KR20040099865A - Polypropylene composition provided by the calendering process for transparent film and sheet, and method for preparing polypropylene transparent film and sheet using the same - Google Patents

Polypropylene composition provided by the calendering process for transparent film and sheet, and method for preparing polypropylene transparent film and sheet using the same Download PDF

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KR20040099865A
KR20040099865A KR1020030031993A KR20030031993A KR20040099865A KR 20040099865 A KR20040099865 A KR 20040099865A KR 1020030031993 A KR1020030031993 A KR 1020030031993A KR 20030031993 A KR20030031993 A KR 20030031993A KR 20040099865 A KR20040099865 A KR 20040099865A
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polypropylene
sheet
weight
transparent film
parts
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KR100585541B1 (en
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박종덕
서상원
변영훈
김득식
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한화종합화학 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/24—Calendering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • 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
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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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)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Casting Or Compression Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: A polypropylene composition for a transparent film or sheet is provided, which can be processed by a calender. And a process is also provided to produce the polypropylene transparent film or sheet by using the polypropylene composition. CONSTITUTION: The polypropylene composition contains: 100pts.wt. of a polypropylene resin having a melt flow index of 0.1-4g/10min(230deg.C/2.16kg), an average density of 0.86-0.91g/cm3, and a molecular weight of 560,000-1,200,000mol/g; 1-8pts.wt. of at least one nucleating agent selected from dibenzylidene sorbitol and dimethyl benzylidene sorbitol; 0.2-5pts.wt. of at least one anti-blocking agent selected from methylene bisstearamide or ethylene bisstearamide; 0.2-5pts.wt. of a lubricant selected from calcium stearate, zinc stearate, or stearic acid; 0.1-1pts.wt. of a stabilizer selected from a phosphite or phenol resin. And the process for producing the polypropylene transparent film or sheet contains the steps of: melting the polypropylene composition in a planetary extruder, a one or twin screw extruder, or a kneader, wherein the temperature of the extruder is 210-270deg.C; producing the film or sheet from the molten composition by using the calender, wherein the surface temperature of the calender is 180-250deg.C; cooling the produced film or sheet rapidly to 80-110deg.C.

Description

캘린더가 가능한 투명 필름 및 시트용 폴리프로필렌계 조성물 및 이를 이용한 폴리프로필렌 투명 필름 및 시트의 제조방법 {Polypropylene composition provided by the calendering process for transparent film and sheet, and method for preparing polypropylene transparent film and sheet using the same}Polypropylene composition provided by the calendering process for transparent film and sheet, and method for preparing polypropylene transparent film and sheet using the same }

본 발명은 캘린더가 가능한 투명 필름 및 시트용 폴리프로필렌계 조성물 및 이를 이용한 폴리프로필렌 투명 필름 및 시트의 제조방법에 관한 것으로, 좀 더 구체적으로는 폴리프로필렌 수지에 대하여 디벤질리덴 솔비톨 및 디메틸 벤질리덴 솔비톨을 포함하는 군으로부터 선택되는 적어도 하나의 핵제, 메틸렌 비스스테아라마이드 또는 에틸렌 비스스테아라마이드로 선택되는 적어도 하나의 블록킹 방지제, 칼슘 스테아레이트, 징크 스테아레이트 또는 스테아릭산으로 이루어진 군으로부터 선택되는 활제, 및 포스파이트 또는 폐놀계 수지로 이루어진 군으로부터 선택되는 안정제를 포함하는 캘린더가 가능한 투명 필름 및 시트용 폴리프로필렌계 조성물, 및 이를 이용한 폴리프로필렌 투명 필름 및 시트의 제조방법에 관한 것이다.The present invention relates to a polypropylene-based composition for calendars and sheets capable of calendering, and to a method for producing a polypropylene transparent film and sheet using the same, and more specifically, to a polypropylene resin, dibenzylidene sorbitol and dimethyl benzylidene sorbitol. At least one nucleating agent selected from the group comprising: at least one antiblocking agent selected from methylene bis stearamide or ethylene bis stearamide, lubricants selected from the group consisting of calcium stearate, zinc stearate or stearic acid, And it relates to a polypropylene-based composition for a calendar capable transparent film and sheet comprising a stabilizer selected from the group consisting of phosphite or phenolic resin, and a method for producing a polypropylene transparent film and sheet using the same.

종래의 캘린더(calender) 가공의 공정 및 설비는 고무 시트(rubber sheet)를 제조하는데 적용되었으며 점차적으로 PVC 필름 및 시트를 제조하기 위해 사용되는공정 및 설비로서, 폴리프로필렌을 가공하기에는 어려움이 많았다. 그 주요원인으로는 폴리프로필렌을 캘린더 가공할 경우 캘린더 롤(calender roll) 표면에 폴리프로필렌이 점착되어 가공이 불가능하다는 점과 폴리프로필렌의 용융강도(melt strength)가 약하여 캘린더 롤간에 필름이나 시트의 전이가 어려운 점을 들 수 있다. 따라서, 통상적으로 폴리프로필렌 필름 또는 시트는 T-다이(die) 압출방식이나 브로운(blown) 공법을 생산하는 경우가 많았다.Conventional calender process and equipment has been applied to the production of rubber sheets (rubber sheet) and gradually used to manufacture PVC films and sheets, it was difficult to process polypropylene. The main reason is that when calendering polypropylene, it is impossible to process because the polypropylene adheres to the surface of the calender roll and the melt strength of polypropylene is weak so that the film or sheet transfers between calender rolls. This is difficult. Accordingly, polypropylene films or sheets have often produced T-die extrusion or blown processes.

