KR102129008B1 - Plastic composition using oyster chells and manufacturing method of artificial shell for oyster farming comprising the plastic composition - Google Patents
Plastic composition using oyster chells and manufacturing method of artificial shell for oyster farming comprising the plastic composition Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 229920003023 plastic Polymers 0.000 title claims abstract description 37
- 239000004033 plastic Substances 0.000 title claims abstract description 37
- 241000237502 Ostreidae Species 0.000 title claims abstract description 36
- 235000020636 oyster Nutrition 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000009313 farming Methods 0.000 title claims abstract description 19
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 110
- 239000000843 powder Substances 0.000 claims abstract description 66
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 33
- 239000000454 talc Substances 0.000 claims abstract description 15
- 229910052623 talc Inorganic materials 0.000 claims abstract description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 14
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000077 silane Inorganic materials 0.000 claims abstract description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims description 27
- 238000000465 moulding Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010298 pulverizing process Methods 0.000 abstract description 5
- -1 hydroxycarboxylic acid ester Chemical class 0.000 description 25
- 239000000155 melt Substances 0.000 description 25
- 239000004743 Polypropylene Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 229920001155 polypropylene Polymers 0.000 description 18
- 239000004014 plasticizer Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 239000005038 ethylene vinyl acetate Substances 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- 238000001125 extrusion Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 5
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 3
- GIEGKXINITVUOO-UHFFFAOYSA-N 2-methylidenebutanedioic acid Chemical compound OC(=O)CC(=C)C(O)=O.OC(=O)CC(=C)C(O)=O GIEGKXINITVUOO-UHFFFAOYSA-N 0.000 description 2
- ZKGBTVUYBKEWEZ-UHFFFAOYSA-N 5-butyl-6-hydroxyundecane-4,5,6-tricarboxylic acid tributyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound C(CCC)C(C(C(C(=O)O)(CCCC)CCCC)(O)C(=O)O)C(=O)O.C(CC(O)(C(=O)OCCCC)CC(=O)OCCCC)(=O)OCCCC ZKGBTVUYBKEWEZ-UHFFFAOYSA-N 0.000 description 2
- 229920000426 Microplastic Polymers 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000003306 harvesting Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000004006 olive oil Substances 0.000 description 2
- 235000008390 olive oil Nutrition 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 235000015170 shellfish Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 241000237509 Patinopecten sp. Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000020637 scallop Nutrition 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
- C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
- A01K61/00—Culture of aquatic animals
- A01K61/50—Culture of aquatic animals of shellfish
- A01K61/54—Culture of aquatic animals of shellfish of bivalves, e.g. oysters or mussels
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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
- C08K3/34—Silicon-containing compounds
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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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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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
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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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
- C08K5/54—Silicon-containing compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
- Y02A40/81—Aquaculture, e.g. of fish
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Marine Sciences & Fisheries (AREA)
- Zoology (AREA)
- Animal Husbandry (AREA)
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Abstract
Description
본 발명은 굴 패각을 이용한 플라스틱 조성물 및 이를 포함하는 굴 양식용 인조패각의 제조방법에 관한 것으로, 더욱 상세하게는 굴패각분말에 무수말레인산(maleic anhydride), 이타콘산(itaconic acid), 실란(silane) 및 활석(talc) 중에서 선택되는 적어도 어느 하나의 상용화제와 폴리올레핀계 수지를 포함하여 구성되는 혼합조성물로, 상기 혼합조성물은 평균 용융지수(MI)가 10 내지 50을 갖는 것을 특징으로 하는 굴 패각을 이용한 플라스틱 조성물 및 이를 포함하는 굴 양식용 인조패각의 제조방법에 관한 것이다. The present invention relates to a method for manufacturing a plastic composition using oyster shells and artificial shells for oyster farming including the same, and more specifically, maleic anhydride, itaconic acid and silane in oyster shell powder And talc (talc) is a mixed composition consisting of at least one compatibilizer selected from at least one compatibilizer and a polyolefin-based resin, the mixed composition has an average melt index (MI) of 10 to 50 characterized in that the oyster shell It relates to a plastic composition used and a method of manufacturing an artificial shell for oyster farming including the same.
우리나라의 연간 굴 패각(Oyster shells) 발생량은 28만톤에 달하며, 발생되는 패각 중 대부분은 산업 폐기물로 처리되고 일부만 재활용되고 있다. 특히, 2010년부터는 굴 패각 발생량의 약 26%가 매립지 확보 등의 어려움으로 제대로 처리되지 못해 연안의 공터에 야적되거나 방치되고 있다. 폐기되는 굴 패각은 심각한 공해문제를 발생시키고, 방치된 굴 패각은 경관을 훼손시키며 패각류에 부착된 육질에 의해 미생물이 번식하면서 악취 및 침출수 누출을 유발하는 문제가 있어, 이러한 굴 패각의 처리방법을 비롯한 굴 패각의 재활용, 또는 자원화에 대한 요구가 증가하고 있다.The annual amount of oyster shells produced in Korea reaches 280,000 tons, and most of the shells generated are treated as industrial waste and only partially recycled. In particular, since 2010, about 26% of the amount of oyster shelling has not been properly handled due to difficulties such as securing a landfill site, and it has been accumulated or neglected on the coastal vacant land. Discarded oyster shells cause serious pollution problems, neglected oyster shells damage the landscape, and there is a problem that microorganisms propagate by the flesh attached to the shellfish and cause odor and leachate leakage. There is an increasing demand for recycling or recycling of oyster shells.
일반적으로 굴 패각에는 약 95% 정도의 탄산칼슘(CaCO3)이 함유되어 있으며 그 외에 탄산마그네슘(MgCO3)와 황산칼슘(CaSO4)이 소량 포함되어 있다. 이에, 종래에는 굴 패각을 분쇄하여 비료, 탄산칼슘의 제조, 각종 충전제, 종이 코팅제, 안료 등의 산업용 원료, 화장품 및 의약품 원료 등으로 사용하거나 가리비 껍데기와 함께 굴 채묘용으로 활용되었다. 하지만, 굴 양식을 위하여 채묘용으로 재활용되는 자연산 굴 패각은 바닷물의 흐름에 따라 서로 부딪히면서 종패가 이탈되어 주변 환경을 오염시키거나, 각기 다른 크기의 패각을 관리하고 일정한 줄에 끼우기 위해 천공하는 작업이 요구되어 인건비 및 작업시간 상승으로 경제성이 낮아져, 최근에는 굴 양식용 인조 패각이 도입되고 있다.In general, oyster shells contain about 95% calcium carbonate (CaCO 3 ), and in addition, a small amount of magnesium carbonate (MgCO 3 ) and calcium sulfate (CaSO 4 ). Thus, conventionally, oyster shells were crushed to be used as fertilizer, calcium carbonate production, various fillers, paper coatings, industrial raw materials such as pigments, and raw materials for cosmetics and pharmaceuticals, or used for oyster harvesting with scallop shells. However, for oyster farming, natural oyster shells, which are recycled for harvesting, collide with each other according to the flow of seawater, causing the sheds to escape, contaminating the surrounding environment, or managing different sizes of shells and punching them to fit on certain rows. Due to the increase in labor costs and working hours, economic efficiency is lowered, and artificial shells for oyster farming have recently been introduced.
