KR20240044089A - Manufacturing method of Antimicrobial PP Waterproof Sheet Using Shell and the Antimicrobial PP Waterproof Sheet - Google Patents
Manufacturing method of Antimicrobial PP Waterproof Sheet Using Shell and the Antimicrobial PP Waterproof Sheet Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 230000000845 anti-microbial effect Effects 0.000 title 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 92
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 49
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011787 zinc oxide Substances 0.000 claims abstract description 46
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 239000002699 waste material Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000010304 firing Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 14
- 238000004078 waterproofing Methods 0.000 abstract description 10
- 238000004090 dissolution Methods 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 8
- 238000000746 purification Methods 0.000 abstract description 4
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 3
- 239000004743 Polypropylene Substances 0.000 description 65
- 238000011002 quantification Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 10
- 238000007922 dissolution test Methods 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 6
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 241000588724 Escherichia coli Species 0.000 description 3
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 241000242757 Anthozoa Species 0.000 description 1
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000237891 Haliotidae Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 235000015170 shellfish Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
- C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
-
- 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
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명은 물탱크, 저수조, 배수지, 정수장, 염전, 화학공장, 폐기물처리장 등 각종 토목, 건축 구조물 표면의 방수처리에 유리하게 사용하기 위한 방수시트에 관한 것으로, 더욱 상세하게는 항균성 재료로 폐기되는 폐각를 적극적으로 활용하면서 더불어 산화아연도 적절하게 활용하여 항균성과 함께 용출 안전성을 확보한 항균성 PP방수시트의 바람직한 제조방법에 관한 것이다.
본 발명에 따른 폐각을 이용한 항균성 PP방수시트 제조방법은, PPP방수시트 제조방법에서, 폐각을 소성하여 분말화한 폐각미분과 PP수지혼합물을 배합하여 폐각 마스터배치를 제조하는 제1단계; 폐각 마스터배치를 PP수지 베이스의 방수시트 조성물에 혼입하여 항균성 PP방수시트로 제조하는 제2단계;를 포함하는 것을 특징으로 한다. 여기서 제1단계는 산화아연과 PP수지혼합물을 배합하여 산화아연 마스터배치를 더 제조하면서 실시하고 제2단계는 산화아연 마스터배치를 더 혼입하면서 실시할 수 있으며, 더욱 바람직하게는 제1단계는 폐각미분 10~12중량%;와 PP수지혼합물 88~90중량%;로 배합하여 폐각 마스터배치를 제조하는 한편 산화아연 10~12중량%;와 PP수지혼합물 88~90중량%;로 배합하여 산화아연 마스터배치를 제조하면서 실시하고, 제2단계는 폐각 마스터배치와 산화아연 마스터배치를 1:1의 중량비로 하여 PP수지 베이스의 방수시트 조성물에서 20~45중량%의 함유량으로 혼입하면서 실시할 수 있다.The present invention relates to a waterproof sheet for use in waterproofing the surfaces of various civil engineering and building structures such as water tanks, water storage tanks, drainage basins, water purification plants, salt farms, chemical plants, and waste treatment plants, and more specifically, to a waterproofing sheet that is disposed of as an antibacterial material. This relates to a preferred method of manufacturing an antibacterial PP waterproof sheet that secures antibacterial properties and dissolution safety by actively utilizing waste shell and appropriately utilizing zinc oxide.
The method of manufacturing an antibacterial PP waterproof sheet using waste shell according to the present invention includes the first step of producing a waste shell masterbatch by mixing waste shell fine powder and PP resin mixture powdered by baking the waste shell in the PPP waterproof sheet manufacturing method; A second step of mixing the closed masterbatch into a PP resin-based waterproof sheet composition to produce an antibacterial PP waterproof sheet. Here, the first step can be performed by mixing the zinc oxide and PP resin mixture to further prepare the zinc oxide masterbatch, and the second step can be performed by mixing the zinc oxide masterbatch. More preferably, the first step is performed by mixing the zinc oxide and PP resin mixture. A waste shell masterbatch was prepared by mixing 10-12% by weight of fine powder and 88-90% by weight of PP resin mixture, while 10-12% by weight of zinc oxide was mixed with 88-90% by weight of PP resin mixture to prepare zinc oxide. It is carried out while manufacturing the masterbatch, and the second step can be carried out by mixing the waste shell masterbatch and zinc oxide masterbatch in a 1:1 weight ratio in a PP resin-based waterproof sheet composition at a content of 20 to 45% by weight. .
