevenness to the cooling roll.

일반적으로, 상기 첫번째 방법은 코팅 및 건조 설비 등의 후가공 설비가 별도로 필요하여 흔히 이용되지 않고, 상업적으로는 상기 둘째, 셋째, 넷째의 방법, 및 이들의 혼합방법을 사용하고 있다.In general, the first method is not commonly used because it requires a separate post-processing equipment, such as coating and drying equipment, commercially, the second, third, fourth method, and mixing methods thereof are used.

또한, 폴리올레핀 필름의 제조방법은 크게 세 가지로 나누어 볼 수 있는데, 혼합수지의 용융지수(meld index, MI) 차이가 클수록 유리한 무광특성을 얻기 위해 통상적으로 많이 사용하지만, 일반적으로 연신공정을 필요로 하기 때문에 연신공정에서 가공안정성이 일정 수준이상이 되도록 조정해야 하는 한계가 있는 일자형 다이(T-die)를 이용하는 캐스팅 성형방법; 제조설비가 저렴하고 인열강도의 발란스가 양호하여 충격강도 및 인열강도가 우수하기 때문에 많이 사용되는, 둥근 다이를 사용하는 블로운 필름(blown film) 성형방법 및 연신과정이 필요 없고 버블 안정성이 비교적 양호하며 또한 가공기기도 다른 방법의 기기들에 비해 상대적으로 저렴한 인플레이션 필름(inflation film) 성형방법이 있다.In addition, a method of manufacturing a polyolefin film can be broadly divided into three types. The larger the melt index (MI) of the mixed resin is, the more commonly used to obtain advantageous matt characteristics, but generally requires a drawing process. Cast molding method using a straight die (T-die) has a limit to be adjusted so that the processing stability in the stretching process to a certain level or more; Because of low cost of manufacturing equipment and good balance of tear strength, excellent impact strength and tear strength, there is no need for blow film forming method and drawing process using round die, which is widely used. There is a relatively good method of forming an inflation film, which is also relatively inexpensive compared to other methods.

그 중 상기 블로운 필름 성형방법은 버블(bubble)의 연신을 통하여 필름을 제조하기 때문에 사용되는 수지의 버블 안정성이 일정 수준이상이 되어야 하는 한계가 있었다.Among them, the blown film forming method has a limitation in that the bubble stability of the resin to be used is higher than or equal to a predetermined level because the film is manufactured by stretching the bubble.

미국특허 제5,560,885호에는, 폴리올레핀 혼합물을 이용하여 무광특성을 갖는 수지 조성물 및 이의 성형기술이 기재되어 있다. 상기 특허에 게시된 내용에 의하면, 상기 수지 조성물은 비상용성을 가지는 에틸렌-알파올레핀 코폴리머와 프로필렌-알파올레핀 코폴리머 또는 그들의 터폴리머 블렌드를 이용하고, 캐스팅 성형방법에 의한 시트 생산 이후, 이축연신하는 방법을 사용하고 있고, 이 때의 연신온도는 40∼100℃이며 연신비는 32배 내지 70배이다. 또한, 사용하는 수지의 MI(용융지수)는 1.5g/min∼12g/min이며 바람직하게는 2.5∼6g/min이라고 알려져 있다.US Pat. No. 5,560,885 describes a resin composition having matt properties and a molding technique thereof using a polyolefin mixture. According to the contents disclosed in the patent, the resin composition is biaxially stretched after sheet production by a casting molding method using an incompatible ethylene-alpha olefin copolymer and propylene-alpha olefin copolymer or a terpolymer blend thereof In this case, the stretching temperature is 40 to 100 占 폚 and the stretching ratio is 32 to 70 times. In addition, MI (melt index) of resin to be used is 1.5 g / min-12 g / min, Preferably it is known as 2.5-6 g / min.