근래에 들어서면서 폴리프로필렌을 캘린더 공법으로 제조하기 위한 시도가 많이 진행되고 있으나, 주로 TPO(thermoplastic polyolefin)을 재료로 하는 것에 그치며 범용 폴리프로필렌을 사용하는 캘린더 기술은 매우 드물고, 중합단계에서 TPO를 결합시켜서 캘린더 가공이 가능하게 하기도 하지만 상기 TPO가 매우 고가인 단점이 있다.In recent years, many attempts have been made to produce polypropylene by calendering. However, calender technology using general polypropylene is very rare, and TPO is combined at the polymerization stage. Even though the calendering is possible, the TPO is very expensive.

근래 캘린더 가공 공정을 이용하여 폴리올레핀계 필름 및 시트를 제조하는 방법으로서, 미국특허 제4,144,304호에는 25∼75중량%의 폴리올레핀계 수지를 25∼75중량%의 식물성 섬유와 혼합하여 약 170℃로 유지되는 밴버리 믹서에서 혼련 후 캘린더 롤에서 필름 및 시트를 제조하는 방법이 개시되어 있다. 이들 용융물은 시트의 제조공정 중 식물성 섬유에 의해 캘린더 롤에 점착되지 않음으로써 캘린더링이 가능하였다.Recently, a method for producing a polyolefin-based film and sheet using a calendering process, US Patent No. 4,144,304 is a mixture of 25 to 75% by weight of polyolefin resin with 25 to 75% by weight of vegetable fibers and maintained at about 170 ℃ A method for producing films and sheets in calender rolls after kneading in a Banbury mixer is disclosed. These melts could be calendered by not sticking to the calender rolls by the vegetable fibers during the manufacturing process of the sheet.

또한, 미국특허 제4,345,046호에는 활제를 상호 조합한 배합으로 폴리프로필렌계 수지를 캘린더 가공하는 방법이 게시되어 있다. 폴리프로필렌계 수지로는 호모폴리머와 코폴리머를 사용하였고, 활제 배합으로는 N, N'-에틸렌 비스 아민 지방산을 60-70중량부, 하이드록시-치환 지방산을 22-32중량부 및 금속염 지방산을 3∼13중량부로 사용하여 캘린더링이 가능하도록 하였다. 가공공정은 밴버리 믹서에서 혼련 후 캘린더에서 필름을 제조하는 방법을 사용하였다.In addition, U.S. Patent No. 4,345,046 discloses a method for calendering a polypropylene-based resin in a combination of lubricants. As the polypropylene resin, homopolymer and copolymer were used, and as a lubricant, 60-70 parts by weight of N, N'-ethylene bisamine fatty acid, 22-32 parts by weight of hydroxy-substituted fatty acid and metal salt fatty acid were used. 3 to 13 parts by weight was used to enable calendaring. The processing process used a method of producing a film on a calender after kneading in a Banbury mixer.

미국특허 제5,439,628호에는 폴리프로필렌 배합에 많은 양의 충진제를 첨가시킴으로써 캘린더 롤의 표면과 용융물 사이에 점착성을 감소시켜 필름 및 시트를 제조하는 방법이 개시되어 있다. 배합으로는 폴리프로필렌 수지 70 내지 100중량부에 대하여 폴리에틸렌 수지를 0 내지 30중량부 사용하였다. 또한, 폴리프로필렌 배합의 가공성을 높이기 위해 EPDM 엘라스토머 2 내지 40중량부를 첨가하였고, 충진제 100 내지 400중량부를 사용하였다. 그 외의 가공조제로 스테아레이트 금속을 0 내지 5중량부 사용하였다. 이러한 혼합물을 170∼210℃의 온도로 유지되는 니이더(kneader)에서 혼련한 다음, 캘린더링하고 권취롤을 이용하여 상온으로 냉각한 후 필름을 제조한다.U. S. Patent No. 5,439, 628 discloses a method for producing films and sheets by reducing the adhesion between the surface of the calender roll and the melt by adding a large amount of filler to the polypropylene blend. As a mix | blending, 0-30 weight part of polyethylene resins were used with respect to 70-100 weight part of polypropylene resins. In addition, 2 to 40 parts by weight of EPDM elastomer was added to increase the processability of the polypropylene blend, and 100 to 400 parts by weight of filler was used. As other processing aids, 0 to 5 parts by weight of stearate metal was used. This mixture is kneaded in a kneader maintained at a temperature of 170-210 ° C., then calendered and cooled to room temperature using a winding roll to prepare a film.