Description
본 발명은 물탱크, 저수조, 배수지, 정수장, 염전, 화학공장, 폐기물처리장 등 각종 토목, 건축 구조물 표면의 방수처리에 유리하게 사용하기 위한 방수시트에 관한 것으로, 더욱 상세하게는 항균성 재료로 폐기되는 폐각를 적극적으로 활용하면서 더불어 산화아연도 적절하게 활용하여 항균성과 함께 용출 안전성을 확보한 항균성 PP방수시트의 바람직한 제조방법에 관한 것이다. The present invention relates to a waterproof sheet for use in waterproofing the surfaces of various civil engineering and building structures such as water tanks, water storage tanks, drainage basins, water purification plants, salt farms, chemical plants, and waste treatment plants, and more specifically, to a waterproofing sheet that is disposed of as an antibacterial material. This relates to a preferred method of manufacturing an antibacterial PP waterproof sheet that secures antibacterial properties and dissolution safety by actively utilizing waste shell and appropriately utilizing zinc oxide.
물탱크, 배수지, 정수장, 염전, 화학공장, 폐기물처리장, 주유소, 세차장, 터널을 포함하는 각종 토목, 건축 구조물 표면에는 구조물의 내구성을 확보하기 위해 통상 방수공사를 실시한다. 특히 물탱크, 취수장, 정수장, 배수지, 염전 등의 구조물에는 대량의 물을 담수하기 위한 콘크리트조나 철골조의 저수조가 있게 마련인데, 저수조 내부는 방수공사를 실시하여 저수조의 내구성을 확보하는 한편 저수조에 담수된 물의 오염을 방지한다.Waterproofing work is usually performed on the surfaces of various civil engineering and architectural structures, including water tanks, drainage ponds, water purification plants, salt farms, chemical plants, waste treatment plants, gas stations, car washes, and tunnels, to ensure the durability of the structures. In particular, structures such as water tanks, water intake plants, water purification plants, drainage ponds, salt farms, etc. have concrete or steel-framed water storage tanks to capture large amounts of water. The interior of the water tank is waterproofed to ensure the durability of the water tank and to ensure the durability of the water tank. Prevent contamination of contaminated water.
방수공사는 에폭시 수지 또는 유리섬유를 보강한 열경화성 수지로 도포하는 습식방법이 일반적이다. 그러나 습식방법은 현장작업이 번거로울 뿐만 아니라 유해한 작업환경이 우려되고 균일한 방수품질을 확보하기 어려운 단점이 있다. 이러한 단점 때문에 최근에는 스테인리스나 폴리에틸렌 계열의 방수시트 등을 부착 설치하는 건식방법이 제안되어 적용되고 있다.Waterproofing work generally involves a wet method of applying epoxy resin or thermosetting resin reinforced with glass fiber. However, the wet method has the disadvantages of not only being cumbersome in field work, but also raising concerns about a harmful working environment and making it difficult to secure uniform waterproofing quality. Because of these shortcomings, a dry method of attaching and installing stainless steel or polyethylene-based waterproofing sheets has been proposed and applied recently.
하지만 종래 건식방법에서 스테인리스를 이용한 경우는 설치 비용이 비쌀 뿐만 아니라 스테인리스의 용접 부분에서 저수조에 담수된 물이 반응하면서 오염을 일으키거나 스테인리스의 강도를 떨어뜨리는 등의 문제가 초래되기 쉽다. 폴리에틸렌 계열의 방수시트를 이용한 경우는 겹침 이음부에서 방수시트가 들뜨기 쉬어 하자 우려가 크고 또한 겹침 이음부에 물때 등 이물질이 끼는 문제가 있었다.However, when stainless steel is used in the conventional dry method, not only is the installation cost expensive, but it is also easy to cause problems such as contamination or a decrease in the strength of the stainless steel as the fresh water in the reservoir reacts at the welded part of the stainless steel. In the case of using polyethylene-based waterproofing sheets, there was a great concern that the waterproofing sheets were prone to lifting at the overlap joints, and there was also a problem of foreign substances such as water stains getting stuck in the overlap joints.
위와 같은 종래 건식방법의 단점을 개선하고자 폴리프로필렌 계열의 PP방수시트가 개발된 바 있으며, 관련 특허로 제10-1142123호, 제10-1418537호가 있다. 특허 제10-1142123호는 경질의 폴리프로필렌을 연질화하여 PP방수시트를 얇은 두께의 롤시트 타입으로 제조하는 방법에 관한 것이고, 특허 제10-1418537호는 특허 제10-1142123호를 더욱 개선하여 저수조에 담수된 물의 오염 방지에 유리하게 역할하면서 경제적으로 제조할 수 있는 PP롤 항균 방수시트에 관한 것이다. In order to improve the above-mentioned shortcomings of the conventional dry method, a polypropylene-based PP waterproof sheet has been developed, and related patents include Nos. 10-1142123 and 10-1418537. Patent No. 10-1142123 relates to a method of manufacturing PP waterproof sheets into thin roll sheet types by softening hard polypropylene, and Patent No. 10-1418537 is a further improvement of Patent No. 10-1142123. This relates to a PP roll antibacterial waterproof sheet that plays an advantageous role in preventing contamination of fresh water in a water tank and can be manufactured economically.