또한, 미국특허 제5,473,016호에는 무광특성을 갖는 필름이나 시트를 생산할 수 있는 수지 조성물에 관해 기재되어 있는데, 이러한 수지 혼합물은 1) MI가 1∼20g/min인 폴리올레핀 공중합체 10∼80중량%, 2) 밀도가 0.86∼0.91g/cm3인 수퍼 저밀도 에틸렌-알파올레핀 공중합체 5∼30중량%, 및 3) MI가 0.1∼2.0g/10min인 변형된 폴리올레핀 수지 5∼85중량%로 이루어지며, 캐스팅 방법에 의해 필름을 제조한다.In addition, U. S. Patent No. 5,473, 016 describes a resin composition capable of producing a film or sheet having matt properties, such a resin mixture comprising: 1) 10 to 80% by weight of a polyolefin copolymer having a MI of 1 to 20 g / min, 2) 5-30% by weight of a super low density ethylene-alphaolefin copolymer having a density of 0.86-0.91 g / cm 3 , and 3) 5-85% by weight of a modified polyolefin resin having a MI of 0.1-2.0 g / 10min. , The film is produced by the casting method.

상기 종래 문헌들을 통해 볼 수 있는 캐스팅 방법으로 제조된 필름은 일축 또는 이축연신의 영향으로 인해, 인열강도 및 충격강도가 약한 단점이 있으며, 공정이 복잡하고 초기 투자비가 많이 드는 단점이 있으며, 캐스팅 방법으로 제조한 필름은 쇼핑백 등 포장용 봉투 제조시 2차 실링공정이 필요한 단점을 갖는다.Film produced by the casting method can be seen through the conventional literature, due to the effect of uniaxial or biaxial stretching, has a disadvantage of weak tear strength and impact strength, the process is complicated and the initial investment costs a lot of disadvantages, casting The film produced by the method has a disadvantage in that a second sealing process is required when manufacturing a packaging bag such as a shopping bag.

또한, 미국특허 제3,361,704호에는 무기물을 첨가하여 폴리올레핀 필름에 무광 특성을 부여하는 방법이 기재되어 있는데, 무기물을 30∼80% 첨가하는 경우는 수지와 상용성이 전혀 없는 무기물에 의한 물성 저하 현상이 나타남으로써 인열, 인장, 충격강도 등이 저하되고, 무기물 혼합을 위한 별도의 (컴파운딩) 장비가 필요한 문제점이 있다.In addition, U.S. Patent No. 3,361,704 describes a method of adding matte properties to a polyolefin film by adding an inorganic material. In the case of adding 30 to 80% of an inorganic material, there is a phenomenon of deterioration of physical properties due to an inorganic material having no compatibility with a resin. By appearing, tearing, tensile strength, impact strength is lowered, there is a problem that requires a separate (compounding) equipment for mixing the inorganic material.

또한, 본출원인에 의해 출원된 한국특허출원 제2000-32370호에는 인플레이션 필름 성형방법을 이용하여 제조할 수 있는 무광택 필름의 제조방법이 기재되어 있다.In addition, Korean Patent Application No. 2000-32370, filed by the present applicant, describes a method of manufacturing a matte film that can be manufactured using an inflation film molding method.

한편, 무광택 특성을 갖는 폴리올레핀 필름을 제조함에 있어서 블로운 필름을 성형하기 위해서는 수지의 융용강도가 높고, MI가 1이하인 것이 바람직하지만, 이러한 물질에 의한 블로운 성형방법에 의해 제조된 예는 찾아볼 수 없다.On the other hand, in the production of a polyolefin film having a matte property, in order to mold the blown film, the melt strength of the resin is high and MI is preferably 1 or less, but examples of the manufacture by the blow molding method using such materials are found. Can't.

이에 본 발명자들이 상술한 문제점들을 해결하기 위해 연구검토한 결과, 에틸렌-알파올레핀 공중합수지 및 랜덤폴리프로필렌 수지로 이루어진 무광특성을 갖는 폴리올레핀 수지 조성물을 발견하였으며, 본 발명은 이에 기초하여 완성되었다.As a result of the present inventor's study to solve the above-mentioned problems, the inventors have found a polyolefin resin composition having a matte property consisting of ethylene-alpha olefin copolymer resin and random polypropylene resin, and the present invention has been completed based on this.

따라서, 본 발명의 목적은 무광특성을 갖는 필름의 제조에 있어서 종래 다른 기술들과는 다른 방식의 블로운 필름 성형방법을 사용하여, 무광특성이 우수한 무광필름을 제조할 수 있는 폴리올레핀 수지 조성물을 제공하는데 있다.Accordingly, an object of the present invention is to provide a polyolefin resin composition capable of producing a matte film having excellent matte properties by using a blown film forming method of a method different from the prior arts in the manufacture of a film having a matte property. .