한편, 본출원인에 의한 한국등록특허 제220892호에 의해 폴리프로필렌 수지에 대한 충진제의 사용량을 줄이면서도 캘린더 가공할 수 있는 조성물이 발견되었는데, 상기 조성물은 용융흐름지수(230℃/2.16kg)가 0.1 내지 4g/10min이고, 평균밀도는 0.86 내지 0.91g/cm3의 범위이며 분자량이 560,000 내지 1,200,000mol/g인 폴리프로필렌 수지 100중량부에 대하여 용융흐름지수(190℃/2.1kg)가 0.2 내지 5g/10min이고, 밀도가 0.94∼0.96g/cm3인 고밀도 폴리에틸렌 및 용융흐름지수(190℃/2.16kg)가 0.8 내지 5g/10min이고, 밀도가 0.91 내지 0.94g/cm3인 선형저밀도 폴리에틸렌으로 이루어진 군으로부터 선택된 폴리에틸렌 수지 0.01∼50중량부, 충진제 30∼70중량부, 실리카 겔 0.5∼4.0중량부, 활제 0.1∼2중량부 및 안정제 0.1∼1중량부로 이루어진다.On the other hand, according to the Korean Patent No. 220892 by the present applicant was found a composition that can be calendered while reducing the amount of filler for polypropylene resin, the composition has a melt flow index (230 ℃ / 2.16kg) of 0.1 Melt flow index (190 DEG C / 2.1 kg) of 0.2 to 5 g / g with respect to 100 parts by weight of polypropylene resin having a molecular weight of 560,000 to 1,200,000 mol / g, with an average density ranging from 0.86 to 0.91 g / cm < 3 > 10min and a density of 0.94~0.96g / cm 3 of high density polyethylene and a melt flow index (190 ℃ / 2.16kg) of 0.8 to 5g / 10min, the group consisting of linear density of 0.91 to 0.94g / cm 3 with low density polyethylene 0.01 to 50 parts by weight of polyethylene resin, 30 to 70 parts by weight of filler, 0.5 to 4.0 parts by weight of silica gel, 0.1 to 2 parts by weight of lubricant and 0.1 to 1 part by weight of stabilizer.

또한 본출원인에 의한 한국특허출원 제2000-44677호에는, 용융흐름지수(230℃/2.16kg)가 0.1 내지 4g/10min이고, 평균밀도는 0.86 내지 0.91g/cm3의 범위이며, 분자량이 560,000 내지 1,200,000mol/g인 폴리프로필렌 수지 100중량부에 대하여 탄산칼슘, 탈크, 카올린, 셀룰로오스 파우더 및 이산화티타늄으로 이루어진 군으로부터 선택된 적어도 하나의 충진제 0∼200중량부, 실리카, 메틸렌 비스스테아라마이드, 에틸렌 비스스테아라마이드 또는 이들의 혼합물로 이루어진 군으로부터 선택된 적어도 하나의 블록킹 방지제 0.4∼5중량부, 칼슘 스테아레이트, 징크 스테아레이트 또는 스테아릭산으로 이루어진 군으로부터 선택된 활제 0.2∼3중량부 및 안정제 0.1∼1중량부를 포함하는 캘린더가 가능한 데코시트용 폴리프로필렌계 조성물이 기재되어 있다.In addition, Korean Patent Application No. 2000-44677 by the present applicant has a melt flow index (230 ° C./2.16 kg) of 0.1 to 4 g / 10 min, an average density of 0.86 to 0.91 g / cm 3 , and a molecular weight of 560,000. 0 to 200 parts by weight of at least one filler selected from the group consisting of calcium carbonate, talc, kaolin, cellulose powder and titanium dioxide, based on 100 parts by weight of polypropylene resin having a weight of from 1,200,000 mol / g, silica, methylene bis stearamide, ethylene 0.4 to 5 parts by weight of at least one antiblocking agent selected from the group consisting of bis stearamide or mixtures thereof, 0.2 to 3 parts by weight of a lubricant selected from the group consisting of calcium stearate, zinc stearate or stearic acid and 0.1 to 1 stabilizer A polypropylene-based composition for a decor sheet capable of calendering containing a weight part is described.

그러나 폴리프로필렌계 투명 필름 및 시트의 경우, 가공성에 도움을 주는 무기 충진물을 사용할 수 없기 때문에 캘린더 가공의 어려움은 더하게 된다. 뿐만 아니라, 플리프로필렌 소재의 특성상 용융된 폴리프로필렌의 냉각 공정을 통한 필름화 과정에서 투명성은 일반 PVC 냉각 가공공정의 방법으로는 얻을 수 없기 때문에 폴리프로필렌 필름의 투명성 확보를 위해서는 결정화도 제어기술이 필요하다. 따라서, 현재까지 폴리프로필렌 소재의 물리화학적 특성상 캘린더 가공을 통한 상용화의 가능성이 매우 어렵고, 캘린더 가공방법으로 폴리프로필렌 투명 필름 및 시트를 제조하는 것은 매우 곤란한 것으로 여겨져 왔다.However, in the case of polypropylene-based transparent films and sheets, it is difficult to use calendering because inorganic fillers that help processability can not be used. In addition, due to the characteristics of the polypropylene material, transparency in the film forming process through the cooling process of the molten polypropylene cannot be obtained by the general PVC cooling process, so crystallinity control technology is required to secure the transparency of the polypropylene film. . Therefore, until now, the possibility of commercialization through calendering is very difficult due to the physicochemical properties of polypropylene, and it has been considered very difficult to manufacture polypropylene transparent films and sheets by calendering.

따라서, 본 발명의 목적은, 상기 종래기술의 문제점을 해결하고, 종래 캘린더 설비로 가공할 수 있는 재료를 PVC 소재 뿐만 아니라 폴리프로필렌 소재로 확대하며, 투명 필름 및 시트 생산까지 가능하게 다양화함으로써 캘린더 설비의 효율성을 극대화할 수 있고, 또한 폴리프로필렌의 종래 가공방식인 압출 T-다이 및 브로운 방식보다 생산성이 우수하여 폴리프로필렌 투명 필름 및 시트의 생산원가를 절감할 수 있는 폴리프로필렌계 조성물 및 이를 이용하여 폴리프로필렌 투명 필름 및 시트를 제조하는 방법을 제공하는데 있다.Accordingly, an object of the present invention is to solve the problems of the prior art, and to expand the material that can be processed by conventional calendar equipment to not only PVC material but also polypropylene material, and to diversify to the production of transparent film and sheet as possible Polypropylene-based composition capable of maximizing the efficiency of the equipment and reducing the production cost of the polypropylene transparent film and sheet due to the higher productivity than the conventional polypropylene extrusion T-die and blow method. It is to provide a method for producing a polypropylene transparent film and sheet using.

