KR100544398B1 - Polypropylene-based composition for calendar sheet capable of calendering and method for producing polypropylene film and sheet using same - Google Patents
Polypropylene-based composition for calendar sheet capable of calendering and method for producing polypropylene film and sheet using same Download PDFInfo
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- KR100544398B1 KR100544398B1 KR1020000044677A KR20000044677A KR100544398B1 KR 100544398 B1 KR100544398 B1 KR 100544398B1 KR 1020000044677 A KR1020000044677 A KR 1020000044677A KR 20000044677 A KR20000044677 A KR 20000044677A KR 100544398 B1 KR100544398 B1 KR 100544398B1
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- -1 Polypropylene Polymers 0.000 title claims abstract description 55
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 54
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 54
- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 238000003490 calendering Methods 0.000 title abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- 239000003381 stabilizer Substances 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 8
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000008116 calcium stearate Substances 0.000 claims abstract description 7
- 235000013539 calcium stearate Nutrition 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 5
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008117 stearic acid Substances 0.000 claims abstract description 5
- 239000000454 talc Substances 0.000 claims abstract description 5
- 229910052623 talc Inorganic materials 0.000 claims abstract description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims abstract description 5
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920001519 homopolymer Polymers 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- 229920000747 poly(lactic acid) Polymers 0.000 claims 1
- 239000004626 polylactic acid Substances 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 229920006124 polyolefin elastomer Polymers 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract 1
- 239000005038 ethylene vinyl acetate Substances 0.000 abstract 1
- AJDORVSWJRNUEA-UHFFFAOYSA-N octadecanoyloxymethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCOC(=O)CCCCCCCCCCCCCCCCC AJDORVSWJRNUEA-UHFFFAOYSA-N 0.000 abstract 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- 229940078456 calcium stearate Drugs 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 229960004274 stearic acid Drugs 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 229940057977 zinc stearate Drugs 0.000 description 3
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 229920005673 polypropylene based resin Polymers 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 229940114926 stearate Drugs 0.000 description 1
Classifications
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
-
- 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
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
Landscapes
- 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)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
본 발명은 캘린더가 가능한 데코시트용 폴리프로필렌계 조성물 및 이를 이용한 폴리프로필렌 필름 및 시이트의 제조방법에 관한 것으로, 좀 더 구체적으로는 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 100-200중량부, 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 조성물, 및 이를 이용한 폴리프로필렌 필름 및 시이트의 제조방법에 관한 것이다. 본 발명에 따른 조성물은 캘린더 생산품의 부가가치를 높이고 생산물질을 다양할 수 있으며, 폴리프로필렌 필름 및 시이트의 생산성을 향상시키고 생산원가를 절감할 수 있다.The present invention relates to a polypropylene-based composition for calendar sheets capable of calendering, and a method for producing a polypropylene film and sheet using the same. More specifically, the melt flow index (230 ° C / 2.16kg) is 0.1 to 4 g / 10 min. Average density is in the range of 0.86 to 0.91 g / cm 3 , at least 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 molecular weight of 560,000 to 1,200,000 mol / g. 100-200 parts by weight of one filler, 0.4-5 parts by weight of at least one antiblocking agent selected from the group consisting of silica, methylene bis stearamide, ethylene bis stearamide or mixtures thereof, calcium stearate, zinc stearate or 0.2-3 parts by weight of a lubricant selected from the group consisting of stearic acid and 0.1-1 part by weight of a stabilizer It is a calendar available decor sheet a polypropylene-based composition, and the poly using the same a method of manufacturing a polypropylene film and a sheet. The composition according to the present invention can increase the added value of the calendered product and can vary the production material, improve the productivity of the polypropylene film and sheet and reduce the production cost.