또한, 본 발명의 다른 목적은 상기 폴리올레핀 수지 조성물을 블로운 필름 성형방법을 이용하여 제조하는 무광택 필름을 제공하는데 있다.In addition, another object of the present invention to provide a matte film for producing the polyolefin resin composition using a blown film molding method.

상기 목적을 달성하기 위한 본 발명의 무광특성을 갖는 폴리올레핀 수지 조성물은 용융지수가 0.01∼0.4g/10min이고 밀도가 0.930∼0.970g/cm3이며 탄소수가 1 내지 10의 알파올레핀과 에틸렌의 공중합수지 또는 에틸렌 단독 중합수지 30∼70중량%; 및 용융지수가 0.1∼10g/10min이며 에틸렌-프로필렌 공중합체를 포함하는 임팩트 폴리프로필렌 수지 또는 에틸렌 및/또는 부텐-1을 포함하는 랜덤 폴리프로필렌 수지 70∼30중량%로 구성된다.Polyolefin resin composition having a matte property of the present invention for achieving the above object has a melt index of 0.01 ~ 0.4g / 10min, a density of 0.930 ~ 0.970g / cm 3 and a copolymer of alpha olefin and ethylene having 1 to 10 carbon atoms Or 30 to 70% by weight of ethylene homopolymer resin; And an impact polypropylene resin having a melt index of 0.1 to 10 g / 10 min and a random polypropylene resin comprising ethylene and / or butene-1 and 70 to 30 wt%.

상기 다른 목적을 달성하기 위한 본 발명의 무광택 필름은, 용융지수가 0.01∼0.4g/10min이고 밀도가 0.930∼0.970g/cm3이며 탄소수가 1 내지 10의 알파올레핀과 에틸렌의 공중합수지 또는 에틸렌 단독 중합수지 30∼70중량%; 및 용융지수가 0.1∼10g/10min이며 에틸렌-프로필렌 공중합체를 포함하는 임팩트 폴리프로필렌 수지 또는 에틸렌 및/또는 부텐-1을 포함하는 랜덤 폴리프로필렌 수지 70∼30중량%로 구성되는 무광특성을 갖는 폴리올레핀 수지 조성물을 블로운 필름 성형방법을 이용하여 제조된다.Matte film of the present invention for achieving the above another object, the melt index is 0.01 ~ 0.4g / 10min, the density is 0.930 ~ 0.970g / cm 3 and the carbon resin of 1 to 10 alpha olefin and ethylene copolymer or ethylene alone 30 to 70% by weight of polymerized resin; And a polyolefin having a matte property, having a melt index of 0.1 to 10 g / 10 min and consisting of an impact polypropylene resin comprising an ethylene-propylene copolymer or a 70 to 30 wt% random polypropylene resin comprising ethylene and / or butene-1. The resin composition is prepared using a blown film molding method.

이하 본 발명을 좀 더 구체적으로 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.

전술한 바와 같이, 본 발명에 따른 조성물은 용융지수가 0.01∼0.4g/10min이고 밀도가 0.930∼0.970g/cm3이며 탄소수가 1 내지 10의 알파올레핀과 에틸렌의 공중합수지 또는 에틸렌 단독 중합수지(제1성분) 30∼70중량%; 및 용융지수가 0.1∼10g/10min이며 에틸렌-프로필렌 공중합체를 포함하는 임팩트 폴리프로필렌 수지 또는 에틸렌 및/또는 부텐-1을 포함하는 랜덤 폴리프로필렌 수지(제2성분)70∼30중량%로 구성되고, 선택적으로 과산화물 10∼300ppm(제3성분)을 더욱 선택적으로 포함한다.As described above, the composition according to the present invention has a melt index of 0.01 to 0.4 g / 10 min, a density of 0.930 to 0.970 g / cm 3 and a copolymer of alpha olefin and ethylene having 1 to 10 carbon atoms or ethylene homopolymer resin ( First component) 30 to 70% by weight; And an impact polypropylene resin having a melt index of 0.1 to 10 g / 10 min and an ethylene-propylene copolymer or 70 to 30 wt% of a random polypropylene resin (second component) comprising ethylene and / or butene-1, And optionally 10 to 300 ppm (third component) of the peroxide.