상기 목적을 달성하기 위한 본 발명의 캘린더가 가능한 투명 필름 및 시트용 폴리프로필렌계 조성물은, 용융흐름지수(230℃/2.16kg)가 0.1 내지 4g/10min이고, 평균밀도는 0.86 내지 0.91g/cm3의 범위이며, 분자량이 560,000 내지 1,200,000mol/g인 폴리프로필렌 수지 100중량부에 대하여 디벤질리덴 솔비톨 및 디메틸 벤질리덴 솔비톨을 포함하는 군으로부터 선택되는 적어도 하나의 핵제 1∼8중량부, 메틸렌 비스스테아라마이드 또는 에틸렌 비스스테아라마이드로 선택되는 적어도 하나의 블록킹 방지제 0.2∼5중량부, 칼슘 스테아레이트, 징크 스테아레이트 또는 스테아릭산으로 이루어진 군으로부터 선택되는 활제 0.2∼5중량부, 및 포스파이트 또는 폐놀계 수지로 이루어진 군으로부터 선택되는 안정제 0.1∼1중량부를 포함한다.The polypropylene-based composition for calendars and transparent films and sheets of the present invention for achieving the above object has a melt flow index (230 ° C./2.16 kg) of 0.1 to 4 g / 10 min and an average density of 0.86 to 0.91 g / cm 1 to 8 parts by weight of methylene bis, at least one nucleating agent selected from the group comprising dibenzylidene sorbitol and dimethyl benzylidene sorbitol with respect to 100 parts by weight of a polypropylene resin having a molecular weight of 560,000 to 1,200,000 mol / g 0.2-5 parts by weight of at least one antiblocking agent selected from stearamide or ethylene bis stearamide, 0.2-5 parts by weight of a lubricant selected from the group consisting of calcium stearate, zinc stearate or stearic acid, and phosphite or It contains 0.1 to 1 part by weight of a stabilizer selected from the group consisting of phenolic resins.

상기 다른 목적을 달성하기 위한 본 발명에 따른 폴리프로필렌 투명 필름 및 시트의 제조방법은, 상기 조성물을 210∼270℃로 유지된 플레네터리 압출기나 일축 또는 이축 압출기, 또는 버스 니이더에서 용융시키는 단계; 제조된 용융물을 캘린더롤 표면온도가 180∼250℃로 유지된 캘린더를 이용하여 필름 및 시트로 제조하는 단계; 및 형성된 필름 및 시트를 80∼110℃로 급속 냉각시키는 단계;를 포함한다.Method for producing a polypropylene transparent film and sheet according to the present invention for achieving the above another object, the step of melting the composition in a planetary extruder or single or twin screw extruder, or bus kneader maintained at 210 to 270 ℃ ; Preparing the prepared melt into a film and a sheet using a calender whose calender roll surface temperature is maintained at 180 to 250 ° C; And rapidly cooling the formed film and sheet to 80 to 110 ° C.

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

일반적으로 캘린더 가공에 사용되는 폴리프로필렌 수지의 용융흐름지수(Melt Flow Index, 230℃/2.16kg ASTM D-1238; MFI)는 2 내지 10g/10min 정도이고, 분자량이 100,000 내지 700,000정도를 사용하지만, 본 발명에서는 호모폴리머와 에틸렌 프로필렌 러버와 프로필렌 코폴리머를 사용하였고, 분자량은 560,000 내지 1,200,000mol/g이며, MFI(230℃/2.16kg)는 0.1 내지 4g/10min 범위가 바람직하고, 밀도는 0.86 내지 0.91g/cm3범위이다.In general, the melt flow index (Melt Flow Index, 230 ° C./2.16 kg ASTM D-1238; MFI) of polypropylene resin used for calendering is about 2 to 10 g / 10 min, and its molecular weight is about 100,000 to 700,000. In the present invention, a homopolymer, an ethylene propylene rubber, and a propylene copolymer were used, and the molecular weight is 560,000 to 1,200,000 mol / g, MFI (230 ° C./2.16 kg) is preferably in the range of 0.1 to 4 g / 10 min, and the density is 0.86 to 0.91 g / cm 3 .

