KR20220160225A - Resin Composite Including Cellulose and Polyketone and Method for Preparation of the Same - Google Patents
Resin Composite Including Cellulose and Polyketone and Method for Preparation of the Same Download PDFInfo
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- KR20220160225A KR20220160225A KR1020210068129A KR20210068129A KR20220160225A KR 20220160225 A KR20220160225 A KR 20220160225A KR 1020210068129 A KR1020210068129 A KR 1020210068129A KR 20210068129 A KR20210068129 A KR 20210068129A KR 20220160225 A KR20220160225 A KR 20220160225A
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- cellulose
- polyketone
- resin composite
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- 229920001470 polyketone Polymers 0.000 title claims abstract description 81
- 229920002678 cellulose Polymers 0.000 title claims abstract description 74
- 239000001913 cellulose Substances 0.000 title claims abstract description 74
- 239000000805 composite resin Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title description 5
- 239000004014 plasticizer Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 15
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 15
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 9
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 9
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920001046 Nanocellulose Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 2
- YTNWDIVKHHKRFX-UHFFFAOYSA-N 4-hydroxy-1,3-dioxolan-2-one Chemical compound OC1COC(=O)O1 YTNWDIVKHHKRFX-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000875 Dissolving pulp Polymers 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 239000000178 monomer Substances 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 11
- 230000004888 barrier function Effects 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- -1 aryl aliphatic hydrocarbons Chemical class 0.000 description 8
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 230000035699 permeability Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BYYLJVQCWRRFMP-UHFFFAOYSA-N 1-ethenyl-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(C=C)=C1 BYYLJVQCWRRFMP-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L73/00—Compositions of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08L59/00 - C08L71/00; Compositions of derivatives of such polymers
-
- 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
- C08J3/12—Powdering or granulating
-
- 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
-
- 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
- C08K5/07—Aldehydes; Ketones
-
- 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
- C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
본 발명은 셀룰로오스와 폴리케톤이 포함되어 있고 가스 차단성이 우수한 수지 복합체 및 그것을 제조하는 방법에 관한 것이다.The present invention relates to a resin composite containing cellulose and polyketone and having excellent gas barrier properties and a method for preparing the same.
폴리케톤은 일산화탄소와 적어도 1종의 에틸렌계 불포화 단량체의 중합체, 특히 일산화탄소 유래의 반복단위와 에틸렌성 불포화 단량체 유래의 반복단위가 교대로 연결된 구조로 이루어져 있고, 통상적으로 팔라듐(palladium), 코발트(cobalt), 니켈(nikel) 중에서 선택된 VIII족 금속의 화합물과, 비하이드로 할로겐 강산(strongon-hydrohalogentic acid)의 음이온과, 인, 비소 또는 안티몬(Antimon)의 2좌 배위자로부터 생성되는 촉매 조성물을 사용하여 제조할 수 있다.Polyketone is a polymer of carbon monoxide and at least one ethylenically unsaturated monomer, in particular, a structure in which carbon monoxide-derived repeating units and ethylenically unsaturated monomer-derived repeating units are alternately connected, and are typically palladium or cobalt. ), prepared using a catalyst composition produced from a compound of a group VIII metal selected from among nickel, an anion of strongon-hydrohalogentic acid, and a bidentate ligand of phosphorus, arsenic or antimony can do.
이러한 폴리케톤은 우수한 기계적 성질과 열적 성질을 가지는 바, 내마모성이 높아서 자동차의 기어 등의 부품, 내약품성이 높아서 화학수송 파이프의 라이닝재, 각종 약품병 등, 가스 차단성이 높아서 경량 가솔린 탱크 등에 이용 가능하다.These polyketones have excellent mechanical and thermal properties, and are used for parts such as automobile gears due to their high abrasion resistance, lining materials for chemical transport pipes and various medicine bottles due to their high chemical resistance, and lightweight gasoline tanks due to their high gas barrier properties. It is possible.