수지 혼합물에 있어서, 용융지수(ASTM D1238)가 매우 낮은 에틸렌-알파올레핀 공중합수지 또는 에틸렌 단독 중합수지의 제1성분을 사용함으로써 매트릭스 상(Matrix Phase)을 구성하며 이로써 수지 혼합물의 버블 안정성을 향상 및 유지시킴으로써 가공시 블로운 필름 성형방법을 사용할 수 있게 되며, 이러한 용융지수가 0.01∼0.4g/10min이고 밀도가 0.930∼0.970g/cm3이며 탄소수가 1 내지 10의 알파올레핀과 에틸렌의 공중합수지 또는 에틸렌 단독 중합수지로부터 선택되는 수지의 사용량은 30∼70중량%이다. 상기 용융지수가 0.01g/10min 미만이면 압출기에서의 가공에 어려움이 있고, 0.4g/10min을 초과하면 무광효과 및 버블안정성에 문제가 있으며, 밀도가 0.0930g/cm3미만이면 무광효과가 감소되는 문제가 있다. 또한, 상기 제1성분의 함량이 30중량% 미만이거나 70중량%를 초과하면 무광효과가 감소한다.In the resin mixture, a matrix phase is formed by using a first component of ethylene-alpha olefin copolymer resin or ethylene homopolymer resin having a very low melt index (ASTM D1238), thereby improving bubble stability of the resin mixture and It is possible to use a blown film forming method during the processing, such melt index of 0.01 ~ 0.4g / 10min, density of 0.930 ~ 0.970g / cm 3 and a copolymer of alpha olefin and ethylene having 1 to 10 carbon atoms or The usage-amount of resin chosen from ethylene homopolymerization resin is 30 to 70 weight%. If the melt index is less than 0.01g / 10min, it is difficult to process in the extruder, if it exceeds 0.4g / 10min there is a problem in the matte effect and bubble stability, if the density is less than 0.0930g / cm 3 the matte effect is reduced there is a problem. In addition, when the content of the first component is less than 30% by weight or more than 70% by weight, the matt effect is reduced.

또한 분산상(Dispersed Phase)으로 매트릭스 수지인 상기 제1성분과의 굴절율/흐름성/수축율의 차이로 인하여 필름 표면에 요철을 주어 무광특성을 부여하기 위해 첨가되는 제2성분은, 용융지수가 0.1∼10g/10min이며 에틸렌-프로필렌 공중합체를 포함하는 임팩트 폴리프로필렌 수지 또는 에틸렌 및/또는 부텐-1을 포함하는 랜덤 폴리프로필렌 수지로부터 선택되는 수지이며, 이러한 수지는 70∼30중량%를 포함하는데, 이때 용융지수가 0.1g/10min 미만의 수지는 생산성이 좋지 않아 생산되지 않으며, 10g/10min을 초과하면 버블안정성이 취약하게 되며, 그 함량이 30중량% 미만이거나, 70중량%를 초과하면 무광효과가 감소하는 문제가 있다.In addition, due to the difference in refractive index / flow / shrinkage with the first component, which is a matrix resin, as a dispersed phase, the second component added to impart unevenness to the film surface to give matt characteristics, has a melt index of 0.1 to An impact polypropylene resin of 10 g / 10 min and comprising an ethylene-propylene copolymer or a random polypropylene resin comprising ethylene and / or butene-1, including from 70 to 30% by weight, wherein If the melt index is less than 0.1g / 10min, the resin is not produced because of poor productivity, and if it exceeds 10g / 10min, the bubble stability becomes weak. If the content is less than 30% by weight or more than 70% by weight, the matt effect is achieved. There is a decreasing problem.

한편, 수지의 무광특성은 일차적으로 제1성분 및 제2성분의 용융지수의 차이가 클수록 점도 및 흐름성 차이로 인한 상분리 및 표면거침 현상이 커지기 때문에 무광특성이 더 양호하게 나타난다.On the other hand, the matte properties of the resin is primarily because the greater the difference between the melt index of the first component and the second component, the better the matte characteristics due to the phase separation and surface roughness due to the difference in viscosity and flowability.