구체적으로, 선행기술1(대한민국 등록특허 제10-1624943호)에는 굴 껍데기 분말을 활용하여 강도나 탄성이 증대된 굴 양식용 인조패각에 대해 개시되어 있다. 하지만, 선행기술1은 굴 껍데기 분말의 함유량이 13 내지 25 중량% 정도로 인조패각의 대부분의 구성이 플라스틱 함량이 높아 장시간 바닷물에 배치시 미세플라스틱 유출로 인한 해양오염의 문제가 있으며, 플라스틱의 고 함량에 의한 제조단가가 높은 단점이 있다. 이에, 굴 껍데기 분말의 함량을 높이기 위한 연구가 진행되었으나, 혼합되는 수지와의 상용성이 낮아 성형품의 품질이 저하되어, 개선이 필요한 실정이다.Specifically, prior art 1 (Republic of Korea Patent Registration No. 10-1624943) discloses an artificial shell for oyster farming with increased strength or elasticity by utilizing oyster shell powder. However, the prior art 1 has a problem of marine pollution due to microplastic spillage when placed in sea water for a long time because the plastic content of most of the artificial shells is about 13 to 25% by weight of the oyster shell powder. There is a disadvantage in that the manufacturing cost is high. Accordingly, studies have been conducted to increase the content of the oyster shell powder, but the compatibility with the resin to be mixed is low, and the quality of the molded product is deteriorated, requiring improvement.
상술한 문제점을 해결하기 위하여, 본 발명은 굴 패각 분말 함량을 최대화하여 굴 패각의 활용도를 높이면서 인조패각 제조시 생산비용을 절감할 수 있는, 굴 패각을 이용한 플라스틱 조성물을 제공하는 데에 있다. In order to solve the above-mentioned problems, the present invention is to provide a plastic composition using oyster shell, which can reduce the production cost when manufacturing artificial shell while increasing the utilization of oyster shell by maximizing the content of oyster shell powder.
또한, 본 발명은 첨가되는 수지의 용융특성을 조절하여 형성된 플라스틱 조성물을 성형성을 향상시킬 수 있는, 굴 패각을 이용한 플라스틱 조성물을 제공하는 데에 있다.In addition, the present invention is to provide a plastic composition using an oyster shell, which can improve the moldability of the plastic composition formed by adjusting the melting properties of the resin to be added.
아울러, 본 발명은 굴 패각 분말 함량을 최대화하면서도 수지와의 상용성을 높여 이를 포함하는 성형제품의 품질을 높일 수 있는, 굴 양식용 인조패각의 제조방법을 제공하는 데에 있다.In addition, the present invention is to provide a method for manufacturing an artificial shell for oyster farming, which can increase the quality of a molded product including the same by maximizing the content of the oyster shell powder while increasing the compatibility with the resin.
상기 과제를 이루기 위하여 본 발명의 일 측면은 굴 패각을 분쇄시킨 굴패각분말; 무수말레인산(maleic anhydride), 이타콘산(itaconic acid), 실란(silane) 및 활석(talc) 중에서 선택되는 적어도 어느 하나의 상용화제; 및 폴리올레핀계 수지를 포함하여 구성되는 혼합조성물로, 상기 혼합조성물은 평균 용융지수(MI)가 10 내지 50을 갖는 것을 특징으로 하는 굴 패각을 이용한 플라스틱 조성물을 제공한다.One aspect of the present invention in order to achieve the above object is the oyster shell powder crushed oyster shell; At least one compatibilizing agent selected from maleic anhydride, itaconic acid, silane and talc; And a polyolefin-based resin, wherein the mixed composition provides a plastic composition using oyster shells, which has an average melt index (MI) of 10 to 50.
본 발명의 일 실시예에 있어서, 상기 굴패각분말 100중량부에 대하여, 상기 상용화제는 2 내지 5중량부의 비율로 혼합되는 것일 수 있다.In one embodiment of the present invention, with respect to 100 parts by weight of the oyster shell powder, the compatibilizer may be mixed in a proportion of 2 to 5 parts by weight.
본 발명의 일 실시예에 있어서, 상기 굴패각분말 및 상기 상용화제의 혼합물 80 내지 90중량부에 대하여, 상기 폴리올레핀계 수지는 10 내지 20중량부의 비율로 혼합되는 것일 수 있다.In one embodiment of the present invention, with respect to 80 to 90 parts by weight of the mixture of the oyster shell powder and the compatibilizer, the polyolefin-based resin may be mixed at a ratio of 10 to 20 parts by weight.
본 발명의 일 실시예에 있어서, 상기 플라스틱 조성물에는 가소제가 더 포함되며, 상기 가소제는, 트리부틸시트레이트(tributyl citrate), 트리부틸아세틸시트레이트(tributyl o-acetylcitrate) 및 트리에틸아세틸시트레이트(triethyl o-acetylcitrate) 중 어느 하나의 하이드록시카본엑시드에스터(hydroxycarboxylic acid ester)계 가소제 또는 산화된 피마자유, 산화된 팜유 및 산화된 올리브유 중 어느 하나의 천연오일 가소제 중 어느 하나 이상을 사용하는 것일 수 있다.In one embodiment of the invention, the plastic composition further includes a plasticizer, the plasticizer, tributyl citrate (tributyl citrate), tributyl acetyl citrate (tributyl o-acetylcitrate) and triethylacetyl citrate ( It may be to use any one or more of hydroxycarboxylic acid ester plasticizer of triethyl o-acetylcitrate or natural oil plasticizer of any one of oxidized castor oil, oxidized palm oil, and oxidized olive oil. have.
본 발명의 일 실시예에 있어서, 상기 가소제는 상기 굴패각분말 및 상기 상용화제의 혼합물 80 내지 90중량부에 대하여, 5 내지 10중량부의 혼합비율로 첨가되는 것일 수 있다.In one embodiment of the present invention, the plasticizer may be added at a mixing ratio of 5 to 10 parts by weight with respect to 80 to 90 parts by weight of the mixture of the oyster shell powder and the compatibilizer.