그러나, 폴리케톤은 섭씨 230 내지 270도의 고온에서 사출 또는 압출 성형으로 제품화되므로, 그러한 고온에서 물성을 유지하기 어렵거나 변질 내지 분해되는 소재와는 사용되기 어려운 문제점을 가지고 있다. 예를 들어, 가스 차단성을 높이기 위해 셀룰로오스계 물질을 폴리케톤에 혼합하여 사용하는 경우, 섭씨 210도 이상에서 대부분의 셀룰로오스계 물질이 분해되기 시작하고 (July 2014. Cellulose Chemistry and Technology 48(5-6): 461-467) 그 이상의 온도에서는 변색되면서 연소되므로, 셀룰로오스계 물질의 기본 물성을 유지하기 매우 어렵다.However, since polyketone is commercialized by injection or extrusion molding at a high temperature of 230 to 270 degrees Celsius, it has a problem in that it is difficult to maintain physical properties at such a high temperature or to be used with materials that deteriorate or decompose. For example, when cellulose-based materials are mixed with polyketone to increase gas barrier properties, most cellulose-based materials begin to decompose at 210 degrees Celsius or higher (July 2014. Cellulose Chemistry and Technology 48(5- 6): 461-467) It is very difficult to maintain the basic physical properties of a cellulose-based material because it is discolored and burned at a temperature higher than that.
따라서, 폴리케톤과 함께 셀룰로오스계 물질을 사용할 때, 셀룰로오스계 물질의 특성을 그대로 유지할 수 있는 기술에 대한 필요성이 높은 실정이다.Therefore, when using a cellulose-based material together with polyketone, there is a high need for a technology capable of maintaining the properties of the cellulose-based material as it is.
따라서, 본 발명은 상기와 같은 종래기술의 문제점과 과거로부터 요청되어온 기술적 과제를 해결하는 것을 목적으로 한다.Accordingly, an object of the present invention is to solve the problems of the prior art and the technical problems that have been requested from the past.
본 출원의 발명자들은 심도 있는 연구와 다양한 실험들을 통해, 폴리케톤과 셀룰로오스계 물질이 조합된 새로운 개념의 수지 복합체를 개발하게 되었고, 이러한 수지 복합체는 제조과정에서 셀룰로오스계 물질이 손상되지 않으면서 폴리케톤과의 조합에 의해 매우 우수한 가스 차단성을 발휘할 수 있음을 확인하고, 본 발명을 완성하기에 이르렀다.The inventors of the present application have developed a new concept of resin composite in which polyketone and cellulose-based materials are combined through in-depth research and various experiments, and this resin composite is polyketone without damaging the cellulose-based material during the manufacturing process. It was confirmed that excellent gas barrier properties can be exhibited by the combination with and, and the present invention has been completed.
이러한 목적을 달성하기 위한 본 발명에 따른 수지 복합체는, 폴리케톤 100 중량부에 대해 셀룰로오스 또는 셀룰로오스 유도체 10 내지 90 중량부, 및 폴리케톤 가소제 1 내지 30 중량부를 포함하고 있고, 상기 셀룰로오스 또는 셀룰로오스 유도체는 폴리케톤과 수소결합을 이루고 있는 것을 특징으로 한다.The resin composite according to the present invention for achieving this object contains 10 to 90 parts by weight of cellulose or a cellulose derivative and 1 to 30 parts by weight of a polyketone plasticizer based on 100 parts by weight of polyketone, and the cellulose or cellulose derivative is It is characterized by forming a hydrogen bond with polyketone.
본 발명에 따른 수지 복합체는, 폴리케톤 가소제에 의해 폴리케톤의 융점을 섭씨 210도 이하로 낮추어, 폴리케톤과의 수지 복합체를 형성하는 과정에서 셀룰로오스계 물질의 변질 내지 분해가 초래되지 않고, 각각 가스 차단성이 우수한 폴리케톤과 셀룰로오스계 물질의 조합과 폴리케톤의 카르보닐기와 셀룰로오스계 물질의 하이드록시 간의 수소결합에 의해 더욱 우수한 가스 차단성과 물리적 특성을 발휘할 수 있다.In the resin composite according to the present invention, the melting point of polyketone is lowered to 210 degrees Celsius or less by a polyketone plasticizer, so that the cellulose-based material does not deteriorate or decompose in the process of forming the resin composite with polyketone, and each gas Further excellent gas barrier properties and physical properties can be exhibited by the combination of polyketone with excellent barrier properties and a cellulose-based material and the hydrogen bond between the carbonyl group of the polyketone and the hydroxyl of the cellulose-based material.
본 발명의 수지 복합체에서 폴리케톤은, 앞서 설명한 바와 같이, 실질적으로 에틸렌계 불포화 단량체 각 분자에 대해 한 분자의 일산화탄소를 포함하고 있다. CO에서 유래한 부분은 에틸렌계 불포화 단량체에서 유래한 부분과 번갈아 존재한다.As described above, the polyketone in the resin composite of the present invention substantially contains one molecule of carbon monoxide for each molecule of the ethylenically unsaturated monomer. Moieties derived from CO alternate with moieties derived from ethylenically unsaturated monomers.