특허 제10-1418537호에는 항균 소재로 고분자 항균재가 제안되어 있는데, 본 발명자들은 PP방수시트에 적용 가능한 천연 유래의 항균 소재를 새로 연구하게 되었다. 천연 유래의 항균 소재로는 구리, 은 등의 금속 소재가 대표적인데, 이들 금속 소재는 항균물질의 용출로 인한 수질 오염의 문제가 우려된다. 이에 PP방수시트에 적용 가능한 새로운 항균 소재로 용출의 안전성을 담보할 수 있는 소재의 개발이 요구된다.Patent No. 10-1418537 proposes a polymer antibacterial material as an antibacterial material, and the present inventors conducted a new study on an antibacterial material of natural origin that can be applied to PP waterproof sheets. Representative natural antibacterial materials include metal materials such as copper and silver, and there are concerns that these metal materials may cause water pollution due to the elution of antibacterial substances. Accordingly, the development of a new antibacterial material applicable to PP waterproof sheets that can guarantee the safety of dissolution is required.
본 발명은 PP방수시트에 적용 가능한 새로운 항균 소재를 개발하고자 안출된 것으로서, 폐기되는 폐각과 함께 산화아연을 항균 소재로 활용함으로써 항균성과 함께 용출의 안정성을 확보하고 더불어 경제성을 확보한 항균성 PP방수시트의 바람직한 제조방법을 제공하는데 기술적 과제가 있다.The present invention was developed to develop a new antibacterial material that can be applied to PP waterproof sheets. By utilizing zinc oxide as an antibacterial material along with discarded waste shell, the antibacterial PP waterproof sheet secures the stability of dissolution along with antibacterial properties and secures economic feasibility. There is a technical challenge in providing a preferred manufacturing method.
상기한 기술적 과제를 해결하기 위해 본 발명은, PP방수시트 제조방법에서, 폐각을 소성하여 분말화한 폐각미분과 PP수지혼합물을 배합하여 폐각 마스터배치를 제조하는 제1단계; 폐각 마스터배치를 PP수지 베이스의 방수시트 조성물에 혼입하여 항균성 PP방수시트로 제조하는 제2단계;를 포함하는 것을 특징으로 하는 폐각을 이용한 항균성 PP방수시트 제조방법을 제공한다. 여기서 제1단계는 산화아연과 PP수지혼합물을 배합하여 산화아연 마스터배치를 더 제조하면서 실시하고 제2단계는 산화아연 마스터배치를 더 혼입하면서 실시할 수 있다. 더욱 바람직하게는 제1단계는 폐각미분 8~16중량%;와 PP수지혼합물 84~92중량%;로 배합하여 폐각 마스터배치를 제조하는 한편, 산화아연 8~16중량%;와 PP수지혼합물 84~92중량%;로 배합하여 산화아연 마스터배치를 제조하면서 실시하고, 제2단계는 폐각 마스터배치와 산화아연 마스터배치를 1:1의 중량비로 하여 PP수지 베이스의 방수시트 조성물에서 20~45중량%의 함유량으로 혼입하면서 실시할 수 있다.In order to solve the above-described technical problem, the present invention, in a method for manufacturing a PP waterproof sheet, includes the first step of producing a waste shell masterbatch by mixing waste shell fine powder powdered by baking waste shell and a PP resin mixture; A second step of mixing the closed shell masterbatch into a PP resin-based waterproof sheet composition to produce an antibacterial PP waterproof sheet is provided. Here, the first step can be performed by mixing the zinc oxide and PP resin mixture to further prepare the zinc oxide masterbatch, and the second step can be performed by mixing the zinc oxide masterbatch. More preferably, the first step is to prepare a waste shell masterbatch by mixing 8 to 16% by weight of dead shell fine powder and 84 to 92% by weight of a PP resin mixture, while 8 to 16% by weight of zinc oxide and 84 to 92% by weight of a PP resin mixture are mixed together in the first step. ~92% by weight; is carried out while manufacturing the zinc oxide masterbatch, and the second step is to mix the waste shell masterbatch and the zinc oxide masterbatch at a weight ratio of 1:1 and add 20 to 45 weight of the PP resin-based waterproof sheet composition. It can be carried out while mixing in % content.