또한, 폴리프로필렌과 폴리에틸렌의 상용화제로 작용하여 상분리된 수지상의 크기를 작게 해 주기 때문에 은은한 감촉의 시각적 특성을 부여하는 등의, 상기 수지 조성물에 무광택 필름 표면의 시각적 촉감을 조절하기 위하여 필요한 성분인 제3성분은 과산화물(Peroxide)로서 10∼300ppm을 더욱 선택적으로 포함하는데, 이 때 과산화물의 함량이 10ppm 미만이면 첨가효과가 거의 없으며, 300ppm을 초과하면 냄새 및 이물질 발생 가능성이 있다.In addition, since it acts as a compatibilizer of polypropylene and polyethylene to reduce the size of the phase-separated dendritic phase to provide a soft touch visual characteristics, such a component necessary for controlling the visual feel of the matte film surface to the resin composition The three components include 10 to 300 ppm more selectively as peroxides. At this time, if the content of the peroxide is less than 10 ppm, there is little effect of addition, and if it exceeds 300 ppm, odors and foreign substances may be generated.

이렇게 상기 제1성분 내지 제3성분으로 구성된 무광특성을 갖는 폴리올레핀 수지 조성물을 무광택 필름으로 제조하기 위한 가공기기 및 가공조건은, 통상적으로 사용되고 있는 단층 또는 다층의 폴리올레핀 필름 제조용 블로운 필름 기기로서, 고밀도/중밀도/(선형)저밀도 폴리에틸렌, 폴리에틸렌비닐아세테이트 수지 등의 필름 제조용 블로운 필름기기를 사용하며, 그 가공조건은 다이에서 압출되는 수지의 온도가 180∼250℃이며, 상기 다이에서 압출되는 수지의 온도가 180℃ 미만인 경우 필름표면에 멜트 프랙션(Melt Fracture)이 발생하여 필름표면이 곱지 않으며 250℃를 초과하면 버블안정성이 낮아져 균일한 필름의 성형이 불가능하게 된다. 또한 버블의 BUR(blow up ratio)은 0.9∼3.0으로 하며, 상기 BUR은 높을수록 기계방향과 기계수지의 방향의 필름 물성의 균형이 맞아 바람직하지만, 3.0을 초과하면버블의 안정성을 해치게 된다.The processing equipment and processing conditions for producing the polyolefin resin composition having a matte property composed of the first component to the third component into the matte film are a blown film device for producing a polyolefin film of a single layer or a multilayer which is commonly used. Blown film machine for film production, such as medium / low density polyethylene (polyethylene vinyl acetate resin), and the processing conditions are 180-250 ° C. of the resin extruded from the die, and resin extruded from the die. If the temperature is less than 180 ℃ melt fracture (melt fracture) occurs on the film surface does not multiply the surface of the film, if it exceeds 250 ℃ bubble stability is lowered, it is impossible to form a uniform film. In addition, the bubble up ratio (BUR) is 0.9 to 3.0, and the higher the BUR, the better the balance between the physical properties of the film in the machine direction and the direction of the machine resin, but exceeding 3.0 deteriorates the stability of the bubble.

또한, 상기 단층 또는 다층의 폴리올레핀 필름 제조용 블로운 필름 기기를 이용하여 제조되는 필름은 단층 또는 다층구조를 이루며, 상기 조성물은 그 필름의 표면층을 구성하게 되며, 필름이 다층구조인 경우에는 적어도 하나이상의 표면층을 이룰수 있다.In addition, the film produced using the blown film device for producing a single layer or multi-layer polyolefin film forms a single layer or a multilayer structure, and the composition constitutes the surface layer of the film, when the film is a multilayer structure, at least one Surface layer can be achieved.