상기 에틸렌계 불포화 단량체는 20개, 더욱 상세하게는 10개까지의 탄소 원자를 가질 수 있다. 예를 들어, 에텐(ethane), 프로펜(propene), 1-부텐(butene), 이소부텐(iso-butene), 1-헥센(hexene), 1-옥텐(octene)과 같은 지방족의 단량체이거나 또는 다른 지방족 분자상에 아릴(aryl) 치환기를 포함하고, 특히 에틸렌계 불포화 탄소 원자상에 아릴 치환기를 포함하고 있는 아릴 지방족의 단량체일 수 있다. 에틸렌계 불포화 단량체 중에서 아릴 지방족 탄화수소의 단량체 예로는 스틸렌(styrene), p-메틸 스틸렌(p-methyl styrene), p-에틸 스틸렌(p-ethyl styrene) 및 m-이소프로필 스틸렌(m-isopropyl styrene)을 들 수 있다.The ethylenically unsaturated monomer may have 20, more specifically up to 10 carbon atoms. For example, an aliphatic monomer such as ethane, propene, 1-butene, iso-butene, 1-hexene, 1-octene, or It may be an aryl aliphatic monomer containing an aryl substituent on another aliphatic molecule, in particular an aryl substituent on an ethylenically unsaturated carbon atom. Examples of monomers of aryl aliphatic hydrocarbons among ethylenically unsaturated monomers include styrene, p-methyl styrene, p-ethyl styrene and m-isopropyl styrene can be heard
동일한 폴리머 내에 다수의 상이한 에틸렌계 불포화 단량체를 사용하는 것이 가능하지만, 하나의 구체적인 예에서, 상기 폴리케톤은 하기 화학식 1로 표시되고 일산화탄소와 적어도 2개의 탄소 원자를 가지는 에틸렌계 불포화 단량체를 포함하는 호모 폴리머(homopolymer), 또는 하기 화학식 2로 표시되고 일산화탄소, 에틸렌 및 적어도 3개의 탄소 원자를 가지는 에틸렌계 불포화 단량체, 특히 프로필렌과 같은 α-올레핀을 포함하는 선형 교대 코폴리머(copolymer)이다.Although it is possible to use a number of different ethylenically unsaturated monomers in the same polymer, in one specific example, the polyketone is represented by Formula 1 below and includes carbon monoxide and an ethylenically unsaturated monomer having at least two carbon atoms. A homopolymer or a linear alternating copolymer represented by formula 2 below and containing carbon monoxide, ethylene and an ethylenically unsaturated monomer having at least 3 carbon atoms, in particular an α-olefin such as propylene.
(1) (One)
(2) (2)
상기 식에서,In the above formula,
A는 적어도 2개의 탄소 원자를 가진 에틸렌계 불포화 단량체로부터 유래된 지방족 탄화수소이며;A is an aliphatic hydrocarbon derived from an ethylenically unsaturated monomer having at least 2 carbon atoms;
u는 2 내지 100이고;u is 2 to 100;
v는 10 내지 100이며, w는 1 내지 50이고, v/w의 비율은 2 내지 100이다. v is 10 to 100, w is 1 to 50, and the ratio of v/w is 2 to 100.
화학식 2의 폴리케톤이 본 발명의 수지 복합체의 주성분으로 사용되는 경우에는, 적어도 3개의 탄소 원자를 가진 에틸렌계 불포화 단량체로부터 유래된 지방족 탄화수소를 포함하고 있는 단위가 약 10개 내지 100개 정도 존재하고, 이러한 지방족 탄화수소를 포함하고 있는 각 단위당 에틸렌으로부터 유래된 지방족 탄화수소를 포함하는 단위가 코폴리머 내에 적어도 2개 존재한다. 또한, 에틸렌으로부터 유래된 지방족 탄화수소를 포함하는 단위와 상기 지방족 탄화수소를 포함하는 단위는 폴리머 체인 전체에 걸쳐 랜덤으로 발견된다.When the polyketone of Formula 2 is used as the main component of the resin composite of the present invention, there are about 10 to 100 units containing an aliphatic hydrocarbon derived from an ethylenically unsaturated monomer having at least 3 carbon atoms, , At least two units containing an aliphatic hydrocarbon derived from ethylene per unit containing such aliphatic hydrocarbon are present in the copolymer. Also, units containing an aliphatic hydrocarbon derived from ethylene and units containing the aliphatic hydrocarbon are found randomly throughout the polymer chain.