본 발명의 다른 측면은, 무수말레인산(maleic anhydride), 이타콘산(itaconic acid), 실란(silane) 및 활석(talc) 중에서 선택되는 적어도 어느 하나의 상용화제가 공급된 분위기에서 굴 패각을 분쇄하여 굴패각분말을 형성하는 제 1단계, 상기 제 1단계에서 형성된 굴패각분말에 폴리올레핀계 수지를 혼합하여 평균 용융지수(MI)가 10 내지 50을 갖는 혼합조성물을 형성하는 제 2단계 및 상기 제 2단계에서 형성된 혼합조성물을 성형하는 제 3단계를 포함하여 구성되는 것을 특징으로 하는 굴 양식용 인조패각의 제조방법을 제공한다.In another aspect of the present invention, oyster shell powder is crushed by grinding oyster shells in an atmosphere supplied with at least one compatibilizing agent selected from maleic anhydride, itaconic acid, silane, and talc. The first step of forming, the second step of mixing the olefin shell powder formed in the first step to form a mixed composition having an average melt index (MI) of 10 to 50 by mixing the polyolefin-based resin and the mixture formed in the second step It provides a method for manufacturing an artificial shell for oyster farming, characterized in that it comprises a third step of molding the composition.
본 발명의 굴 패각을 이용한 플라스틱 조성물은 굴 패각 분말 함량을 최대화하여 굴 패각의 활용도를 높이고, 인조패각 제조시 생산비용을 절감할 수 있다.The plastic composition using the oyster shell of the present invention can maximize the content of the oyster shell powder to maximize the utilization of the oyster shell, and reduce the production cost when manufacturing the artificial shell.
또한, 본 발명의 굴 패각을 이용한 플라스틱 조성물은 첨가되는 수지의 용융특성을 조절하여 형성된 플라스틱 조성물의 성형성을 향상시킬 수 있다.In addition, the plastic composition using the oyster shell of the present invention can improve the moldability of the formed plastic composition by controlling the melting properties of the added resin.
아울러, 본 발명의 굴 양식용 인조패각의 제조방법은 굴 패각이 분쇄되는 과정 중에 상용화제를 공급하여 선처리함으로써, 형성된 굴패각분말과 폴리올레핀계 수지와의 상용성을 높일 수 있어, 인조패각 제조시 성형된 인조패각 제품의 품질을 높일 수 있다. In addition, the method of manufacturing an artificial shell for oyster farming of the present invention can improve the compatibility between the formed oyster shell powder and a polyolefin resin by supplying a pre-treatment agent during the process of crushing the oyster shell, forming during artificial shell manufacturing The quality of artificial shellfish products can be improved.
다만, 발명의 효과는 상기에서 언급한 효과로 제한되지 아니하며, 언급되지 않은 또 다른 효과들을 하기의 기재로부터 당업자에게 명확히 이해될 수 있을 것이다.However, the effects of the invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.
도 1은 본 발명의 일 실시예에 따른 굴 패각을 이용한 플라스틱 조성물을 포함하는 굴 양식용 인조패각의 제조방법을 보인 순서도.
도 2는 본 발명의 비교예3에서 형성된 플라스틱 조성물의 사출 스트랜더 성형품을 나타낸 실제 이미지.
도 3은 본 발명의 실시예4에서 형성된 플라스틱 조성물의 사출 스트랜더 성형품을 나타낸 실제 이미지.1 is a flow chart showing a method of manufacturing an artificial shell for oyster farming, including a plastic composition using an oyster shell according to an embodiment of the present invention.
Figure 2 is a real image showing an injection strander molded article of the plastic composition formed in Comparative Example 3 of the present invention.
Figure 3 is an actual image showing an injection strander molded article of the plastic composition formed in Example 4 of the present invention.
이하, 본 발명에 의한 굴 패각을 이용한 플라스틱 조성물 및 이를 포함하는 굴 양식용 인조패각의 제조방법의 바람직한 실시예 및 도면을 참고하여 상세하게 설명한다. Hereinafter, with reference to the preferred embodiments and drawings of a method for producing a plastic composition using the oyster shell according to the present invention and artificial shell for oyster farming including the same will be described in detail.
본 발명의 일 측면은, 굴 패각을 이용한 플라스틱 조성물을 제공한다. 구체적으로, 상기 플라스틱 조성물은 굴 패각을 분쇄시킨 굴패각분말과, 무수말레인산(maleic anhydride), 이타콘산(itaconic acid), 실란(silane) 및 활석(talc) 중에서 선택되는 적어도 어느 하나의 상용화제와, 폴리올레핀계 수지를 포함하여 구성되는 혼합조성물로, 상기 혼합조성물은 평균 용융지수(MI)가 10 내지 50을 갖는 것일 수 있다. One aspect of the present invention provides a plastic composition using an oyster shell. Specifically, the plastic composition and the oyster shell powder crushed oyster shell shell, maleic anhydride (maleic anhydride), itaconic acid (itaconic acid), silane (silane) and talc (talc) at least one compatibilizer selected from, As a mixed composition comprising a polyolefin-based resin, the mixed composition may have an average melt index (MI) of 10 to 50.
먼저, 본 발명의 플라스틱 조성물의 기재로 굴 패각 분말이 마련된다. 상기 굴 패각 분말은 굴 껍데기를 의미하는 것으로, 전처리된 굴 패각을 분쇄시켜 제조된 것일 수 있다. 상기 굴 패각의 전처리는 통상의 방법을 이용하는 것일 수 있다. 구체적으로, 상기 굴 패각을 끓는 물에 투입하여 굴 패각에 부착된 오염물과 염분을 제거하고 고유의 악취를 탈취시킬 수 있다. 또한, 실시예에 따라, 상기 굴 패각을 가열하여 생석회화시켜 용이한 분쇄공정을 위해 경도를 낮출 수 있다. 전처리된 굴 패각의 분쇄는 통상의 분쇄기를 사용할 수 있다.First, an oyster shell powder is prepared as a base material of the plastic composition of the present invention. The oyster shell powder refers to an oyster shell, and may be prepared by crushing a pre-treated shell shell. The pre-treatment of the oyster shell may be a conventional method. Specifically, the oyster shell may be introduced into boiling water to remove contaminants and salts attached to the oyster shell and deodorize the intrinsic odor. In addition, according to the embodiment, the oyster shell can be heated to calcify to lower the hardness for an easy grinding process. The pulverization of the pre-treated oyster shell may use a conventional grinder.