이하 실시예를 통하여 본 발명을 좀 더 상세히 설명하지만 이에 본 발명의 범주가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

실시예 1 내지 2Examples 1-2

각 성분을 하기 표 1에 따라 포함하는 수지 조성물을 30ψ 2축 혼련기(Twin Screw Compounder)를 이용하여 200℃에서 혼련하였고, 저밀도 폴리에틸렌 블로운 필름 성형기기를 이용하여 무광택 필름을 제조하였다. 이 때 다이 온도는 200℃, BUR은 1.6이었다. 제조된 무광택 필름의 물성을 측정하기 위해, 광택도 측정기(gloss detecter)로 무광특성(gloss), 버블안정성 결과를 하기 표 1에 비교하여 나타내었다.The resin composition containing each component according to Table 1 was kneaded at 200 ° C. using a 30ψ twin screw compounder, and a matt film was prepared using a low density polyethylene blown film forming machine. At this time, die temperature was 200 degreeC and BUR was 1.6. In order to measure the properties of the manufactured matte film, the glossiness (gloss), bubble stability results with a glossiness detector (gloss detector) is shown in Table 1 below.

이 때 무광특성은 빛을 일정한 각도(45°)에서 시험재료에 비추고 반사광을 입사광과 똑같은 각도에서 빛을 받았을 때 빛의 강도를 굴절률이 1.567인 유리표면에 광택을 100으로 했을 때의 값(%)으로 표시하였다.At this time, the matte property is the value when light is reflected on the test material at a certain angle (45 °) and the reflected light is received at the same angle as the incident light. ).

비교예 1Comparative Example 1

하기 표 1과 같이 구성되는 수지 조성물을 상기 실시예와 같은 방법으로 실시하여 필름을 제조하였고, 이의 분석결과를 하기 표 1에 비교분석하였다.To prepare a film was carried out in the same manner as in the above-described resin composition composed as shown in Table 1, the analysis results thereof were compared to Table 1 below.

구 성 비Composition rain 무광특성(gloss)Gloss 버블안정성Bubble stability 제1성분First ingredient 제2성분Second ingredient 비교예 1Comparative Example 1 100%밀도=0.919MI=1.0100% Density = 0.919MI = 1.0 -- 25(하)25 (bottom) medium 실시예 1Example 1 50%밀도=0.954MI=0.04750% Density = 0.954MI = 0.047 50%C2=5.9%MI=0.550% C 2 = 5.9% MI = 0.5 6.8(상)6.8 (up) medium 실시예 2Example 2 50%밀도=0.945MI=0.3350% Density = 0.945MI = 0.33 50%C2=5.9%MI=0.550% C 2 = 5.9% MI = 0.5 7.3(상)7.3 (up) medium

상기 표 1에서 알 수 있는 바와 같이, 본 발명에 따른 필름이 비교예의 필름에 비해, 우수한 무광특성을 나타냄을 알 수 있다.As can be seen in Table 1, it can be seen that the film according to the present invention exhibits excellent matt properties, compared to the film of the comparative example.

상기 실시예 및 비교예를 통해 알 수 있는 바와 같이, 본 발명에 따라 제조된 필름은 표면에 미세한 요철이 형성되어 빛이 난반사되어 우수한 무광특성을 가지게 되며, 일반 블로운 필름 성형기기로도 가공이 가능한 고급스러운 무광필름을 제조할 수 있다.As can be seen through the above examples and comparative examples, the film produced according to the present invention has fine matte irregularities formed on the surface is diffusely reflected light has excellent matt properties, even processing with a general blown film forming machine Higher quality matte film can be produced.

Claims (6)