추가적인 단량체 역시 사용할 수 있으며 여전히 본 명세서에 설명된 폴리케톤의 범위 안에 포함된다. 즉, 폴리케톤은 넷, 다섯, 또는 더 많은 단량체의 조합에서 만들어질 수도 있다.Additional monomers may also be used and are still included within the scope of the polyketones described herein. That is, polyketones may be made from combinations of four, five, or more monomers.
겔 투과 크로마토그래피로 측정하여 수평균 분자량이 약 1000 내지 약 200,000인 폴리케톤, 특히 수평균 분자량이 약 20,000 내지 약 90,000인 폴리케톤이 특히 바람직하다. 폴리머의 물리적 속성은 폴리머가 호모 폴리머인지 코폴리머인지에 관계 없이 분자량에 의존하고, 코폴리머의 경우, 존재하는 지방족 탄화수소의 비율이나 특성에도 부분적으로 의존할 것이다.Particularly preferred are polyketones having a number average molecular weight of about 1000 to about 200,000, particularly polyketones having a number average molecular weight of about 20,000 to about 90,000 as determined by gel permeation chromatography. The physical properties of a polymer, whether it is a homopolymer or a copolymer, will depend in part on its molecular weight and, in the case of copolymers, on the proportion or nature of the aliphatic hydrocarbons present.
이러한 폴리케톤의 제조 방법은 앞서 설명한 바와 같이, 미국특허 제4,843,144호에 공지되어 있으므로, 그에 대한 자세한 설명은 본 명세서에서 생략한다.As described above, the method for producing such a polyketone is known from US Patent No. 4,843,144, so a detailed description thereof is omitted herein.
상기 셀룰로오스 또는 셀룰로오스 유도체는, 예를 들어, 카르복시메틸 셀룰로오스, 하이드록시에틸 셀룰로오스 및 나노 셀룰로오스로 이루어진 군에서 선택되는 하나 이상일 수 있다.The cellulose or cellulose derivative may be, for example, at least one selected from the group consisting of carboxymethyl cellulose, hydroxyethyl cellulose, and nano cellulose.
상기 나노 셀룰로오스는 셀룰로오스 사슬이 다발을 이루며 빽빽하게 결합한 나노 또는 마이크로미터 크기의 막대형태 입자 혹은 섬유를 말하며, 바이오 매스에서 추출하는 방법에 따라 크게 셀룰로오스 나노섬유(cellulose nanofibril, CNF)와 셀룰로오스 나노결정(cellulose nanocrystal, CNC)으로 나눌 수 있다. 셀룰로오스 나노섬유는 보통 직경(폭)이 5~100 nm, 길이가 수에서 수십 ㎛인 섬유로서 기계적 처리(mechanical treatment)를 통해 제조할 수 있다. 반면에, 셀룰로오스 나노결정은 직경(폭)이 2~20 nm이고 길이가 100~600 nm인 막대기 모양의 결정으로서 산 가수분해에 의한 화학적 처리(chemical treatment)를 통해 제조될 수 있다.The nano-cellulose refers to nano- or micrometer-sized rod-shaped particles or fibers in which cellulose chains form a bundle and are tightly coupled, and depending on the method of extraction from biomass, cellulose nanofibril (CNF) and cellulose nanocrystals nanocrystal, CNC). Cellulose nanofibers are fibers having a diameter (width) of 5 to 100 nm and a length of several to several tens of μm, and can be prepared through mechanical treatment. On the other hand, cellulose nanocrystals are rod-shaped crystals with a diameter (width) of 2 to 20 nm and a length of 100 to 600 nm, and can be prepared through chemical treatment by acid hydrolysis.
본 발명의 수지 복합체에서 셀룰로오스 또는 셀룰로오스 유도체의 함량은 앞서 정의한 바와 같이 폴리케톤 100 중량부에 대해 10 내지 90 중량부이고, 그것의 함량이 너무 적으면 셀룰로오스계 물질의 특성을 발휘하기 어렵고, 반대로 너무 많으면 적절한 성형성을 가진 수지 복합체의 제조가 어려울 수 있으므로, 바람직하지 않다.As defined above, the content of cellulose or cellulose derivative in the resin composite of the present invention is 10 to 90 parts by weight based on 100 parts by weight of polyketone, and if the content is too small, it is difficult to exhibit the characteristics of a cellulose-based material, and conversely, If it is too large, production of a resin composite having appropriate moldability may be difficult, which is not preferable.