또한, 본 발명의 플라스틱 조성물에는 무수말레인산(maleic anhydride), 이타콘산(itaconic acid), 실란(silane) 및 활석(talc) 중에서 선택되는 적어도 어느 하나의 상용화제가 혼합된다. 상기 상용화제는 상기 굴패각분말에 첨가되어 상기 굴패각분말의 분산도를 높이면서 조성물 전체의 물성을 향상시키는 것일 수 있다. 일 구현예에서, 상기 상용화제는 상기 폴리올레핀계 수지가 첨가되기 이전에 상기 굴패각분말과 혼합되는 것이 바람직하다. 이는, 상기 폴레올레핀계 수지와 혼합되기 이전에, 상기 굴패각분말과 상기 상용화제를 혼합함으로써 상기 굴패각분말이 상기 폴레올레핀계 수지와 혼합시의 상용성을 최대화하기 위한 것일 수 있다.In addition, at least one compatibilizing agent selected from maleic anhydride, itaconic acid, silane and talc is mixed in the plastic composition of the present invention. The compatibilizer may be added to the oyster shell powder to increase the dispersion degree of the oyster shell powder and improve the properties of the entire composition. In one embodiment, the compatibilizer is preferably mixed with the oyster shell powder before the polyolefin-based resin is added. This may be to maximize compatibility when the oyster shell powder is mixed with the polyolefin resin by mixing the oyster shell powder and the compatibilizer before being mixed with the polyolefin resin.
본 발명의 일 실시예에 있어서, 상기 굴패각분말 100중량부에 대하여 상기 상용화제는 2 내지 5중량부의 비율로 혼합되는 것일 수 있다. 상기 굴 패각 분말 100중량부에 대하여 상기 상용화제의 혼합비율이 2 중량부 미만인 경우, 분산도가 낮아져 성형된 제품의 내구성이 낮아질 수 있다. 또한, 상기 굴 패각 분말 100중량부에 대하여 상기 상용화제의 혼합비율이 5 중량부를 초과하는 경우, 물성이 저하되어 성형된 제품의 인장강도가 낮아질 수 있다. In one embodiment of the present invention, the compatibilizer may be mixed at a ratio of 2 to 5 parts by weight based on 100 parts by weight of the oyster shell powder. When the mixing ratio of the compatibilizer is less than 2 parts by weight with respect to 100 parts by weight of the oyster shell powder, the degree of dispersion may be lowered and durability of the molded product may be lowered. In addition, when the mixing ratio of the compatibilizer exceeds 5 parts by weight based on 100 parts by weight of the oyster shell powder, physical properties may be lowered and tensile strength of the molded product may be lowered.
그리고, 본 발명의 조성물에는 폴리올레핀계 수지가 혼합된다. 상기 폴리올레핀계 수지로는 저밀도폴리에틸렌(low density polyethylene, LDPE), 선형저밀도폴리에틸렌(linear low density polyethylene, LLDPE), 폴리프로필렌(polypropylene), 에틸렌비닐아세테이트공중합체(ethylene vinyl acetate copolymer, EVA), 에틸렌부텐공중합체(ethylene butane copolymer) 및 에틸렌옥텐공중합체(ethylene octane copolymer, EOR) 중에서 단독 또는 2종 이상을 병용하여 사용할 수 있다. Then, a polyolefin-based resin is mixed with the composition of the present invention. The polyolefin-based resins include low density polyethylene (LDPE), linear low density polyethylene (LDDPE), polypropylene, ethylene vinyl acetate copolymer (EVA), and ethylene butene Copolymers (ethylene butane copolymer) and ethylene octane copolymer (ethylene octane copolymer, EOR) may be used alone or in combination of two or more.
상기 폴리올레핀계 수지는 최종 형성된 혼합조성물의 평균 용융지수가 10 내지 50 g/10min을 갖도록 용융지수가 다른 폴리올레핀계 수지들의 첨가량을 조합하여 혼합하는 것일 수 있다. 일반적으로, 용융지수(Melt Index, MI)는 일정 하중, 일정 온도에서 가지는 수지의 용융 흐름성을 나타내는 것으로, 고분자의 용융특성은 제품의 가공성에 관계되며 성형된 제품의 물성에 영향을 준다. The polyolefin-based resin may be mixed by mixing the addition amount of polyolefin-based resins having different melt indexes so that the average melt index of the finally formed mixed composition is 10 to 50 g/10min. In general, the melt index (Melt Index, MI) indicates the melt flowability of a resin having a constant load and a certain temperature, and the melting properties of the polymer are related to the processability of the product and affect the properties of the molded product.
본 발명의 혼합조성물의 평균 용융지수(MI)가 10 미만인 경우에는, 낮은 용융지수로 인해 굴패각분말과 혼합이 잘 이뤄지지 않아, 형성된 플라스틱 조성물로 인조패각 제조시 성형작업이 어려워지고 제품의 불량율이 높아질 수 있다. 또한, 본 발명의 혼합조성물의 평균 용융지수(MI)가 50을 초과하는 경우에는, 높은 용융지수로 인해 형성된 플라스틱 조성물로 인조패각 제조시 제품의 인장강도가 낮아져 제품품질이 저하될 수 있다. When the average melt index (MI) of the mixed composition of the present invention is less than 10, it is difficult to mix with the oyster shell powder due to the low melt index, and thus the molding process becomes difficult when the artificial shell is manufactured with the formed plastic composition and the defect rate of the product increases. Can. In addition, when the average melt index (MI) of the mixed composition of the present invention exceeds 50, the tensile strength of the product may be lowered when the artificial shell is manufactured with a plastic composition formed due to the high melt index.
상기와 같이, 본 발명의 플라스틱 조성물에 첨가되는 폴리올레핀계 수지 조성물은 후술하는 굴 양식용 인조패각의 제조방법을 통해 인조패각으로 성형되기에 용이하도록 첨가되는 평균 용융지수가 10 내지 50을 갖도록 구성되는 것일 수 있다. As described above, the polyolefin-based resin composition added to the plastic composition of the present invention is configured to have an average melt index of 10 to 50, which is added to facilitate molding into an artificial shell through a method of manufacturing an artificial shell for oyster farming, which will be described later. May be
구체적으로, 상기 폴리올레핀계 수지 첨가시 한 종류의 수지를 단독으로 사용하는 경우, 형성된 혼합조성물의 평균 용융지수(MI)가 10 내지 50을 갖도록 조절하는 것일 수 있다. 일 구현예에서, 상기 폴리올레핀계 수지로 용융지수가 25인 폴리프로필렌과 용융지수가 140인 폴리프로필렌을 사용하여, 형성된 혼합조성물의 평균 용융지수가 10 내지 50의 범위를 갖도록 용융지수가 다른 폴리프로필렌의 혼합양을 조절하는 것일 수 있다. Specifically, when one type of resin is used alone when the polyolefin-based resin is added, the average melt index (MI) of the formed mixed composition may be adjusted to have 10 to 50. In one embodiment, the polyolefin-based resin using polypropylene having a melt index of 25 and polypropylene having a melt index of 140, polypropylene having a different melt index so as to have an average melt index in the range of 10 to 50 of the formed mixed composition. It may be to control the mixing amount of.