한편, 본 발명에서는 바람직한 MFI 값을 결정하기 위해 다음과 같은 실험을 수행하였다. 즉, 약 200℃로 유지는 6' 믹싱롤에서 MFI가 2g/10min인 폴리프로필렌계 수지 100중량부와 활제 1중량부만을 사용하여 롤 밀링시킨 경우, 롤 표면과 폴리프로필렌 수지 용융물과 점착이 발생하여 롤밀 자체가 불가능하였다. MFI가 0.5인 폴리프로필렌 수지 100중량부에 활제 1중량부만을 사용하여 롤밀시켜 가공성을살펴본 결과, 폴리프로필렌계 용융물이 믹싱롤 표면과 점착성이 줄어들고, 롤밀이 가능함을 발견할 수 있었다. 이러한 결과로부터 상기 MFI값과 각 성분들의 양을 결정할 수 있었다.Meanwhile, in the present invention, the following experiment was performed to determine a preferable MFI value. That is, when the roll milling using only 100 parts by weight of polypropylene-based resin and 1 part by weight of polypropylene-based resin having an MFI of 2 g / 10 min on a 6 'mixing roll maintained at about 200 ° C., the roll surface and the polypropylene resin melt and adhesion occurred. The roll mill itself was not possible. As a result of roll milling using only 1 part by weight of lubricating agent in 100 parts by weight of polypropylene resin having an MFI of 0.5, it was found that the polypropylene melt was reduced in adhesion to the mixing roll surface and roll mill was possible. From these results, the MFI value and the amount of each component could be determined.

전술한 바와 같이, 종래 폴리프로필렌 필름 및 시트를 캘린더 공법으로 제조할 수 없었던 가장 큰 이유는 캘린더 롤의 표면에 용융된 폴리프로필렌이 점착되어 가공이 불가능하다는 점이었다.As described above, the biggest reason why the conventional polypropylene film and sheet could not be produced by the calendering method was that molten polypropylene adhered to the surface of the calender roll, and thus processing was impossible.

따라서, 본 발명에서는 점착성 문제를 해결하기 위해 슬립성을 증가시킬 수 있는 메틸렌 비스스테아라마이드 및 에틸렌 비스스테아라마이드로 이루어진 군으로부터 적어도 하나 선택된 블록킹 방지제(anti-blocking agent)를 첨가하였다. 본 발명에 따른 캘린더 공정에서 상기 블록킹 방지제를 사용함으로써, 상기 블록킹 방지제가 필름이나 시트의 표면에 노출된 상태로 존재하게 되어 폴리프로필렌 용융물과 캘린더 롤 표면에 점착성을 줄일 수 있었다. 또한, 본 발명에 따른 조성물에서 폴리프로필렌 100중량부에 대하여 블록킹 방지제를 0.2∼5중량부로 사용하는데, 0.2중량부 미만이면 캘린더 롤에 용융물이 점착되어 가공이 불가능하였고, 5중량부를 초과하면 시트의 표면이 거칠어지는 단점이 있다.Therefore, in the present invention, at least one anti-blocking agent selected from the group consisting of methylene bis stearamide and ethylene bis stearamide, which can increase slip property, is added to solve the problem of adhesion. By using the antiblocking agent in the calendering process according to the present invention, the antiblocking agent was present in the state exposed to the surface of the film or sheet, thereby reducing the adhesion to the polypropylene melt and the calender roll surface. In addition, the anti-blocking agent is used in an amount of 0.2 to 5 parts by weight based on 100 parts by weight of polypropylene in the composition according to the present invention. The disadvantage is that the surface is rough.

또한, 본 발명에 있어서 투명 필름이나 시트의 투명성의 제고를 위하여 핵제를 폴리프로필렌 100중량부에 대하여 1∼8중량부로 사용함으로써, 핵의 밀도를 높이고 결정크기를 빛의 파장보다 작게 미세화시켜 광산란을 억제하여 투명성을 향상시킨다. 본 발명에서 사용가능한 핵제는 디벤질리덴 솔비톨 및 디메틸 벤질리덴 솔비톨을 포함하는 군으로부터 적어도 하나 이상 선택하여 사용할 수 있다. 상기 핵제의 첨가량이 1중량부 미만이면 투명성이 현저히 떨어지고, 8중량%를 초과하면 핵제 상호간의 응집에 의해 투명성 효과증진을 나타내지 못한다.In addition, in the present invention, the nucleating agent is used in an amount of 1 to 8 parts by weight based on 100 parts by weight of polypropylene to enhance the transparency of the transparent film or sheet. It suppresses and improves transparency. The nucleating agent usable in the present invention may be used by selecting at least one from the group containing dibenzylidene sorbitol and dimethyl benzylidene sorbitol. If the added amount of the nucleating agent is less than 1 part by weight, the transparency is significantly lowered. If the nucleating agent is more than 8% by weight, the transparency effect is not enhanced by aggregation between the nucleating agents.

본 발명에서 상기 조성물의 분산성 및 가공성을 향상시키기 위해 활제를 사용하며, 그 사용량은 0.2∼5중량부가 바람직하고, 예를 들어 칼슘-스테아레이트, 징크-스테아레이트, 스테아릭산 등을 들 수 있다.In the present invention, a lubricant is used to improve the dispersibility and processability of the composition, and the amount thereof is preferably 0.2 to 5 parts by weight, and examples thereof include calcium stearate, zinc stearate, stearic acid, and the like. .

또한, 안정제는 0.1∼1중량부로 사용되며, 시판되는 광안정제 또는 열안정제를 사용할 수 있으며, 포스파이트 및 페놀계 수지를 들 수 있다.In addition, the stabilizer is used in 0.1 to 1 parts by weight, commercially available light stabilizers or heat stabilizers can be used, phosphite and phenolic resins.

또한, 빛, 온도, 습도, 산소 등의 환경요인에 의해 쉽게 분해되어 표면변색, 크랙 등의 광학적 성질 변화 뿐만 아니라, 충격강도, 인장강도, 신율 등의 물리적 성질이 저하되는 문제를 방지하기 위해 기타 첨가제로서, UV 안정화제인 벤조트리아졸계 수지를 0.1∼5중량부로 더욱 사용할 수 있다.In addition, it is easily decomposed by environmental factors such as light, temperature, humidity, and oxygen, so as to prevent not only optical properties such as surface discoloration and cracks, but also physical problems such as impact strength, tensile strength and elongation deteriorate. As an additive, the benzotriazole type resin which is a UV stabilizer can further be used in 0.1-5 weight part.