폴리프로필렌 필름, 메틸렌 비스스테아레이트, 폴리올레핀 에라스토머, 충진제, 블록킹 방지제, 활제, 안정제, 에틸렌 비닐아세테이트Polypropylene film, methylene bisstearate, polyolefin elastomer, filler, antiblocking agent, lubricant, stabilizer, ethylene vinyl acetate
Description
본 발명은 캘린더가 가능한 데코시트용 폴리프로필렌계 조성물 및 이를 이용한 폴리프로필렌 필름 및 시이트의 제조방법에 관한 것으로, 좀 더 구체적으로는 폴리프로필렌 수지에 대하여 탄산칼슘, 탈크, 카올린, 셀룰로오스 파우더 및 이산화티타늄으로 이루어진 군으로부터 선택된 적어도 하나의 충진제, 실리카, 메틸렌 비스스테아라마이드, 에틸렌 비스스테아라마이드 또는 이들의 혼합물로 이루어진 군으로부터 선택된 적어도 하나의 블록킹 방지제, 칼슘 스테아레이트, 징크 스테아레이트 또는 스테아릭산으로 이루어진 군으로부터 선택된 활제 및 안정제를 포함하는 캘린더가 가능한 데코시트용 폴리프로필렌계 조성물 및 이를 이용한 폴리프로필렌 필름 및 시이트의 제조방법에 관한 것이다.The present invention relates to a polypropylene-based composition for calendar sheet capable of calendering and to a method for producing a polypropylene film and sheet using the same, and more specifically, to a polypropylene resin, calcium carbonate, talc, kaolin, cellulose powder and titanium dioxide. At least one filler selected from the group consisting of: at least one antiblocking agent selected from the group consisting of silica, methylene bis stearamide, ethylene bis stearamide or mixtures thereof, calcium stearate, zinc stearate or stearic acid The present invention relates to a polypropylene-based composition for calendars capable of calendars containing a lubricant and a stabilizer selected from the group, and a method for producing a polypropylene film and a sheet using the same.
종래의 캘린더(calender) 가공의 공정 및 설비는 고무 시이트(rubber sheet)를 제조하는데 적용되었으며 점차적으로 PVC 필름 및 시이트를 제조하기 위해 사용 되는 공정 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 시이트의 전이가 어려운 점을 들 수 있다. 따라서, 통상적으로 폴리프로필렌 필름 또는 시이트는 T-다이(die) 압출방식이나 브로운(blown) 공법을 생산하는 경우가 많았다.Conventional calender process and equipment has been applied to the production of rubber sheet (rubber sheet) and gradually used to manufacture PVC film and sheet, it was difficult to process polypropylene. Its main causes are when polypropylene is calendered, polypropylene adheres to the surface of the calender roll, making it impossible to process, and the melt strength of polypropylene is so weak that the film or sheet is transferred 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 시이트를 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 시이트를 제조하는 방법을 게시하고 있다. 이들 용융물은 시이트의 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 25-75% by weight of polyolefin resin with 25-75% by weight of vegetable fibers and maintained at about 170 ℃ A method of making films and sheets from calender rolls after kneading in a Banbury mixer is disclosed. These melts were calendered by not sticking to the calender rolls by the vegetable fibers during the sheet manufacturing process.
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 지방 산을 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 3 to 13 parts by weight 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 시이트를 제조하는 방법이 게시되어 있다. 배합으로는 폴리프로필렌 수지 70 내지 100중량부에 대하여 폴리에틸렌 수지를 0 내지 30중량부 사용하였다. 또한, 폴리프로필렌 배합의 가공성을 높이기 위해 EPDM 에라스토머 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 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 take-up 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 폴리 에틸렌으로 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 ° C./2.1 kg) of 0.2 to 5 g based on 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) a 0.8 to 5g / 10min, a density of 0.91 to 0.94g / cm 3 linear 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.
본 발명자들은 폴리프로필렌, 충진제, 블록킹 방지제, 활제 및 안정제를 이용하여 캘린더로 생산할 수 있는 데코시트용 폴리프로필렌계 조성물을 얻을 수 있음을 발견하였고, 이에 기초하여 본 발명이 완성되었다.The present inventors have found that polypropylene-based compositions for decorates that can be produced in calendars using polypropylene, fillers, antiblocking agents, lubricants and stabilizers have been obtained, and the present invention has been completed based on this.
따라서, 본 발명의 목적은 캘린더 가공이 가능한 데코시트용 폴리프로필렌계 조성물을 제공하는데 있다.Accordingly, an object of the present invention is to provide a polypropylene composition for decor sheet capable of calendering.
본 발명의 다른 목적은 상기 조성물을 이용하여 폴리프로필렌 필름 및 시이트를 제조하는 방법을 제공하는데 있다.Another object of the present invention to provide a method for producing a polypropylene film and sheet using the composition.
상기 목적을 달성하기 위한 본 발명의 캘린더가 가능한 데코시트용 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 탄산칼슘, 탈크, 카올린, 셀룰로오스 파우더 및 이산화티타늄으로 이루어진 군으로부터 선택된 적어도 하나의 충진제 100-200중량부, 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 포함한다.In order to achieve the above object, the polypropylene-based composition for a calender-coated sheet of the present invention 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 3 . 100-200 parts by weight of at least one filler selected from the group consisting of calcium carbonate, talc, kaolin, cellulose powder and titanium dioxide with respect to 100 parts by weight of polypropylene resin having a molecular weight of 560,000 to 1,200,000 mol / g, silica, methylene bis 0.4-5 parts by weight of at least one antiblocking agent selected from the group consisting of stearamide, ethylene bis stearamide or mixtures thereof, 0.2-3 parts by weight of lubricant selected from the group consisting of calcium stearate, zinc stearate or stearic acid And 0.1-1 part by weight of stabilizer.