또한, 상기 폴리올레핀계 수지로 2종 이상을 병용하여 사용하는 경우, 형성된 혼합조성물의 평균 용융지수(MI)가 10 내지 50을 갖도록 조절하여 사용하는 것을 의미할 수 있다. 일 구현예에서, 상기 폴리올레핀계 수지로 용융지수 140을 갖는 폴리프로필렌과 용융지수 20을 갖는 폴리에틸렌을 사용하여, 형성된 혼합조성물의 평균 용융지수가 10 내지 50의 범위를 갖도록 폴리프로필렌과 폴리에틸렌의 혼합양을 조절하는 것일 수 있다.In addition, when two or more kinds of the polyolefin-based resin are used in combination, it may mean that the formed mixed composition has an average melt index (MI) of 10 to 50. In one embodiment, using polypropylene having a melt index of 140 and polyethylene having a melt index of 20 as the polyolefin-based resin, the mixing amount of polypropylene and polyethylene so as to have an average melt index of 10 to 50 in the formed mixed composition. It may be to adjust.
본 발명의 일 실시예에 있어서, 상기 굴패각분말 및 상기 상용화제의 혼합물 80 내지 90중량부에 대하여, 상기 폴리올레핀계 수지는 10 내지 20중량부의 비율로 혼합되는 것일 수 있다. 상기 굴패각분말 및 상기 상용화제의 혼합물 80 내지 90중량부에 대한 상기 폴리올레핀계 수지의 혼합비율이 10중량부 미만인 경우, 굴패각분말 함량이 너무 많아짐에 따라 형성된 플라스틱 조성물의 성형성 및 물성이 낮아질 수 있다. 또한, 상기 굴패각분말 및 상기 상용화제의 혼합물 80 내지 90중량부에 대한 상기 폴리올레핀계 수지의 혼합비율이 20중량부를 초과하는 경우, 제조단가가 상승할 수 있어 제품의 경제성이 저하될 수 있다.In one embodiment of the present invention, with respect to 80 to 90 parts by weight of the mixture of the oyster shell powder and the compatibilizer, the polyolefin-based resin may be mixed at a ratio of 10 to 20 parts by weight. When the mixing ratio of the polyolefin-based resin to 80 to 90 parts by weight of the mixture of the oyster shell powder and the compatibilizer is less than 10 parts by weight, the moldability and physical properties of the formed plastic composition may be lowered as the content of the oyster shell powder becomes too large. . In addition, when the mixing ratio of the polyolefin-based resin to 80 to 90 parts by weight of the mixture of the oyster shell powder and the compatibilizer exceeds 20 parts by weight, the manufacturing cost may increase and the economics of the product may deteriorate.
본 발명의 일 실시예에 있어서, 상기 굴 패각을 이용한 상기 플라스틱 조성물에는 가소제가 더 포함될 수 있다. 구체적으로, 상기 가소제는, 트리부틸시트레이트(tributyl citrate), 트리부틸아세틸시트레이트(tributyl o-acetylcitrate) 및 트리에틸아세틸시트레이트(triethyl o-acetylcitrate) 중 어느 하나의 하이드록시카본엑시드에스터(hydroxycarboxylic acid ester)계 가소제 또는 산화된 피마자유, 산화된 팜유 및 산화된 올리브유 중 어느 하나의 천연오일 가소제 중 어느 하나 이상을 사용하는 것일 수 있다. 첨가된 가소제에 의해 상기 플라스틱 조성물의 공정특성이 향상될 수 있다. In one embodiment of the present invention, the plastic composition using the oyster shell may further include a plasticizer. Specifically, the plasticizer, tributyl citrate (tributyl citrate), tributyl acetyl citrate (tributyl o-acetylcitrate) and triethyl acetyl citrate (triethyl o-acetylcitrate) of any one of the hydroxy carboxylic acid ester (hydroxycarboxylic acid) acid ester)-based plasticizer or oxidized castor oil, oxidized palm oil, and oxidized olive oil. Process characteristics of the plastic composition may be improved by the added plasticizer.
본 발명의 일 실시예에서, 상기 가소제는 상기 굴패각분말 및 상기 상용화제의 혼합물 80 내지 90중량부에 대하여, 5 내지 10중량부의 혼합비율로 첨가되는 것일 수 있다. 상기 가소제의 혼합비율이 5 중량부 미만인 경우, 최종형성되는 상기 플라스틱 조성물의 가소성이 낮아 성형작업이 어려워질 수 있다. 또한, 상기 가소제의 혼합비율이 10중량부를 초과하는 경우, 환경호르몬 발생이나 미세플라스틱 등의 환경문제나 제품의 안전성을 저감시킬 수 있어, 상술한 범위 내에서 첨가되는 것일 수 있다. In one embodiment of the present invention, the plasticizer may be added at a mixing ratio of 5 to 10 parts by weight with respect to 80 to 90 parts by weight of the mixture of the oyster shell powder and the compatibilizer. When the mixing ratio of the plasticizer is less than 5 parts by weight, the plasticity of the plastic composition to be finally formed may be low, and molding operation may be difficult. In addition, when the mixing ratio of the plasticizer exceeds 10 parts by weight, environmental problems such as generation of environmental hormones or microplastics, or safety of products can be reduced, and may be added within the aforementioned range.
다음으로, 본 발명에 의한 굴 패각을 이용한 플라스틱 조성물을 포함하여 굴 양식용 인조패각을 제조하는 과정을 살펴본다.Next, look at the process of manufacturing a synthetic shell for oyster farming, including the plastic composition using the oyster shell according to the present invention.
도 1은 본 발명의 일 실시예에 따른 굴 패각을 이용한 플라스틱 조성물을 포함하는 굴 양식용 인조패각의 제조방법을 보인 순서도이다.1 is a flow chart showing a method of manufacturing an artificial shell for oyster farming, including a plastic composition using an oyster shell according to an embodiment of the present invention.
도 1을 참조하면, 본 발명의 굴 양식용 인조패각의 제조방법은, 무수말레인산(maleic anhydride), 이타콘산(itaconic acid), 실란(silane) 및 활석(talc) 중에서 선택되는 적어도 어느 하나의 상용화제가 공급된 분위기에서 굴 패각을 분쇄하여 굴패각분말을 형성하는 제 1단계(S10)와, 상기 제 1단계에서 형성된 굴패각분말에 폴리올레핀계 수지를 혼합하여 평균 용융지수(MI)가 10 내지 50을 갖는 혼합조성물을 형성하는 제 2단계(S20)와, 상기 제 2단계에서 형성된 혼합조성물을 성형하는 제 3단계(S30)를 포함하여 구성될 수 있다.Referring to Figure 1, the method of manufacturing the artificial shell for oyster farming of the present invention, maleic anhydride (maleic anhydride), itaconic acid (itaconic acid), silane (silane) and talc (talc) selected from at least one commercialization The first step (S10) of crushing the oyster shell in the atmosphere where I was supplied to form the oyster shell powder and the polyolefin resin mixed with the oyster shell powder formed in the first step have an average melt index (MI) of 10 to 50 It may be configured to include a second step (S20) of forming a mixed composition, and a third step (S30) of molding the mixed composition formed in the second step.