본 발명에서 사용되는 폴리올레핀 엘라스토머 또는 에틸렌 비스아세테이트는 최종 조성물로 제조된 시트에 연성을 부여하고, 상기 폴리프로필렌 수지 100중량부에 대하여 50중량부 미만의 범위로 첨가된다. 폴리올레핀 엘라스토머 또는 에틸렌 비스아세테이트의 사용량이 폴리프로필렌 100중량부에 대해 50중량부를 초과하면 용융물의 캘린더롤 점착성이 강하여 캘린더 가공이 어려워지는 문제가 있다.The polyolefin elastomer or ethylene bisacetate used in the present invention imparts ductility to the sheet made of the final composition and is added in a range of less than 50 parts by weight based on 100 parts by weight of the polypropylene resin. If the amount of the polyolefin elastomer or ethylene bisacetate exceeds 50 parts by weight with respect to 100 parts by weight of polypropylene, there is a problem that the calender roll adhesion of the melt is strong and the calendering becomes difficult.

전술한 조성물을 플레네터리 압출기나 일축 또는 이축 압출기, 또는 버스 니이더에서 용융시키는데, 이 때의 압출기의 온도는 210∼270℃로 유지되는 것이 바람직하다. 이렇게 용융된 폴리프로필렌계 혼합물은 압출기 다이를 통과하여 믹싱롤 또는 워밍롤로 이송된다. 믹싱롤 또는 워밍롤은 150∼200℃로 유지되면서 용융물을혼련시켜 주거나 일시저장하는 역할을 한다. 믹싱롤 또는 워밍롤에서 혼련된 용융물은 5cm폭으로 권취된 이송장치를 따라 L자형 캘린더 장치에 보급된다. L자형의 캘린더에서 필름 또는 시트로로 제조되며 캘린더 롤의 표면온도는 180∼250℃의 범위가 바람직하다. 제조된 필름 또는 시트를 80∼110℃로 급속히 냉각하여 폴리프로필렌의 결정화도를 적절히 제어할 수 있다. 상기 급속 냉각공정을 통해 가시광선의 파장보다 작게 폴리프로필렌의 결정화도를 유도하면서 필름 또는 시트의 투명성을 극대화시키는 한편, 정면 롤러나 경면 스틸 벨트(steel belt)에 의해 필름 또는 시트의 표면 평활성을 확보하고 일정한 고광택 표면을 만들어 내어 가시광선이 난반사하지 못하도록 할 수 있다. 이때 급속 냉각이라 하면 캘린더 롤을 거친 180∼250℃의 시트를 냉각 시스템(0∼3℃ 냉각수 투입)에 60∼80m/min의 속도로 투입하여 시트의 온도를 80∼110℃로 냉각함을 의미한다.The above-mentioned composition is melted in a planetary extruder, a single screw or twin screw extruder, or a bus kneader, wherein the temperature of the extruder is preferably maintained at 210 to 270 ° C. The molten polypropylene mixture is passed through an extruder die and transferred to a mixing roll or warming roll. The mixing roll or the warming roll serves to knead or temporarily store the melt while being maintained at 150 to 200 ° C. The melt kneaded in the mixing roll or the warming roll is fed to the L-shaped calender apparatus along a conveying apparatus wound to a width of 5 cm. The L-shaped calender is made of a film or sheet, and the surface temperature of the calender roll is preferably in the range of 180 to 250 ° C. The produced film or sheet can be rapidly cooled to 80 to 110 ° C to appropriately control the crystallinity of the polypropylene. The rapid cooling process maximizes the transparency of the film or sheet while inducing the crystallinity of the polypropylene smaller than the wavelength of visible light, while securing the surface smoothness of the film or sheet by the front roller or mirror steel belt A high gloss surface can be created to prevent visible light from diffusely reflecting. In this case, rapid cooling means that the sheet of 180 to 250 ° C., which has passed through the calender roll, is introduced into the cooling system (0 to 3 ° C. cooling water input) at a speed of 60 to 80 m / min to cool the sheet temperature to 80 to 110 ° C. do.

이와 같이 본 발명에 따른 폴리프로필렌계 조성물 및 이를 이용한 투명 필름 또는 시트의 제조방법으로 인하여, 전통적인 PVC 생산설비인 캘린더 공법의 개념을 탈피하고 탈 PVC 소재로 인하여 친환경적인 투명 제품을 대량 생산할 수 있는 체제가 구축될 수 있다. 또한, 투명 제품의 가공 한계성이 극복됨으로써 폴리프로필렌 소재의 투명성이 요구되는 다양한 용도 개발이 가능해지고, 투명 제품의 용도별 특화 및 고급화가 가능해진다.Thus, due to the polypropylene composition according to the present invention and a method of manufacturing a transparent film or sheet using the same, a system capable of mass-producing eco-friendly transparent products due to the de-PVC material, deviating from the concept of the calendar method, which is a traditional PVC production facility. Can be built. In addition, by overcoming the processing limitations of the transparent product, it is possible to develop various applications in which transparency of the polypropylene material is required, and it is possible to specialize and refine the use of the transparent product.