하나의 바람직한 예에서, 본 발명의 수지 복합체에는 폴리케톤 100 중량부를 기준으로 폴리비닐알코올이 1 내지 30 중량부로 추가로 포함될 수 있고, 이 경우에, 폴리비닐알코올은 셀룰로오스 또는 셀룰로오스 유도체와 수소 결합을 이루고 있다.In one preferred example, the resin composite of the present invention may further include 1 to 30 parts by weight of polyvinyl alcohol based on 100 parts by weight of polyketone, and in this case, polyvinyl alcohol forms a hydrogen bond with cellulose or a cellulose derivative. is fulfilling
폴리비닐알코올은 셀룰로오스계 물질과 마찬가지로 친수성을 가지므로, 이들을 혼합하면, 셀룰로오스계 물질의 하이드록시기와 폴리비닐알코올의 하이드록시기가 수소결합을 통해 겔 형태로 결합한다. 따라서, 보조적으로 폴리비닐알코올을 적용하여 가스 차단성을 더욱 향상시킬 수 있고, 셀룰로오스계 물질을 안정화 할 수 있다. 이러한 폴리비닐알코올은 셀룰로오스 또는 셀룰로오스 유도체의 중량을 기준으로 10 내지 30% 범위로 포함될 수 있다.Since polyvinyl alcohol has hydrophilicity like a cellulose-based material, when they are mixed, the hydroxyl group of the cellulose-based material and the hydroxyl group of polyvinyl alcohol are bonded in the form of a gel through a hydrogen bond. Therefore, by applying polyvinyl alcohol as an aid, gas barrier properties can be further improved and the cellulose-based material can be stabilized. Such polyvinyl alcohol may be included in the range of 10 to 30% based on the weight of cellulose or cellulose derivatives.
상기 폴리케톤 가소제는 화학 구조 중에 폴리케톤의 기본 반복단위와 유사한 구조가 포함되어 있어서, 폴리케톤들 사이로 쉽게 혼화되어 폴리케톤의 융점을 낮추는 작용을 하는 성분이다.The polyketone plasticizer is a component that has a structure similar to the basic repeating unit of polyketone in its chemical structure and is easily miscible with polyketones to lower the melting point of polyketone.
이러한 폴리케톤 가소제의 대표적인 예로는 본 출원인에 의해 제안된 한국특허 제10-2093026호의 가소제를 참고할 수 있으며, 이는 참조로서 본 명세서의 내용에 합체된다.As a representative example of such a polyketone plasticizer, reference may be made to the plasticizer of Korean Patent No. 10-2093026 proposed by the present applicant, which is incorporated herein by reference.
하나의 구체적인 예에서, 상기 폴리케톤 가소제는 하기 화학식 3 및 4에서 선택되는 적어도 하나 이상의 가소제일 수 있다.In one specific example, the polyketone plasticizer may be at least one or more plasticizers selected from Chemical Formulas 3 and 4 below.
(3) (3)
(4) (4)
상기 식에서,In the above formula,
R1 및 R3은 서로 독립적으로 OH, OCH3, OCH2OH, O(CH2)nCH3, O(CH2)nCH2OH, OC6H5, OC6H4OH, O(CH2)nC6H5, O(CH2)nC6H4OH, O(CH2)nC6H4CH2OH, OC6H11, OC6H10OH, OC6H10CH2OH, O(CH2)nC6H11, O(CH2)nC6H10OH 또는 O(CH2)nC6H10CH2OH이고, 여기서, n은 1 내지 20의 자연수, 바람직하게는 1 내지 10의 자연수이며;R 1 and R 3 are independently of each other OH, OCH 3 , OCH 2 OH, O(CH 2 ) n CH 3 , O(CH 2 ) n CH 2 OH, OC 6 H 5 , OC 6 H 4 OH, O( CH 2 ) n C 6 H 5 , O(CH 2 ) n C 6 H 4 OH, O(CH 2 ) n C 6 H 4 CH 2 OH, OC 6 H 11 , OC 6 H 10 OH, OC 6 H 10 CH 2 OH, O(CH 2 ) n C 6 H 11 , O(CH 2 ) n C 6 H 10 OH or O(CH 2 ) n C 6 H 10 CH 2 OH, where n is from 1 to 20; a natural number, preferably a natural number from 1 to 10;