구체적으로, 상기 S10은 세척, 소독 및 탈취 등의 전처리된 굴 패각을 분말형태로 분쇄시에 상용화제를 공급하여 굴 패각을 분쇄시키는 것일 수 있다. 본 발명의 일 실시예에서, 상기 굴 패각을 분쇄시에 상용화제를 공급하는 방법은, 굴 패각을 분쇄하는 분쇄기 내에 사용화제를 분무 또는 분사하거나, 분쇄될 굴 패각에 코팅 또는 전사하는 방법 등을 이용하여 수행하는 것일 수 있다. 이 때, 상기 상용화제는 상기 굴 패각(굴패각분말) 100중량부에 대하여 2 내지 5중량부의 비율로 혼합되도록 공정을 수행할 수 있다.Specifically, the S10 may be to crush the oyster shell by supplying a compatibilizer when pulverizing pre-treated oyster shells such as washing, disinfection and deodorization in powder form. In one embodiment of the present invention, a method of supplying a compatibilizer when crushing the oyster shell is a method of spraying or spraying a use agent in a pulverizer crushing the oyster shell, or coating or transferring the oyster shell to be crushed. It can be done by using. At this time, the compatibilizer may perform a process to be mixed in a ratio of 2 to 5 parts by weight based on 100 parts by weight of the oyster shell (oyster shell powder).
이 후, 상기 S20은 상기 S10에서 형성된 굴패각분말에 폴리올레핀계 수지를 혼합하여 혼합조성물을 형성하는 것일 수 있다. 상기 폴리올레핀계 수지로는 저밀도폴리에틸렌(low density polyethylene, LDPE), 선형저밀도폴리에틸렌(linear low density polyethylene, LLDPE), 폴리프로필렌(polypropylene), 에틸렌비닐아세테이트공중합체(ethylene vinyl acetate copolymer, EVA), 에틸렌부텐공중합체(ethylene butane copolymer) 및 에틸렌옥텐공중합체(ethylene octane copolymer, EOR) 중에서 단독 또는 2종 이상을 병용하여 사용할 수 있다. 상기 폴리올레핀계 수지는 형성된 혼합조성물의 평균 용융지수(MI)가 10 내지 50을 갖도록 서로 다른 용융지수를 가진 폴리올레핀계 수지를 혼합하여 첨가하는 것일 수 있다. 일 실시예에서, 상기 굴패각분말에 상기 폴리올레핀계 수지를 혼합하는 것은 드라이 블렌드(dry blend)를 이용하여 혼합하는 것일 수 있다.Subsequently, the S20 may be a mixture of polyolefin resins in the oyster shell powder formed in S10 to form a mixed composition. The polyolefin-based resins include low density polyethylene (LDPE), linear low density polyethylene (LDDPE), polypropylene, ethylene vinyl acetate copolymer (EVA), and ethylene butene Copolymers (ethylene butane copolymer) and ethylene octane copolymer (ethylene octane copolymer, EOR) may be used alone or in combination of two or more. The polyolefin-based resin may be added by mixing polyolefin-based resins having different melting indices so that the formed composition has an average melt index (MI) of 10 to 50. In one embodiment, mixing the polyolefin-based resin with the oyster shell powder may be mixing using a dry blend.
그런 다음, S30은 상기 S20에서 형성된 혼합조성물을 원하는 형상을 갖도록 성형하는 것일 수 있다. 본 발명에서는 상기 혼합조성물을 압출기를 이용하여 압출시켜 굴 양식용 인조패각 형상을 갖도록 성형하는 것일 수 있다. Then, S30 may be to mold the mixed composition formed in S20 to have a desired shape. In the present invention, the mixed composition may be extruded using an extruder to be molded to have an artificial shell shape for oyster farming.
이하, 상술한 조성물을 포함하는 굴 양식용 인조패각의 제조방법을 사용하여 표 1 및 표 2에 나타난 바와 같은 조성으로 실험한 내용을 상세하게 설명한다.Hereinafter, using the method of manufacturing a synthetic shell for oyster farming containing the above-described composition will be described in detail the experiments with the composition shown in Table 1 and Table 2.
[실시예1][Example 1]
실시예1은 굴 패각 분쇄시에 굴 패각 100중량부에 대하여 상용화제인 이타콘산(itaconic acid)을 2중량부 공급하여 굴 패각을 분쇄시켜 굴패각분말을 제조하였다.In Example 1, oyster shell powder was prepared by crushing oyster shell by supplying 2 parts by weight of itaconic acid, a compatibilizer, to 100 parts by weight of oyster shell during oyster shell crushing.
[실시예2][Example 2]
실시예2는 굴 패각 분쇄시에 굴 패각 100중량부에 대하여 상용화제인 활석(talc)을 3중량부 공급하여 굴 패각을 분쇄시켜 굴패각분말을 제조하였다.In Example 2, oyster shell powder was prepared by pulverizing oyster shell by supplying 3 parts by weight of talc, a compatibilizer, to 100 parts by weight of oyster shell during oyster shell crushing.
[실시예3][Example 3]
실시예3은 굴 패각 분쇄시에 굴 패각 100중량부에 대하여 상용화제인 무수말레인산(maleic anhydride)을 5중량부 공급하여 굴 패각을 분쇄시켜 굴패각분말을 제조하였다.In Example 3, oyster shell powder was prepared by pulverizing oyster shell by supplying 5 parts by weight of maleic anhydride, a compatibilizer, to 100 parts by weight of oyster shell during oyster shell crushing.
[비교예1][Comparative Example 1]
비교예1은 굴 패각을 분쇄시켜 굴패각분말을 제조하였다.In Comparative Example 1, oyster shell powder was pulverized to prepare oyster shell powder.
이 후, 비교예1과 실시예1 내지 실시예3의 굴패각분말에 폴리올레핀계 수지 및 가소제를 표 2에 나타난 바와 같은 조성으로 혼합하여 플라스틱 조성물을 제조하였다. Subsequently, a polyolefin-based resin and a plasticizer were mixed in the oyster shell powders of Comparative Example 1 and Examples 1 to 3 in a composition as shown in Table 2 to prepare a plastic composition.