상기 다른 목적을 달성하기 위한 본 발명의 폴리프로필렌 필름 및 시이트의 제조방법은 상기 조성물을 200-280℃로 유지된 플레네터리 압출기나 일축 또는 이축 압출기, 또는 버스 니이더(buss kneader)에서 용융시킨 다음, 캘린더롤 표면온도가 185-240℃로 유지된 캘린더를 이용하여 필름 및 시이트를 제조하는 것으로 이루어진다.The method for producing a polypropylene film and sheet of the present invention for achieving the above another object is to melt the composition in a planetary extruder or a single or twin screw extruder, or a bus kneader maintained at 200-280 ℃ Next, a film and a sheet are produced using a calender whose calender roll surface temperature is maintained at 185-240 ° 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/cm3 범위이다.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 1중량부 만을 사용하여 롤밀시켜 가공성을 살펴본 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 roll milling using only 100 parts by weight of polypropylene-based resin and 1 part by weight of lubricant having a 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 are generated. As a result, the mill was rolled using only 1 part by weight of lubricant with 100 parts by weight of polypropylene resin having an MFI of 0.5, and found that the polypropylene melt reduced the adhesiveness with the surface of the mixing roll 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 시이트를 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 실리카, 메틸렌 비스스테아라마이드 또는 에틸렌 비스스테아라마이드로 이루어진 군으로부터 적어도 하나 선택된 블록킹 방지제(anti-blocking agent)를 첨가하였다. 본 발명에 따른 캘린더 공정에서 상기 블록킹 방지제를 사용하여 폴리프로필렌 용융물과 캘린더 롤 표면에 점착성을 줄일 수 있었다. 본 발명의 조성물에 사용하는 실리카의 평균입자 크기는 3.5-5.0㎛, 평균밀도는 0.15-0.35g/cm3이고, 표면적은 350-650m2/g이다. 또한, 본 발명에 따른 조성물에서 폴리프로필렌 100중량부에 대하여 블록킹 방지제를 0.4-5.0중량부로 사용하는데, 0.4중량부 미만이면 캘린더 롤에 용융물이 점착되어 가공이 불가능하였고, 5.0중량부를 초과하면 실리카 분산이 잘 이루어지지 않아 시이트의 표면이 거칠어지는 단점이 있다. 상기 실리카의 크기, 밀도, 표면적 등을 한정하는 이유는 배합 후 혼합시 작업성 및 분산성 때문이며, 상기 입자크기보다 작은 경우는 배합후 혼합이 어렵다.Therefore, in the present invention, at least one anti-blocking agent selected from the group consisting of silica, methylene bis stearamide or ethylene bis stearamide may be added to solve the tack problem. The antiblocking agent was used in the calendering process according to the present invention to reduce adhesion to the polypropylene melt and calender roll surface. The average particle size of the silica used in the composition of the present invention is 3.5-5.0 µm, the average density is 0.15-0.35 g / cm 3 , and the surface area is 350-650 m 2 / g. In addition, in the composition according to the present invention, an antiblocking agent is used in an amount of 0.4-5.0 parts by weight based on 100 parts by weight of polypropylene, but less than 0.4 parts by weight of the melt adheres to the calender roll, and thus processing is impossible. There is a disadvantage that the surface of the sheet is rough because it is not made well. The reason for limiting the size, density, surface area, etc. of the silica is due to workability and dispersibility in mixing after mixing, and when mixing smaller than the particle size, mixing after mixing is difficult.
또한, 본 발명에서 상기 조성물의 분산성 및 가공성 향상시키기 위해 활제를 사용하며, 그 사용량은 0.2-3중량부가 바람직하고, 예를 들어 칼슘-스테아레이트, 징크-스테아레이트, 스테아릭산 등을 들 수 있다. 또한, 안정제는 0.1-1중량부로 사용되며, 시판되는 광안정제 또는 열안정제를 사용할 수 있다.In addition, the present invention uses a lubricant to improve the dispersibility and processability of the composition, the amount is preferably 0.2-3 parts by weight, for example calcium-stearate, zinc-stearate, stearic acid and the like. have. In addition, the stabilizer is used in 0.1-1 parts by weight, and commercially available light stabilizers or heat stabilizers may be used.