R2는 (CH2)m, [(CH2)m-C6H4]p, [(CH2)m-C6H10]q, [(CH2)a-X-(CH2)b]s, [(CH2)a-X-(CH2)b-Y-(CH2)c]t 또는 [(CH2)aC(CH3)2(CH2)a'-X-(CH2)bC(CH3)2(CH2)b']s 이고;R 2 is (CH 2 ) m , [(CH 2 ) m -C 6 H 4 ] p , [(CH 2 ) m -C 6 H 10 ] q , [(CH 2 ) a -X-(CH 2 ) b ] s , [(CH 2 ) a -X-(CH 2 ) b -Y-(CH 2 ) c ] t or [(CH 2 ) a C(CH 3 ) 2 (CH 2 ) a' -X- (CH 2 ) b C(CH 3 ) 2 (CH 2 ) b′ ] s ;
여기서, here,
m은 1 내지 20의 자연수, 바람직하게는 1 내지 10의 자연수이며;m is a natural number from 1 to 20, preferably from 1 to 10;
X 및 Y는 서로 독립적으로 C6H4, C6H10, O, CO2, OCO2, O2C 또는 NH이고;X and Y are independently of each other C 6 H 4 , C 6 H 10 , O, CO 2 , OCO 2 , O 2 C or NH;
a, a', b, b' 및 c는 서로 독립적으로 1 내지 20의 자연수, 바람직하게는 1 내지 10의 자연수이며;a, a', b, b' and c are independently of each other a natural number of 1 to 20, preferably a natural number of 1 to 10;
p, q, s 및 t는 서로 독립적으로 1 내지 5의 자연수이고,p, q, s and t are independently of each other a natural number from 1 to 5,
R4 및 R6는 서로 독립적으로 H, CH3, CH2OH, (CH2)nCH3, (CH2)nCH2OH, C6H5, C6H4OH, (CH2)nC6H5, (CH2)nC6H4OH, (CH2)nC6H4CH2OH, C6H11, C6H10OH, C6H10CH2OH, (CH2)nC6H11, (CH2)nC6H10OH, (CH2)nC6H10CH2OH, (CH2)nOCO2(CH2)n'H 또는 (CH2)nOCO2(CH2)n'OH 이고, 여기서, n 및 n'는 1 내지 20의 자연수, 바람직하게는 1 내지 10의 자연수이며;R 4 and R 6 are independently of each other H, CH 3 , CH 2 OH, (CH 2 ) n CH 3 , (CH 2 ) n CH 2 OH, C 6 H 5 , C 6 H 4 OH, (CH 2 ) n C 6 H 5 , (CH 2 ) n C 6 H 4 OH, (CH 2 ) n C 6 H 4 CH 2 OH, C 6 H 11 , C 6 H 10 OH, C 6 H 10 CH 2 OH, ( CH 2 ) n C 6 H 11 , (CH 2 ) n C 6 H 10 OH, (CH 2 ) n C 6 H 10 CH 2 OH, (CH 2 ) n OCO 2 (CH 2 ) n' H or (CH 2 ) n OCO 2 (CH 2 ) n' OH, where n and n' are natural numbers from 1 to 20, preferably from 1 to 10;
R5는 (CH2)m 이고, 여기서, m은 1 내지 20의 자연수, 바람직하게는 1 내지 10의 자연수이며,R 5 is (CH 2 ) m , where m is a natural number from 1 to 20, preferably a natural number from 1 to 10;
상기에서 CH2, (CH2)n, (CH2)m, C6H5, C6H4, C6H11 및 C6H10-은 치환 구조 또는 미치환 구조이며, 치환 구조인 경우에 하나 이상의 수소가 C1-C5 알킬기로 치환되어 있다.In the above, CH 2 , (CH 2 ) n , (CH 2 ) m , C 6 H 5 , C 6 H 4 , C 6 H 11 and C 6 H 10- are substituted structures or unsubstituted structures, and in the case of substituted structures, at least one hydrogen is It is substituted with a C 1 -C 5 alkyl group.