용융지수가 0.01∼0.4g/10min이고 밀도가 0.930∼0.970g/cm3이며 탄소수가 1 내지 10의 알파올레핀과 에틸렌의 공중합수지 또는 에틸렌 단독 중합수지 30∼70중량%; 및A melt index of 0.01 to 0.4 g / 10 min, a density of 0.930 to 0.970 g / cm 3 , and a copolymer resin of alpha olefin and ethylene having 1 to 10 carbon atoms or 30 to 70 wt% of ethylene homopolymerization resin; And 용융지수가 0.1∼10g/10min이며 에틸렌-프로필렌 공중합체를 포함하는 임팩트 폴리프로필렌 수지 또는 에틸렌 및/또는 부텐-1을 포함하는 랜덤 폴리프로필렌 수지 70∼30중량%를 포함하는 것을 특징으로 하는 무광특성을 갖는 블로운 필름용 폴리올레핀 수지 조성물.Matte characteristics, characterized in that the melt index is 0.1 to 10g / 10min and comprises 70 to 30% by weight of an impact polypropylene resin containing an ethylene-propylene copolymer or a random polypropylene resin containing ethylene and / or butene-1 Polyolefin resin composition for blown films having a. 제1항에 있어서, 상기 조성물이 과산화물 10∼300ppm을 더욱 포함하는 것을 특징으로 하는 무광특성을 갖는 블로운 필름용 폴리올레핀 수지 조성물.The polyolefin resin composition for a blown film having a matte property according to claim 1, wherein the composition further comprises 10 to 300 ppm of a peroxide. 용융지수가 0.01∼0.4g/10min이고 밀도가 0.930∼0.970g/cm3이며 탄소수가 1 내지 10의 알파올레핀과 에틸렌의 공중합수지 또는 에틸렌 단독 중합수지 30∼70중량%; 및 용융지수가 0.1∼10g/10min이며 에틸렌-프로필렌 공중합체를 포함하는 임팩트 폴리프로필렌 수지 또는 에틸렌 및/또는 부텐-1을 포함하는 랜덤 폴리프로필렌 수지 70∼30중량%를 포함하는 무광특성을 갖는 폴리올레핀 수지 조성물이 블로운 필름 성형방법을 이용하여 표면층을 이루게 함으로써 제조된 것을 특징으로 하는 무광택 필름.A melt index of 0.01 to 0.4 g / 10 min, a density of 0.930 to 0.970 g / cm 3 , and a copolymer resin of alpha olefin and ethylene having 1 to 10 carbon atoms or 30 to 70 wt% of ethylene homopolymerization resin; And a polyolefin having a matte property including a melt index of 0.1 to 10 g / 10 min and an impact polypropylene resin comprising an ethylene-propylene copolymer or 70 to 30 wt% of a random polypropylene resin comprising ethylene and / or butene-1. Matte film, characterized in that the resin composition was prepared by forming a surface layer using a blown film forming method. 제3항에 있어서, 상기 조성물이 과산화물 10∼300ppm을 더욱 포함하는 것을 특징으로 하는 무광택 필름.4. The matte film of claim 3, wherein the composition further comprises 10-300 ppm of peroxide. 제3항에 있어서, 상기 성형방법이 다이에서 압출되는 수지의 온도가 180∼250℃이며, 버블의 BUR이 0.9∼3.0의 조건에서 수행됨을 특징으로 하는 무광택 필름.The matt film according to claim 3, wherein the molding method is performed at a temperature of 180 to 250 ° C. and a BUR of a bubble is performed at a condition of 0.9 to 3.0. 제3항에 있어서, 상기 필름이 다층구조인 경우에 수지 조성물은 적어도 하나이상의 표면층을 이루는 것을 특징으로 하는 무광택 필름.4. The matte film of claim 3, wherein the resin composition forms at least one surface layer when the film has a multilayer structure.
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EP1396336A1 (en) * 2002-09-05 2004-03-10 SK Corporation Matte biaxially oriented polypropylene film with improved matte property and processability
KR100702979B1 (en) * 2005-01-04 2007-04-05 삼성토탈 주식회사 Polypropylene resin composition with high impact strength and glossless properties
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JPS5811536A (en) * 1981-07-14 1983-01-22 Showa Denko Kk Resin composition
JPS59147045A (en) * 1983-02-14 1984-08-23 Showa Denko Kk Impact-resistant propylene polymer composition
JPH03197541A (en) * 1989-12-26 1991-08-28 Idemitsu Petrochem Co Ltd Low-gloss resin composition for blow molding
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Publication number Priority date Publication date Assignee Title
EP1396336A1 (en) * 2002-09-05 2004-03-10 SK Corporation Matte biaxially oriented polypropylene film with improved matte property and processability
US9454277B2 (en) 2004-05-06 2016-09-27 Apple Inc. Multipoint touchscreen
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AU2013204507B2 (en) * 2006-06-09 2015-06-04 Apple Inc. Touch screen liquid crystal display
US9710095B2 (en) 2007-01-05 2017-07-18 Apple Inc. Touch screen stack-ups
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