이하 실시예를 통하여 본 발명을 좀 더 구체적으로 살펴보지만, 하기 예에 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 to the following examples.

실시예 1Example 1

용융흐름지수(230℃/2.16kg)가 3g/10min, 평균밀도는 0.90g/cm3, 수평균분자량이 600,000mol/g인 폴리프로필렌 수지 100중량부에 대하여, 디벤질리덴 솔비톨 5중량부, 메틸렌 비스스테아라마이드 0.8중량부, 칼슘스테아레이트 0.8중량부 및 안정제(Irganox-B225, 시바가이기) 0.6중량부의 배합물을 240℃로 유지된 프레네터리 압출기에서 용융시킨 다음, 캘린더롤 표면온도가 230℃로 유지된 캘린더를 이용하여 필름을 제조하고, 형성된 필름을 80℃로 급속히 냉각(0∼3℃ 냉각수 투입에 70m/min의 속도로 투입)하여 100㎛ 두께의 최종 필름을 제조하였다. 이것의 투명도(%), 인장강도(Kg/mm2), 신장율(%), 인열강도(Kg/mm) 및 캘린더 가공성을 측정하여 하기 표 1에 나타내었다.5 parts by weight of dibenzylidene sorbitol, based on 100 parts by weight of a polypropylene resin having a melt flow index (230 ° C./2.16 kg) of 3 g / 10 min, an average density of 0.90 g / cm 3 and a number average molecular weight of 600,000 mol / g, A blend of 0.8 parts by weight of methylene bis stearamide, 0.8 parts by weight of calcium stearate and 0.6 parts by weight of stabilizer (Irganox-B225, Ciba-Geigy) was melted in a preener extruder maintained at 240 ° C., and the calender roll surface temperature was A film was prepared using a calender maintained at 230 ° C., and the formed film was rapidly cooled to 80 ° C. (added at a rate of 70 m / min to 0-3 ° C. cooling water input) to prepare a final film having a thickness of 100 μm. Its transparency (%), tensile strength (Kg / mm 2 ), elongation (%), tear strength (Kg / mm) and calender workability was measured and shown in Table 1 below.

실시예 2Example 2

용융흐름지수(230℃/2.16kg)가 3g/10min, 평균밀도는 0.90g/cm3, 수평균분자량이 600,000mol/g인 폴리프로필렌 수지 100중량부에 대하여, 디벤질리덴 솔비톨 5중량부, 메틸렌 비스스테아라마이드 0.8중량부, 칼슘스테아레이트 0.8중량부, 안정제(Irganox-B225, 시바가이기) 0.6중량부 및 폴리올레핀 엘라스토머 25중량부의 배합물을 이용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 캘린더 가공을 실시하였다. 이것의 투명도(%), 인장강도(Kg/mm2), 신장율(%), 인열강도(Kg/mm) 및 캘린더 가공성을 측정하여 하기 표 1에 나타내었다.5 parts by weight of dibenzylidene sorbitol, based on 100 parts by weight of a polypropylene resin having a melt flow index (230 ° C./2.16 kg) of 3 g / 10 min, an average density of 0.90 g / cm 3 and a number average molecular weight of 600,000 mol / g, The same procedure as in Example 1 was carried out except that 0.8 parts by weight of methylene bis stearamide, 0.8 parts by weight of calcium stearate, 0.6 parts by weight of stabilizer (Irganox-B225, Ciba-Geigy) and 25 parts by weight of polyolefin elastomer were used. Calendering was performed. Its transparency (%), tensile strength (Kg / mm 2 ), elongation (%), tear strength (Kg / mm) and calender workability was measured and shown in Table 1 below.

실시예 1Example 1 실시예 2Example 2 인장강도The tensile strength MDMD 2.982.98 3.13.1 TDTD 2.72.7 2.92.9 신장율Elongation MDMD 450450 550550 TDTD 350350 400400 인열강도Tear strength MDMD 15.515.5 14.114.1 TDTD 14.814.8 14.014.0 캘린더가공성Calendar processability 양호Good 양호Good 투명도(haze %)Transparency (haze%) 6.96.9 13.513.5

이렇게 제조된 본 발명에 따른 시트는 캘린더 설비를 이용하여 가공하는 것이 가능하기 때문에, 캘린더 롤간의 갭(gap)을 조절하여 시트의 두께를 0.08∼0.60mm의 두께로 조정할 수 있으며, 텐터설비를 통해서는 0.08mm 이하의 두께로도 조정이 가능하다.Since the sheet according to the present invention can be processed using a calendar facility, the thickness of the sheet can be adjusted to a thickness of 0.08 to 0.60 mm by adjusting the gap between the calender rolls, and through the tenter facility Can be adjusted to a thickness of 0.08 mm or less.

또한, 캘린더의 스톡 가이드(stock guide)를 통해서 시트의 폭을 760∼1450mm로 조정할 수 있고, 정면 롤러나 경면 스틸 벨트(steel belt)에 의해 필름 또는 시트의 표면 평활성을 확보하고 급냉시 고광택 유광, 서냉시 무광(반광)으로 광택도 조절이 가능하다.In addition, the width of the sheet can be adjusted to 760 to 1450 mm through the stock guide of the calender, and the surface smoothness of the film or the sheet is ensured by the front roller or the mirrored steel belt, and the high gloss gloss during quenching, Gloss can be adjusted by matte (glow) in slow cooling.