본 발명에서 사용되는 폴리올레핀 에라스토머 또는 에틸렌 비스아세테이트는 최종 조성물로 제조된 시이트에 연성을 부여하고, 충진제 분산을 향상시켜 표면 평활성을 높이기 위해 첨가되며, 상기 폴리프로필렌 수지 100중량부에 대하여 50중량부 미만의 범위로 첨가된다. 폴리올레핀 에라스토머 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 is added to impart ductility to the sheet made of the final composition, improve filler dispersion and increase surface smoothness, and 50 weight parts based on 100 parts by weight of the polypropylene resin. It is added in less than a range. When the amount of polyolefin elastomer or ethylene bisacetate is used exceeds 50 parts by weight with respect to 100 parts by weight of polypropylene, calender roll adhesion of the melt is strong and there is a problem that calendering becomes difficult.
또한, 본 발명에 사용되는 충진제는 100 내지 200중량부를 첨가한다. 이 때, 사용량이 200중량부를 초과하면 폴리프로필렌 필름 및 시이트의 물성이 떨어지는 문제점이 있다. 상기 충진재로는 탄산칼슘, 탈크, 카올린, 셀룰로오스 파우더, 또는 이산화티타늄으로 이루어진 군으로부터 선택되어 사용될 수 있다. 상기 탄산칼슘은 평균입자 크기가 5-10㎛범위이고, 평균밀도는 2.5-2.9g/cm3의 범위이다. 상기 이산화티타늄은 평균입자크기가 0.1-0.22㎛ 범위이고, 평균밀도는 평균밀도는 4.0-4.2g/cm3의 범위이다. 상기 셀룰로오스 파우더의 평균입자는 32-100㎛이다.In addition, the filler used in the present invention is added to 100 to 200 parts by weight. At this time, when the amount of use exceeds 200 parts by weight, there is a problem that the physical properties of the polypropylene film and the sheet are inferior. The filler may be selected from the group consisting of calcium carbonate, talc, kaolin, cellulose powder, or titanium dioxide. The calcium carbonate has an average particle size in the range of 5-10 μm and an average density in the range of 2.5-2.9 g / cm 3 . The titanium dioxide has an average particle size in the range of 0.1-0.22 μm, and the average density is in the range of 4.0-4.2 g / cm 3 . The average particle of the cellulose powder is 32-100 μm.
이러한 조성물을 플레네터리 압출기나 일축 또는 이축 압출기, 또는 버스 니이더에서 용융시키는데, 이 때의 압출기의 온도는 200-280℃로 유지되는 것이 바람직하다. 이렇게 용융된 폴리프로필렌계 혼합물은 압출기 다이를 통과하여 워밍롤로 이송된다. 워밍롤은 150-170℃로 유지되면서 용융물을 혼련시켜 주거나 일시저장하는 역할을 한다. 워밍롤에서 혼련된 용융물은 5cm폭으로 권취된 이송장치를 따라 L자형 캘린더 장치에 보급된다. L자형의 캘린더에서 필름으로 제조되며 캘린더 롤의 표면온도는 185-240℃의 범위가 바람직하다. 제조된 필름은 권취롤에서 권취하며 온도범위는 40-150℃이다.The composition is melted in a planetary extruder, single screw or twin screw extruder, or bus kneader, wherein the temperature of the extruder is preferably maintained at 200-280 ° C. The molten polypropylene mixture is passed through a extruder die to a warming roll. The warming roll serves to knead or temporarily store the melt while being maintained at 150-170 ° C. The melt kneaded in the warming roll is fed to the L-shaped calender with a feeder wound 5 cm wide. The L-shaped calender is made of a film and the surface temperature of the calender roll is preferably in the range of 185-240 ° C. The produced film is wound on a take-up roll and the temperature range is 40-150 ° C.
이하 실시예와 비교예를 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 Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples.
실시예 1Example 1
폴리프로필렌 100중량부, 탄산칼슘 100중량부, 이산화티타늄 20중량부, 실리카 1.5중량부, 칼슘스테아레이트 0.8중량부, 안정제(Irganox-B225, 시바가이기) 0.6중량부의 배합물을 240℃로 유지된 프레네터리 압출기에서 용융시킨 다음, 캘린더롤 표면온도가 230℃로 유지된 캘린더를 이용하여 최종 필름의 두께를 100㎛로 제조하였다. 이것의 인장강도(Kg/mm2), 신장율(%), 인열강도(Kg/mm) 및 캘린더 가공성을 측정하여 하기 표 1에 나타내었다.100 parts by weight of polypropylene, 100 parts by weight of calcium carbonate, 20 parts by weight of titanium dioxide, 1.5 parts by weight of silica, 0.8 parts by weight of calcium stearate, 0.6 parts by weight of a stabilizer (Irganox-B225, Ciba-Geigy) was maintained at 240 ° C. After melting in a preener extruder, the thickness of the final film was prepared to 100 μm using a calender with a calender roll surface temperature maintained at 230 ° C. Its tensile strength (Kg / mm 2 ), elongation (%), tear strength (Kg / mm) and calender workability was measured and shown in Table 1 below.