예4practice
Yes 4
예5practice
Example 5
예6practice
Example 6
예7practice
Example 7
예8practice
Yes 8
예9practice
Yes 9
예10practice
Yes 10
예11practice
Yes 11
예2compare
Example 2
예3compare
Yes 3
예4compare
Yes 4
[실시예4][Example 4]
실시예4는 실시예1의 굴 패각 분말 80중량부에 용융지수(MI)가 25g/10min 이내인 폴리프로필렌 15중량부와 용융지수(MI)가 140g/10min 이내인 폴리프로필렌 5중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다. In Example 4, 80 parts by weight of the oyster shell powder of Example 1 was mixed with 15 parts by weight of polypropylene having a melt index (MI) of less than 25 g/10min and 5 parts by weight of polypropylene with a melt index (MI) of less than 140 g/10min. Then, it was manufactured by extruding it into an artificial shell shape.
[실시예5][Example 5]
실시예5는 실시예1의 굴 패각 분말 85 중량부에 용융지수(MI)가 25g/10min 이내인 폴리프로필렌 8중량부와 용융지수(MI)가 140g/10min 이내인 폴리프로필렌 7중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.In Example 5, 85 parts by weight of the oyster shell powder of Example 1 was mixed with 8 parts by weight of polypropylene having a melt index (MI) of less than 25 g/10min and 7 parts by weight of polypropylene with a melt index (MI) of less than 140 g/10min. Then, it was manufactured by extruding it into an artificial shell shape.
[실시예6][Example 6]
실시예6은 실시예2의 굴 패각 분말 80중량부에 용융지수(MI)가 140g/10min 이내인 폴리프로필렌 5중량부와 용융지수(MI)가 20g/10min 이내인 폴리에틸렌 15중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.Example 6 is mixed with 5 parts by weight of polypropylene having a melt index (MI) of 140 g/10min or less and 15 parts by weight of polyethylene having a melt index (MI) of 20 g/10min or less by mixing 80 parts by weight of the oyster shell powder of Example 2 , It was manufactured by extruding it into an artificial shell shape.
[실시예7][Example 7]
실시예7은 실시예2의 굴 패각 분말 85중량부에 용융지수(MI)가 20g/10min 이내인 폴리에틸렌 9중량부와 용융지수(MI)가 150g/10min 이내인 에틸렌비닐아세테이트공중합체 6중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.Example 7 is 85 parts by weight of the oyster shell powder of Example 2 9 parts by weight of polyethylene having a melt index (MI) within 20 g/10min and 6 parts by weight of ethylene vinyl acetate copolymer having a melt index (MI) within 150 g/10 min. After mixing, it was manufactured by extruding it into an artificial shell shape.
[실시예8][Example 8]
실시예8은 실시예3의 굴 패각 분말 85중량부에 용융지수(MI)가 25g/10min 이내인 폴리프로필렌 15중량부와 용융지수(MI)가 150g/10min 이내인 에틸렌비닐아세테이트공중합체 5중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.Example 8 is 15 parts by weight of polypropylene having a melt index (MI) of less than 25 g/10min and 85 weight parts of oyster shell powder of Example 3 and 5 weight of ethylene vinyl acetate copolymer having a melt index (MI) of less than 150 g/10min. After mixing the parts, it was manufactured by extruding it into an artificial shell shape.
[실시예9][Example 9]
실시예9는 실시예3의 굴 패각 분말 90중량부에 용융지수(MI)가 140g/10min 이내인 폴리프로필렌 10중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.Example 9 was prepared by mixing 10 parts by weight of polypropylene having a melt index (MI) of 140 g/10 min or less in 90 parts by weight of oyster shell powder of Example 3, and then extruding it into an artificial shell shape.
[실시예10][Example 10]
실시예10은 실시예3의 굴 패각 분말 80중량부에 용융지수(MI)가 25g/10min 이내인 폴리프로필렌 10중량부와 용융지수(MI)가 400g/10min 이내인 에틸렌비닐아세테이트공중합체 10중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.Example 10 is 10 parts by weight of polypropylene having a melt index (MI) of less than 25 g/10 min and 80 weight parts of oyster shell powder of Example 3 and 10 weight of ethylene vinyl acetate copolymer having a melt index (MI) of less than 400 g/10 min. After mixing the parts, it was manufactured by extruding it into an artificial shell shape.
[실시예11][Example 11]
실시예11은 실시예3의 굴 패각 분말 90중량부에 용융지수(MI)가 25g/10min 이내인 폴리프로필렌 15중량부와 용융지수(MI)가 140g/10min 이내인 폴리프로필렌 5중량부를 혼합하고, 가소제로 트리에틸아세틸시트레이트 5중량부를 첨가하여 블렌딩한 후, 이를 인조패각 형상으로 압출하여 제조하였다.In Example 11, 15 parts by weight of polypropylene having a melt index (MI) of 25 g/10 min or less and 5 parts by weight of polypropylene having a melt index (MI) of 140 g/10 min or less were mixed with 90 parts by weight of the oyster shell powder of Example 3, , And blended by adding 5 parts by weight of triethylacetyl citrate as a plasticizer, and then extruding it into an artificial shell shape.
[비교예2][Comparative Example 2]
비교예2는 실시예1의 굴 패각 분말 80중량부에 용융지수(MI)가 25g/10min 이내인 폴리프로필렌 20중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.Comparative Example 2 was prepared by mixing 20 parts by weight of polypropylene having a melt index (MI) of 25 g/10 min or less by mixing 80 parts by weight of oyster shell powder of Example 1, and then extruding it into an artificial shell shape.
[비교예3][Comparative Example 3]
비교예3은 비교예1의 굴 패각 분말 80중량부에 용융지수(MI)가 25g/10min 이내인 폴리프로필렌 15중량부와 용융지수(MI)가 140g/10min 이내인 폴리프로필렌 5중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.In Comparative Example 3, 80 parts by weight of the oyster shell powder of Comparative Example 1 was mixed with 15 parts by weight of polypropylene having a melt index (MI) of less than 25 g/10min and 5 parts by weight of polypropylene with a melt index (MI) of less than 140 g/10min. Then, it was manufactured by extruding it into an artificial shell shape.
[비교예4][Comparative Example 4]
비교예4는 실시예1의 굴 패각 분말 80중량부에 용융지수(MI)가 400g/10min 이내인 에틸렌비닐아세테이트 20중량부를 혼합한 후, 이를 인조패각 형상으로 압출하여 제조하였다.Comparative Example 4 was prepared by mixing 20 parts by weight of ethylene vinyl acetate having a melt index (MI) of 400 g/10 min or less by mixing 80 parts by weight of the oyster shell powder of Example 1, and then extruding it into an artificial shell shape.
상술한 바와 같은 비교예2 내지 비교예4, 실시예 4 내지 실시예 11 각각의 압출특성, 경도(Hardness), 인장강도(Tensile strength) 및 연신율(Elongation)을 분석하여 표 3에 나타내었다.Extrusion characteristics, hardness, tensile strength and elongation of Comparative Examples 2 to 4 and Examples 4 to 11 as described above were analyzed and are shown in Table 3.