하나의 구체적인 예에서, 상기 C1-C5 알킬기는, 메틸기, 에틸기, 프로필기, 2-메틸 프로필기, 부틸기, 2-메틸 부틸기, 또는 tert-부틸기일 수 있으며, 바람직하게는 메틸기일 수 있다.In one specific example, the C 1 -C 5 alkyl group may be a methyl group, an ethyl group, a propyl group, a 2-methyl propyl group, a butyl group, a 2-methyl butyl group, or a tert-butyl group, preferably a methyl group. can
상기 화학식 3에서, R1 및 R3은, 하나의 바람직한 예에서, 서로 독립적으로 OCH3 또는 O(CH2)nCH3 (n = 1 내지 5의 자연수)일 수 있으며, 더욱 바람직하게는, OCH3, OCH2CH3, OCH2CH2CH3, 또는 OCH2CH2CH2CH3 일 수 있다.In Formula 3, R 1 and R 3 , in one preferred example, may independently be OCH 3 or O(CH 2 ) n CH 3 (n = a natural number of 1 to 5), more preferably, OCH 3 , OCH 2 CH 3 , OCH 2 CH 2 CH 3 , or OCH 2 CH 2 CH 2 CH 3 .
R2는, 하나의 바람직한 예에서, (CH2)m, [(CH2)a-X-(CH2)b]s 또는 [(CH2)a-X-(CH2)b-Y-(CH2)c]t 일 수 있고, 더욱 바람직하게는 [(CH2)a-X-(CH2)b]s 또는 [(CH2)a-X-(CH2)b-Y-(CH2)c]t 일 수 있다. 여기서, 바람직하게는 X 및 Y가 서로 독립적으로 O, CO2, OCO2 또는 O2C일 수 있다.R 2 is, in one preferred example, (CH 2 ) m , [(CH 2 ) a -X-(CH 2 ) b ] s or [(CH 2 ) a -X-(CH 2 ) b -Y- (CH 2 ) c ] t , more preferably [(CH 2 ) a -X-(CH 2 ) b ] s or [(CH 2 ) a -X-(CH 2 ) b -Y-( CH 2 ) c ] t . Here, preferably, X and Y may be each independently O, CO 2 , OCO 2 or O 2 C.
또 다른 바람직한 예에서, R2 부위(moiety)의 분자량은 100 내지 3,000일 수 있고, 더욱 바람직하게는 500 내지 2,000일 수 있다.In another preferred example, the molecular weight of the R 2 moiety may be 100 to 3,000, more preferably 500 to 2,000.
상기 화학식 4에서, R4 및 R6는, 하나의 바람직한 예에서, 서로 독립적으로 (CH2)nCH2OH, (CH2)nOCO2(CH2)n'H 또는 (CH2)nOCO2(CH2)n'OH 이고, 여기서, n 및 n'는 1 내지 5의 자연수일 수 있다.In Formula 4, R 4 and R 6 are, in one preferred example, independently of each other (CH 2 ) n CH 2 OH, (CH 2 ) n OCO 2 (CH 2 ) n' H or (CH 2 ) n OCO 2 (CH 2 ) n' OH, where n and n' may be natural numbers from 1 to 5.
본 발명의 수지 복합체에서 폴리케톤 가소제의 함량은 앞서 정의한 바와 같이 폴리케톤 100 중량부에 대해 1 내지 30 중량부인 바, 가소제의 함량이 너무 적은 경우에는 융점 저하의 목적을 달성하기 어려울 수 있고, 반대로 가소제의 너무 많은 경우에는 지나치게 높은 유동성으로 인해 오히려 성형이 어려울 수 있고 성형품의 물성 저하가 초래될 수 있으므로 바람직하지 않다.As defined above, the content of the polyketone plasticizer in the resin composite of the present invention is 1 to 30 parts by weight based on 100 parts by weight of the polyketone. If the content of the plasticizer is too small, it may be difficult to achieve the purpose of lowering the melting point, and conversely In the case of too much plasticizer, molding may be rather difficult due to excessively high flowability and may result in deterioration of physical properties of a molded article, so it is not preferable.
경우에 따라서는, 상기 폴리케톤 가소제에 대해 혼용성이 있는 에틸렌 카보네이트, 프로필렌 카보네이트, 부틸렌 카보네이트로, 하이드록시에틸렌 카보네이트, 디메틸카보네이트, 및 디에틸 카보네이트로 이루어진 군에서 선택되는 하나 이상을 추가로 포함시켜 가소성을 더욱 높을 수도 있다. 이 경우, 추가되는 카보네이트 화합물은 폴리케톤 가소제의 중량을 기준으로 5 내지 50%의 범위일 수 있다.In some cases, ethylene carbonate, propylene carbonate, butylene carbonate compatible with the polyketone plasticizer, further comprising at least one selected from the group consisting of hydroxyethylene carbonate, dimethyl carbonate, and diethyl carbonate The plasticity may be higher by doing so. In this case, the added carbonate compound may range from 5 to 50% based on the weight of the polyketone plasticizer.