실시예 2Example 2
폴리프로필렌 100중량부, 탄산칼슘 130중량부, 이산화티타늄 20중량부, 실리카 1.5중량부, 칼슘스테아레이트 0.8중량부, 안정제(Irganox-B225, 시바가이기) 0.6중량부 및 폴리올레핀 에라스토머 25중량부의 배합물을 이용한 것을 제외하고는 상기 실시예 1과 동일하게 실시하여 캘린더 가공을 실시하였다. 이것의 인장강도(Kg/mm2), 신장율(%), 인열강도(Kg/mm) 및 캘린더 가공성을 측정하여 하기 표 1에 나타내었다.100 parts by weight of polypropylene, 130 parts by weight of calcium carbonate, 20 parts by weight of titanium dioxide, 1.5 parts by weight of silica, 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 The calendering was carried out in the same manner as in Example 1, except that the negative blend was used. Its tensile strength (Kg / mm 2 ), elongation (%), tear strength (Kg / mm) and calender workability was measured and shown in Table 1 below.
본 발명에 따라 데코시트용 필름 및 시이트는 표면상태가 우수하고 백색도, 은패력, 물성 등이 양호하여 데코레이션용으로 적합하며, 또한 종이 대체용 인쇄용지나 라벨류, 스티커류에 사용될 수 있으며, 내수성과 재활용성이 요구되는 일회용 상자나 쇼핑백, 봉투에 이용될 수 있어 캘린더 생산품의 부가가치를 높이고 생산물질을 다양할 수 있다. 또한 생산성을 향상시키고 생산원가를 절감할 수 있다.According to the present invention, the film and the sheet for decorating sheet have excellent surface condition and have good whiteness, silver squeeze, physical properties, etc., and are suitable for decoration, and can also be used for printing paper, labels or stickers for paper replacement, It can be used in disposable boxes, shopping bags, and bags that require recyclability, increasing the added value of calendar products and producing a variety of materials. It can also improve productivity and reduce production costs.
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| WO2011071272A2 (en) | 2009-12-07 | 2011-06-16 | 주식회사 그린아이에스 | Method for fabricating a polyolefin sheet using a roller device |
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| KR100710552B1 (en) * | 2002-12-10 | 2007-04-24 | 에스케이 주식회사 | Neutral ｐH breathable film composition without moisture during processing |
| KR100691464B1 (en) * | 2005-02-16 | 2007-03-09 | 삼성토탈 주식회사 | Polypropylene Resin Composition for Decor Sheet |
| JP7298137B2 (en) * | 2018-11-08 | 2023-06-27 | 凸版印刷株式会社 | Decorative sheet and its manufacturing method |
| CN116082745B (en) * | 2022-11-18 | 2024-06-25 | 昆山科顺防水材料有限公司 | Preparation method and application of waterproof coiled material sheet |
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| KR960041268A (en) * | 1995-05-25 | 1996-12-19 | 가와노 에이지로 | The polypropylene resin composition |
| KR19980057240A (en) * | 1996-12-30 | 1998-09-25 | 이종학 | Polypropylene-based film and site composition capable of calendering, and a method of manufacturing the same |
| JP2000143933A (en) * | 1998-09-02 | 2000-05-26 | Chisso Corp | Polypropylene composition for calendering |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR960041268A (en) * | 1995-05-25 | 1996-12-19 | 가와노 에이지로 | The polypropylene resin composition |
| KR19980057240A (en) * | 1996-12-30 | 1998-09-25 | 이종학 | Polypropylene-based film and site composition capable of calendering, and a method of manufacturing the same |
| JP2000143933A (en) * | 1998-09-02 | 2000-05-26 | Chisso Corp | Polypropylene composition for calendering |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2011071272A2 (en) | 2009-12-07 | 2011-06-16 | 주식회사 그린아이에스 | Method for fabricating a polyolefin sheet using a roller device |
| CN102712767A (en) * | 2009-12-07 | 2012-10-03 | Sk综合化学株式会社 | Method for fabricating a polyolefin sheet using a roller device |
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