또한 본 발명은 상기와 같은 방법으로 바람지갛게 제조된 항균성 PP방수시트를 제공한다.Additionally, the present invention provides an antibacterial PP waterproof sheet manufactured using the same method as described above.
본 발명에 따르면 다음과 같은 효과를 기대할 수 있다.According to the present invention, the following effects can be expected.
첫째, 본 발명에 따라 제조된 PP방수시트는 대장균과 황색포도상구균 제거에 효과적이고, 유해중금속이 용출되지 아니하기 때문에 항균성과 용출 안전성을 가지는 PP방수시트로 유리하게 활용할 수 있다.First, the PP waterproof sheet manufactured according to the present invention is effective in removing Escherichia coli and Staphylococcus aureus, and because no harmful heavy metals are leached, it can be advantageously used as a PP waterproof sheet with antibacterial properties and leaching safety.
둘째, PP방수시트 제조에 폐기되는 폐각을 활용하기 때문에 자원재활용에 따른 친환경성을 도모할 수 있다. Second, since waste shells that are discarded are used to manufacture PP waterproof sheets, eco-friendliness can be promoted through resource recycling.
셋째, 항균제로 폐각미분과 함께 산화아연을 적절히 사용하기 때문에 경제적으로 PP방수시트를 제조할 수 있다. 또한 폐각미분과 산화아연을 각각 마스터배치로 제조하고 사용량을 정량화하기 때문에 균일한 품질의 제품으로 효율적으로 편리하게 공장생산할 수 있다.Third, because zinc oxide is appropriately used along with waste shell powder as an antibacterial agent, PP waterproof sheets can be manufactured economically. In addition, since waste shell powder and zinc oxide are each manufactured as a masterbatch and the amount used is quantified, products of uniform quality can be produced efficiently and conveniently in the factory.
본 발명은 항균성 PP방수시트 제조방법에 관한 것으로, 폐기되는 폐각을 항균 소재로 활용한다는데 특징이 있다. 본 발명에서 폐각은 죽어 석회화된 산호, 민물 또는 해양에 서식하는 조개류, 고동류, 전복류, 굴류의 패각을 포괄한다. 이러한 폐각은 석회석(CaCO3)이 주성분으로 가열하면 이산화탄소를 휘산하여 생석회(CaO)로 생성되는데, 생석회는 pH 12 이상의 강알칼리성이므로 미생물을 완전분해하여 사멸시킬 수 있다. 본 발명은 이러한 특성의 폐각을 항균 소재로 활용하는 것이다.The present invention relates to a method of manufacturing an antibacterial PP waterproof sheet, and is characterized by using discarded waste shell as an antibacterial material. In the present invention, shells include dead and calcified corals, shellfish, seashells, abalones, and oysters living in freshwater or the ocean. The main ingredient of this waste shell is limestone (CaCO 3 ), and when heated, carbon dioxide volatilizes to produce quicklime (CaO). Quicklime is strongly alkaline with a pH of 12 or higher, so it can completely decompose and kill microorganisms. The present invention utilizes waste shells with these characteristics as an antibacterial material.
구체적으로 본 발명에 따른 항균성 PP방수시트 제조방법은, 폐각을 소성하여 분말화한 폐각미분과 PP수지혼합물을 배합하여 폐각 마스터배치를 제조하는 제1단계; 폐각 마스터배치를 PP수지 베이스의 방수시트 조성물에 혼입하여 항균성 PP방수시트로 제조하는 제2단계;를 포함한다. 여기서 제1단계는 산화아연과 PP수지혼합물을 배합하여 산화아연 마스터배치를 더 제조하면서 실시하고, 제2단계는 산화아연 마스터배치를 더 혼입하면서 실시할 수 있다. 폐각미분과 산화아연 등의 항균 소재를 마스터배치로 제조한 후에 방수시트를 때문에 방수시트에서 항균 소개의 고른 분산이 가능해지며, 이로써 항균성이 균일하게 발현되는 항균성 PP방수시트로 제조할 수 있다.Specifically, the method for manufacturing an antibacterial PP waterproof sheet according to the present invention includes a first step of producing a waste shell masterbatch by mixing waste shell fine powder powdered by baking the waste shell and a PP resin mixture; It includes a second step of mixing the waste shell masterbatch into a PP resin-based waterproof sheet composition to produce an antibacterial PP waterproof sheet. Here, the first step can be performed by mixing the zinc oxide and PP resin mixture to further prepare the zinc oxide masterbatch, and the second step can be performed by mixing the zinc oxide masterbatch. After manufacturing antibacterial materials such as waste shell powder and zinc oxide into a masterbatch, it is possible to evenly distribute antibacterial agents in the waterproof sheet, thereby making it possible to manufacture an antibacterial PP waterproof sheet that exhibits antibacterial properties evenly.