본 발명에 따라 제조된 폴리프로필렌계 투명 필름 및 시트는 종래 캘린더 설비로 가공할 수 있는 재료를 PVC 소재 뿐만 아니라 폴리프로필렌 소재로 확대할 수 있어 캘린더 설비의 효율성을 극대화할 수 있을 뿐만 아니라, 폴리프로필렌의 종래 가공방식인 압출 T-다이 및 브로운 방식보다 생산성이 우수하도록 캘린더에서 고속 및 대량 생산함으로써 폴리프로필렌 투명 필름 및 시트의 생산원가를 절감할 수 있다.The polypropylene-based transparent film and sheet produced according to the present invention can be expanded to the polypropylene material as well as the material that can be processed by conventional calender equipment can maximize the efficiency of the calender equipment, as well as polypropylene It is possible to reduce the production cost of polypropylene transparent film and sheet by high-speed and mass production in the calendar to be more productive than conventional T-die and blow method of the conventional processing method.

또한, 산업자재와 식품 포장 등 재반분야에서 무독성 및 무공해성을 요구하는 세계시장의 흐름에 비추어 볼 때 탈 PVC는 캘린더 가공업체의 당면 과제이며, 이러한 측면에서 폴리프로필렌 투명 필름의 캘린더 생산 기술은 향후 PVC 동 분야의 세계시장을 선도할 수 있는 무한한 가치를 가지게 될 것이다.In addition, de-PVC is a challenge for calender companies in view of the global market demand for non-toxicity and pollution-free in industrial materials and food packaging. In this respect, calendering technology for polypropylene transparent film is It will have infinite value to lead the world market of PVC copper field.

Claims (4)

용융흐름지수(230℃/2.16kg)가 0.1 내지 4g/10min이고, 평균밀도는 0.86 내지 0.91g/cm3의 범위이며, 분자량이 560,000 내지 1,200,000mol/g인 폴리프로필렌 수지 100중량부에 대하여,The melt flow index (230 ° C./2.16 kg) is 0.1 to 4 g / 10 min, the average density is in the range of 0.86 to 0.91 g / cm 3 , and with respect to 100 parts by weight of polypropylene resin having a molecular weight of 560,000 to 1,200,000 mol / g, 디벤질리덴 솔비톨 및 디메틸 벤질리덴 솔비톨을 포함하는 군으로부터 선택되는 적어도 하나의 핵제 1∼8중량부,1 to 8 parts by weight of at least one nucleating agent selected from the group consisting of dibenzylidene sorbitol and dimethyl benzylidene sorbitol, 메틸렌 비스스테아라마이드 또는 에틸렌 비스스테아라마이드로 선택되는 적어도 하나의 블록킹 방지제 0.2∼5중량부,0.2 to 5 parts by weight of at least one antiblocking agent selected from methylene bis stearamide or ethylene bis stearamide, 칼슘 스테아레이트, 징크 스테아레이트 또는 스테아릭산으로 이루어진 군으로부터 선택되는 활제 0.2∼5중량부, 및0.2-5 parts by weight of a lubricant selected from the group consisting of calcium stearate, zinc stearate or stearic acid, and 포스파이트 또는 폐놀계 수지로 이루어진 군으로부터 선택되는 안정제 0.1∼1중량부를 포함하는 것을 특징으로 하는 캘린더가 가능한 투명 필름 및 시트용 폴리프로필렌계 조성물.A polypropylene-based composition for a calendar-capable transparent film and sheet, comprising 0.1 to 1 part by weight of a stabilizer selected from the group consisting of phosphites or phenolic resins. 제1항에 있어서, 상기 조성물이 폴리올레핀 엘라스토머 또는 에틸렌 비닐아세테이트 50중량부 미만을 더욱 포함하는 것을 특징으로 하는 캘린더가 가능한 투명 필름 및 시트용 폴리프로필렌계 조성물.The polypropylene-based composition for a calender capable transparent film and sheet according to claim 1, wherein the composition further comprises less than 50 parts by weight of polyolefin elastomer or ethylene vinyl acetate. 제1항에 있어서, 상기 폴리프로필렌이 호모폴리머 또는 에틸렌 프로필렌 러버와 프로필렌 코폴리머인 것을 특징으로 하는 캘린더가 가능한 투명 필름 및 시트용 폴리프로필렌계 조성물.The polypropylene-based composition for a calendar-capable transparent film and sheet according to claim 1, wherein the polypropylene is a homopolymer or an ethylene propylene rubber and a propylene copolymer. 제1항 내지 제3항 중 어느 한 항에 따른 조성물을 210∼270℃로 유지된 플레네터리 압출기나 일축 또는 이축 압출기, 또는 버스 니이더에서 용융시키는 단계;Melting the composition according to any one of claims 1 to 3 in a planetary extruder or a single or twin screw extruder or a bus kneader maintained at 210 to 270 ° C; 제조된 용융물을 캘린더롤 표면온도가 180∼250℃로 유지된 캘린더를 이용하여 필름 및 시트로 제조하는 단계; 및Preparing the prepared melt into a film and a sheet using a calender whose calender roll surface temperature is maintained at 180 to 250 ° C; And 형성된 필름 및 시트를 80∼110℃로 급속 냉각시키는 단계;Rapid cooling the formed film and sheet to 80-110 ° C .; 를 포함하는 것을 특징으로 하는 폴리프로필렌 투명 필름 및 시트의 제조방법.Method for producing a polypropylene transparent film and sheet comprising a.
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