예4practice
Yes 4
예5practice
Example 5
예6practice
Example 6
예7practice
Example 7
예8practice
Yes 8
예9practice
Yes 9
예10practice
Yes 10
예11practice
Yes 11
예2compare
Example 2
예3compare
Yes 3
예4compare
Yes 4
표 3에 나타난 바와 같이, 실시예들은 비교예2 내지 비교예4에 비해 압출특성이 양호한 것을 확인할 수 있다. 특히, 표 2를 참조하면, 비교예2의 평균 용융지수는 5g/10min으로 실시예들에 비해 현저히 낮아 성형작업이 어려워지면서 표 3과 같이, 압출하여 성형시 제품 불량이 나타나는 것을 알 수 있다.As shown in Table 3, it can be seen that the Examples have better extrusion characteristics than Comparative Examples 2 to 4. In particular, referring to Table 2, the average melting index of Comparative Example 2 is 5 g/10 min, which is significantly lower than in Examples, and as the molding operation becomes difficult, it can be seen that product defects appear during extrusion by molding.
구체적으로, 비교예3과 실시예4의 평균 용융지수는 10.75g/10min으로 동일하나, 비교예3은 무수말레인산(maleic anhydride), 이타콘산(itaconic acid), 실란(silane) 및 활석(talc)과 같은 상용화제의 선처리가 되지 않은 것으로 도 2와 같이 형성된 플라스틱 조성물로 스트랜더 사출시 성형품의 형상이 불규칙한 외관을 띄면서 성형품의 품질이 불량으로 나타났다. 하지만, 상용화제로 선처리가 된 실시예4의 경우, 형성된 플라스틱 조성물로 스트랜더 사출시 도 3과 같이 일정한 형상의 스트랜더를 갖기 때문에 양호한 형태의 제품을 얻을 수 잇다. Specifically, the average melting index of Comparative Example 3 and Example 4 is the same as 10.75 g/10 min, but Comparative Example 3 is maleic anhydride, itaconic acid, silane, and talc. As a plastic composition formed as shown in FIG. 2 as a pretreatment of a compatibilizer as shown in FIG. 2, the appearance of the molded article was irregular and the quality of the molded article was poor. However, in the case of Example 4, which was pre-treated with a compatibilizer, it is possible to obtain a product in a good shape because the formed plastic composition has a uniform shape of a strand as shown in FIG.
또한, 표 2 내지 표 3을 참조하면, 비교예4의 평균 용융지수는 80g/10min으로 실시예들에 비해 현저히 높아 압출시 성형제품의 물성이 나빠져 불량으로 제조되는 것을 알 수 있다. In addition, referring to Tables 2 to 3, the average melt index of Comparative Example 4 is 80 g/10 min, which is significantly higher than in Examples, and it can be seen that the physical properties of the molded product during extrusion are deteriorated and are poorly manufactured.
상기와 같이, 본 발명은 용융지수가 다른 폴리올레핀계 수지들의 첨가량을 조절하여 플라스틱 조성물의 평균 용융지수가 10 내지 50을 갖도록 조성함에 따라 굴패각분말의 함량을 최대화하면서도 압출특성을 유지하며 향상시킬 수 있다. As described above, according to the present invention, as the composition of the plastic composition has an average melt index of 10 to 50 by controlling the amount of polyolefin resins having different melt indexes, the content of oyster shell powder can be maximized while maintaining and improving extrusion characteristics. .
이와 같이, 상술한 본 발명의 기술적 구성은 본 발명이 속하는 기술 분야의 당업자가 본 발명의 그 기술적 사상이나 필수적인 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다.As described above, it will be understood that the above-described technical configuration of the present invention can be implemented in other specific forms by those skilled in the art to which the present invention pertains without changing the technical spirit or essential characteristics of the present invention.
그러므로, 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적인 것이 아닌 것으로서 이해되어야 하고, 본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허청구범위에 의하여 나타나며, 특허청구범위의 의미 및 범위 그리고 그 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all respects, and the scope of the present invention is indicated by the following claims rather than the above detailed description, and the meaning and scope of the claims and It should be construed that any altered or modified form derived from the equivalent concept is included in the scope of the present invention.
Claims (6)
무수말레인산(maleic anhydride), 이타콘산(itaconic acid), 실란(silane) 및 활석(talc) 중에서 선택되는 적어도 어느 하나의 상용화제;및
폴리올레핀계 수지를 포함하여 구성되는 혼합조성물로,
상기 굴패각분말 100중량부에 대하여,
상기 상용화제는 5중량부의 비율로 혼합되고,
상기 굴패각분말과 상기 상용화제의 혼합물 80 내지 85중량부에 대하여,
상기 폴리올레핀계 수지는 20중량부의 비율로 혼합되는 것을 특징으로 하는 굴 패각을 이용한 플라스틱 조성물.Oyster shell powder crushed oyster shell;
At least one compatibilizer selected from maleic anhydride, itaconic acid, silane and talc; and
A mixed composition comprising a polyolefin-based resin,
With respect to 100 parts by weight of the oyster shell powder,
The compatibilizer is mixed in a proportion of 5 parts by weight,
With respect to 80 to 85 parts by weight of the mixture of the oyster shell powder and the compatibilizer,
The polyolefin-based resin is a plastic composition using an oyster shell, characterized in that is mixed in a proportion of 20 parts by weight.
상기 제 1단계에서 형성된 굴패각분말 80 내지 85중량부에 폴리올레핀계 수지 20중량부를 혼합하는 혼합조성물을 형성하는 제 2단계;및
상기 제 2단계에서 형성된 혼합조성물을 성형하는 제 3단계;를 포함하여 구성되는 것을 특징으로 하는 굴 양식용 인조패각의 제조방법.The oyster shell is crushed by crushing the oyster shell in an atmosphere in which 5 parts by weight of at least one compatibilizing agent selected from maleic anhydride, itaconic acid, silane and talc is supplied to 100 parts by weight of the oyster shell. A first step of forming a powder;
A second step of forming a mixing composition in which 20 parts by weight of polyolefin resin is mixed with 80 to 85 parts by weight of the oyster shell powder formed in the first step; and
The third step of molding the mixed composition formed in the second step; Method of manufacturing an artificial shell for oyster farming, characterized in that comprises a.
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| KR102544739B1 (en) | 2022-10-27 | 2023-06-20 | 주식회사 에쓰큐씨 | Plastic Composition Comprising Using Calcium Carbonate From the Shell |
| KR102603860B1 (en) | 2022-08-09 | 2023-11-22 | 윤정식 | Composition containing a high content of shell powder and master batch using thereof |
| KR20230162207A (en) | 2022-05-20 | 2023-11-28 | 주식회사 신진테크해양 | A Artificial Shell Composition and A Artificial Shell Manufacturing Method of That |
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