본 발명에서 제1단계는 폐각미분과 PP수지혼합물로 폐각 마스터배치를 제조하는 과정이다. 폐각미분은 폐각을 세척, 분쇄한 후 분급하여 0.1~0.5㎛ 크기의 미분을 소성하는 방식으로 바람직하게 준비할 수 있다. 바람직하게는 폐각미분을 양이온성 계면 활성제 처리단계를 거쳐 입자의 표면 극성을 낮추고, 이를 구동장치에 의해 회전시키는 고온상태의 원통 소성로에 넣고, PP수지혼합물을 투입하여 구 또는 육각형 형태의 마스터배치를 제조할 수 있다. 여기서 PP수지혼합물은 PP수지 단독으로 준비할 수 있는 것은 물론, 엘라스토머 등 PP방수시트 제조에 사용되는 원재료를 적절히 혼합하여 준비할 수 있다.In the present invention, the first step is the process of producing a waste shell masterbatch using a waste shell fine powder and a PP resin mixture. Closed shell fine powder can be preferably prepared by washing and pulverizing the closed shells, classifying them, and then baking fine powder with a size of 0.1 to 0.5 ㎛. Preferably, the closed-shell fine powder is treated with a cationic surfactant to lower the surface polarity of the particles, placed in a high-temperature cylindrical furnace rotated by a driving device, and a PP resin mixture is added to form a masterbatch in the shape of a sphere or hexagon. It can be manufactured. Here, the PP resin mixture can be prepared not only with the PP resin alone, but also by appropriately mixing raw materials used in manufacturing PP waterproof sheets, such as elastomers.
본 발명에서는 항균 소재로 폐각미분과 함께 산화아연을 사용할 수 있는데, 소성 등을 거쳐 제조되는 폐각미분의 시장가격이 고가인 점을 고려하여 비교적 저가인 산화아연으로 일부 치환하고자 한 것이다. 다만 산화아연으로 일부 치환한 경우 금속의 용출 문제가 우려될 수 있기 때문에 적절한 치환량이 중요하다. 본 발명에서는 시험예를 통해 항균성과 함께 용출 안정성을 확보할 수 있고 동시에 제조편의성과 생산효율성을 확보할 수 있는 배합비를 도출하였으며, 그 결과 폐각 마스터배치는 폐각미분 8~16중량%;와 PP수지혼합물 84~92중량%;로 배합하여 제조하고, 산화아연 마스터배치는 산화아연 8~16중량%;와 PP수지혼합물 84~92중량%;로 배합하여 제조할 것을 제안한다. In the present invention, zinc oxide can be used along with spent shell powder as an antibacterial material, and considering the high market price of spent shell powder manufactured through firing, etc., an attempt was made to partially replace it with relatively inexpensive zinc oxide. However, if it is partially substituted with zinc oxide, there may be concerns about metal elution, so the appropriate amount of substitution is important. In the present invention, through test examples, a mixing ratio was derived that can secure dissolution stability along with antibacterial properties and at the same time secure manufacturing convenience and production efficiency. As a result, the closed shell masterbatch contains 8 to 16% by weight of closed shell fine powder; and PP resin. It is proposed to be manufactured by mixing 84 to 92% by weight of the mixture, and the zinc oxide masterbatch is proposed to be manufactured by mixing 8 to 16% by weight of zinc oxide and 84 to 92% by weight of the PP resin mixture.
본 발명에서 제2단계는 PP수지 베이스의 방수시트 조성물에 마스터배치를 혼입하면서 항균성 PP방수시트를 제조하는 과정이다. 폐각미분 8~16중량%와 PP수지혼합물 84~92중량%로 배합하여 제조된 폐각 마스터배치와 산화아연 8~16중량% PP수지혼합물 84~92중량%로 배합하여 제조된 산화아연 마스터배치를 혼입한다면, 폐각 마스터배치와 산화아연 마스터배치는 1;1로 중량비로 하여 PP수지 베이스의 방수시트 조성물에서 20~45중량%의 함유량으로 혼입하는 것이 바람직하다. 방수시트의 품질과 함께 항균성 및 용출 안정성을 확보하고 제조 편의성과 생산 효율성을 확보할 수 있기 때문이다. 이와 같이 혼입하면, PP수지 베이스의 방수시트 조성물에서 항균 소재(폐각미분:산화아연=1:1)가 2~5중량% 혼입된 결과가 된다.In the present invention, the second step is a process of manufacturing an antibacterial PP waterproof sheet by incorporating a masterbatch into a PP resin-based waterproof sheet composition. A waste shell masterbatch manufactured by mixing 8 to 16% by weight of waste shell fine powder and 84 to 92% by weight of a PP resin mixture, and a zinc oxide masterbatch manufactured by mixing 8 to 16% by weight of zinc oxide with 84 to 92% by weight of a PP resin mixture. If mixed, it is preferable to mix the waste shell masterbatch and the zinc oxide masterbatch at a weight ratio of 1:1 and mix them at a content of 20 to 45% by weight in the PP resin-based waterproof sheet composition. This is because, along with the quality of the waterproof sheet, antibacterial properties and dissolution stability can be secured, as well as manufacturing convenience and production efficiency. When mixed in this way, the result is that 2 to 5% by weight of antibacterial material (closed shell fine powder: zinc oxide = 1:1) is mixed into the PP resin-based waterproof sheet composition.
한편 본 발명에서 PP수지 베이스의 방수시트 조성물은 PP수지, 열가소성 엘라스토머수지, 안정제, UV제, 안료 등으로 조성된 조성물일 수 있는데, PP수지는 기본적인 방수성능과 내열, 내약품성, 내오존성을 확보하고, 열가소성 엘라스토머수지로 경질의 PP를 연질화하면서 인장강도를 향상시키며, 안정제, UV제, 안료 등은 첨가제로 기능성을 부여한다. 특히 PP수지와 열가소성 엘라스토머수지는 특허 제10-1418537호에 개시된 동등 이상의 수지를 적용할 수 있다.Meanwhile, in the present invention, the PP resin-based waterproof sheet composition may be a composition composed of PP resin, thermoplastic elastomer resin, stabilizer, UV agent, pigment, etc., and the PP resin secures basic waterproof performance, heat resistance, chemical resistance, and ozone resistance. Thermoplastic elastomer resin softens hard PP and improves tensile strength, and stabilizers, UV agents, pigments, etc. provide functionality as additives. In particular, PP resin and thermoplastic elastomer resin can be applied as equivalent or higher resins disclosed in Patent No. 10-1418537.
이하에서는 제조예 및 시험예에 의거하여 본 발명을 상세히 살펴본다. 다만, 아래의 제조예 및 시험예는 본 발명을 예시하기 위한 것일 뿐이며, 본 발명의 범위가 이로써 한정되는 것은 아니다.Hereinafter, the present invention will be examined in detail based on manufacturing examples and test examples. However, the following production examples and test examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.
[제조예1] 항균성 PP방수시트 제조[Manufacturing Example 1] Manufacturing of antibacterial PP waterproof sheet
폐각을 세척하여 이물질을 완전히 제거한 후 분쇄하여 분말화하고 분급하여01~05㎛ 크기를 갖는 폐각미분을 회수하고, 회수한 폐각미분을 소성하였다. 소성 폐각미분 25중량%과 PP수지 75중량%로 배합하여 펠렛 형태의 폐각 마스터배치를 제조한 후, 아래 [표 1]과 같은 조성으로 방수시트 조성물을 준비하였다. 준비한 방수시트 조성물을 압출하여 항균성 PP방수시트를 제조하였다.After washing the spent shells to completely remove foreign substances, they were pulverized, powdered, and classified to recover spent shell powder with a size of 01-05㎛, and the recovered shell powder was fired. After preparing a pellet-shaped waste shell masterbatch by mixing 25% by weight of fired shell fine powder and 75% by weight of PP resin, a waterproof sheet composition was prepared with the composition shown in [Table 1] below. An antibacterial PP waterproof sheet was manufactured by extruding the prepared waterproof sheet composition.
[시험예1] 항균성 PP방수시트 항균 시험[Test Example 1] Antibacterial test of antibacterial PP waterproof sheet
[제조예1]에서 제조한 항균성 PP방수시트에 대하여 항균성을 시험하였으며, 시험결과는 아래 [표 2]와 같이 나타냈다. 보는 바와 같이 소성 폐각미분의 혼입으로 항균 효과가 확인되며, 특히 실시예2에서는 99.99%의 항균력이 확인된다. The antibacterial PP waterproof sheet manufactured in [Preparation Example 1] was tested for antibacterial properties, and the test results are shown in [Table 2] below. As can be seen, the antibacterial effect is confirmed by the incorporation of calcined shell powder, and in particular, in Example 2, an antibacterial activity of 99.99% is confirmed.
[시험예2] 항균성 PP방수시트의 용출 시험[Test Example 2] Dissolution test of antibacterial PP waterproof sheet
[제조예1]에서 제조한 항균성 PP방수시트에 대하여 정제수로 용출 시험을 실시하였으며, 시험결과는 아래 [표 3]과 같이 나타냈다. 보는 바와 같이 폐각미분을 혼입한 항균성 PP방수시트는 중금속 및 불순미량 물이 검출되지 아니하였으며, 다만 실시예2에서 칼슘이 검출되기는 하였으나 증발잔류물이 불검출되었다. 이와 같은 결과에서 따라 본 발명에 따라 제조한 항균성 PP방수시트는 안전성이 담보된다고 할 수 있다.A dissolution test was conducted with purified water on the antibacterial PP waterproof sheet manufactured in [Preparation Example 1], and the test results are shown in [Table 3] below. As can be seen, heavy metals and impure traces of water were not detected in the antibacterial PP waterproof sheet containing waste shell powder. However, although calcium was detected in Example 2, no evaporation residue was detected. According to these results, it can be said that the antibacterial PP waterproof sheet manufactured according to the present invention is guaranteed to be safe.
(정량한계 0.0008)Not detected
(Limit of quantification 0.0008)
(정량한계 0.0008)Not detected
(Limit of quantification 0.0008)
(정량한계 0.0005)Not detected
(Limit of quantification 0.0005)
(정량한계 0.0005)Not detected
(Limit of quantification 0.0005)
(정량한계 0.001)Not detected
(Limit of quantification 0.001)
(정량한계 0.001)Not detected
(Limit of quantification 0.001)
(정량한계 0.005)Not detected
(Limit of quantification 0.005)
(정량한계 0.005)Not detected
(Limit of quantification 0.005)
(정량한계 0.0001)Not detected
(Limit of quantification 0.0001)
(정량한계 0.0001)Not detected
(Limit of quantification 0.0001)
(정량한계 2)Not detected
(Limit of quantification 2)
(정량한계 2)Not detected
(Limit of quantification 2)
(정량한계 0.4)Not detected
(Limit of quantification 0.4)
(정량한계 0.4)Not detected
(Limit of quantification 0.4)
(정량한계 0.026)Not detected
(Limit of quantification 0.026)
(정량한계 2)Not detected
(Limit of quantification 2)
(정량한계 2)Not detected
(Limit of quantification 2)
(정량한계 0.001)Not detected
(Limit of quantification 0.001)
(정량한계 0.001)Not detected
(Limit of quantification 0.001)
[제조예2] 항균성 PP방수시트 제조[Manufacturing Example 2] Manufacturing of antibacterial PP waterproof sheet
폐각을 세척하여 이물질을 완전히 제거한 후 분쇄하여 분말화하고 분급하여01~05㎛ 크기를 갖는 폐각미분을 회수하고, 회수한 폐각미분을 소성하였다. 소성 폐각미분 11중량%과 PP수지 89중량%로 배합하여 펠렛 형태의 폐각 마스터배치를 제조하고, 산화아연 11중량%과 PP수지 89중량%로 배합하여 펠렛 형태의 산화아연 마스터배치를 제조하였다. 이후, 아래 [표 4]와 같은 조성으로 방수시트 조성물을 준비하였다. 준비한 방수시트 조성물을 압출하여 항균성 PP방수시트를 제조하였다.After washing the spent shells to completely remove foreign substances, they were pulverized, powdered, and classified to recover spent shell powder with a size of 01-05㎛, and the recovered shell powder was fired. A waste shell masterbatch in the form of a pellet was prepared by mixing 11% by weight of calcined shell fine powder and 89% by weight of PP resin, and a zinc oxide masterbatch in the form of a pellet was prepared by mixing 11% by weight of zinc oxide and 89% by weight of PP resin. Afterwards, a waterproof sheet composition was prepared with the composition shown in [Table 4] below. An antibacterial PP waterproof sheet was manufactured by extruding the prepared waterproof sheet composition.
[시험예3] 항균성 PP방수시트 항균 시험 및 용출 시험[Test Example 3] Antibacterial PP waterproof sheet antibacterial test and dissolution test
[제조예2]에서 제조한 항균성 PP방수시트에 대하여 항균 시험과 용출 시험을 실시하였으며, 시험결과는 아래 [표 5]와 같이 나타냈다. 보는 바와 같이 소성 폐각미분과 산화아연을 함께 사용할 때, 비교예1과 실시예1 모두에서 99.99%의 항균력이 확인되었다. 한편 용출 시험 결과 비교예1에서는 산화아연의 용출이 0.003mg/L가 있었으나, 실시예1에서는 산화아연의 용출이 0.001mg/L이하로 거의 없었다. 이와 같은 결과에 따라 소성 폐각미분과 산화아연을 적절한 사용량으로 사용하면 항균성과 용출 안정성을 동시에 확보할 수 있다.An antibacterial test and a dissolution test were conducted on the antibacterial PP waterproof sheet manufactured in [Preparation Example 2], and the test results are shown in [Table 5] below. As can be seen, when calcined shell powder and zinc oxide were used together, an antibacterial activity of 99.99% was confirmed in both Comparative Example 1 and Example 1. Meanwhile, as a result of the dissolution test, in Comparative Example 1, the dissolution of zinc oxide was 0.003 mg/L, but in Example 1, the dissolution of zinc oxide was almost 0.001 mg/L or less. According to these results, if calcined shell powder and zinc oxide are used in appropriate amounts, antibacterial properties and dissolution stability can be secured at the same time.
Claims (4)
폐각을 소성하여 분말화한 폐각미분과 PP수지혼합물을 배합하여 폐각 마스터배치를 제조하는 제1단계;
폐각 마스터배치를 PP수지 베이스의 방수시트 조성물에 혼입하여 항균성 PP방수시트로 제조하는 제2단계;
를 포함하는 것을 특징으로 하는 폐각을 이용한 항균성 PP방수시트 제조방법.In the PP waterproof sheet manufacturing method,
A first step of producing a waste shell masterbatch by mixing waste shell fine powder obtained by firing and powdering the waste shell and a PP resin mixture;
A second step of mixing the waste shell masterbatch into a PP resin-based waterproof sheet composition to produce an antibacterial PP waterproof sheet;
A method of manufacturing an antibacterial PP waterproof sheet using a closed shell, comprising:
상기 제1단계는, 산화아연과 PP수지혼합물을 배합하여 산화아연 마스터배치를 더 제조하면서 실시하고,
상기 제2단계는, 산화아연 마스터배치를 더 혼입하면서 실시하는 것을 특징으로 하는 폐각을 이용한 항균성 PP방수시트 제조방법.In paragraph 1:
The first step is performed by mixing zinc oxide and PP resin mixture to further prepare a zinc oxide masterbatch,
The second step is a method of manufacturing an antibacterial PP waterproof sheet using closed shell, characterized in that it is carried out while further mixing zinc oxide masterbatch.
상기 제1단계는, 폐각미분 8~16중량%;와 PP수지혼합물 84~92중량%;로 배합하여 폐각 마스터배치를 제조하는 한편, 산화아연 8~16중량%;와 PP수지혼합물 84~92중량%;로 배합하여 산화아연 마스터배치를 제조하면서 실시하고,
상기 제2단계는, 폐각 마스터배치와 산화아연 마스터배치를 1:1의 중량비로 하여 PP수지 베이스의 방수시트 조성물에서 20~45중량%의 함유량으로 혼입하면서 실시하는 것을 특징으로 하는 폐각을 이용한 항균성 PP방수시트 제조방법.In paragraph 2,
In the first step, a waste shell masterbatch is prepared by mixing 8 to 16% by weight of fine powder and 84 to 92% by weight of PP resin mixture, while 8 to 16% by weight of zinc oxide and 84 to 92% by weight of PP resin mixture are mixed. It is carried out while producing a zinc oxide masterbatch by mixing in weight%;
The second step is carried out by mixing the waste shell masterbatch and zinc oxide masterbatch at a weight ratio of 1:1 at a content of 20 to 45% by weight in the PP resin-based waterproof sheet composition. PP waterproof sheet manufacturing method.
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| KR101142123B1 (en) | 2011-10-28 | 2012-05-08 | (주) 바이오 특수 | Process of polypropylene roll-sheet and waterproof lining method using the polypropylene roll-sheet |
| KR101418537B1 (en) | 2013-11-05 | 2014-07-10 | 윤종구 | PP Roll-Sheet for Waterproof Lining, Process thereof and Waterproof Lining Method using the PP Roll-Sheet Sheet |
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| KR101142123B1 (en) | 2011-10-28 | 2012-05-08 | (주) 바이오 특수 | Process of polypropylene roll-sheet and waterproof lining method using the polypropylene roll-sheet |
| KR101418537B1 (en) | 2013-11-05 | 2014-07-10 | 윤종구 | PP Roll-Sheet for Waterproof Lining, Process thereof and Waterproof Lining Method using the PP Roll-Sheet Sheet |
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