본 발명은 또한 상기 수지 복합체를 제조하는 방법을 제공하는 바, 상기 제조방법은, The present invention also provides a method for preparing the resin composite, the manufacturing method comprising:
(a) 셀룰로오스 또는 셀룰로오스 유도체를 용매에 용해시켜 셀룰로오스 용액을 제조하는 과정;(a) preparing a cellulose solution by dissolving cellulose or a cellulose derivative in a solvent;
(b) 상기 셀룰로오스 용액과 폴리케톤 분말을 혼합하여 혼합물을 제조하는 과정;(b) preparing a mixture by mixing the cellulose solution and polyketone powder;
(c) 상기 혼합물에서 용매를 제거하여 셀룰로오스 또는 셀룰로오스 유도체가 코팅된 폴리케톤 분말을 제조하는 과정; 및(c) preparing a polyketone powder coated with cellulose or a cellulose derivative by removing the solvent from the mixture; and
(d) 상기 셀룰로오스 또는 셀룰로오스 유도체가 코팅된 폴리케톤 분말과 폴리케톤 가소제를 혼합한 후 혼합물을 용융하는 과정;(d) mixing the cellulose or cellulose derivative-coated polyketone powder with a polyketone plasticizer and then melting the mixture;
을 포함하는 것으로 구성되어 있다.It consists of including.
상기 용매는 물과 친수성 유기용매로 이루어진 군에서 선택되는 하나 이상일 수 있고, 상기 친수성 유기용매의 예로는 에틸알코올, 이소프로필알코올 등을 들 수 있지만, 이들만으로 한정되지 않음은 물론이다.The solvent may be at least one selected from the group consisting of water and a hydrophilic organic solvent, and examples of the hydrophilic organic solvent include ethyl alcohol and isopropyl alcohol, but are not limited thereto.
상기 과정(b)에서 폴리케톤 분말은 입경 범위가 대략 0.10 mm 내지 0.80 mm일 수 있다.In the process (b), the polyketone powder may have a particle diameter range of approximately 0.10 mm to 0.80 mm.
상기 과정(c)에서 용매의 제거는, 예를 들어, 감압조건에서 혼합물을 승온시켜 수행될 수 있으며, 감압 및 승온 조건은 성분의 변질 등을 유발하지 않으면서 건조의 효율성을 높을 수 있는 범위에서 적절히 선택될 수 있고, 그 예시는 이후 설명하는 실시예들을 참조할 수 있다.Removal of the solvent in the process (c) may be performed, for example, by raising the temperature of the mixture under reduced pressure conditions, and the reduced pressure and elevated temperature conditions are within the range of increasing the efficiency of drying without causing deterioration of components. It may be appropriately selected, and examples thereof may refer to embodiments described later.
상기 과정(d)에서 혼합물을 셀룰로오스 또는 셀룰로오스 유도체의 분해 온도 이하의 범위로 가열하여 용융함으로써 예를 들어 압출 또는 사출할 수 있는데, 이러한 과정에서, 셀룰로오스 또는 셀룰로오스 유도체가 폴리케톤와 수소결합을 이룰 수 있다.In the process (d), the mixture may be melted by heating to a range below the decomposition temperature of the cellulose or cellulose derivative, for example, extruded or injected. In this process, cellulose or cellulose derivative can form a hydrogen bond with polyketone .
본 발명의 수지 복합체는 다양한 형태로 성형될 수 있고, 대표적인 예로 가스 차단성이 우수한 필름으로 제조될 수 있다.The resin composite of the present invention can be molded into various shapes, and as a representative example, it can be made into a film with excellent gas barrier properties.
이상에서 설명한 바와 같이, 본 발명에 따른 수지 복합체는 폴리케톤 가소제에 의해 폴리케톤의 융점을 낮추어, 폴리케톤과의 수지 복합체를 형성하는 과정에서 셀룰로오스계 물질의 변질 내지 분해가 초래되지 않고, 각각 가스 차단성이 우수한 폴리케톤과 셀룰로오스계 물질의 조합과 폴리케톤의 카르보닐기와 셀룰로오스계 물질의 하이드록시 간의 수소결합에 의해 더욱 우수한 가스 차단성과 물리적 특성을 발휘할 수 있다.As described above, in the resin composite according to the present invention, the melting point of polyketone is lowered by the polyketone plasticizer, and in the process of forming the resin composite with polyketone, the cellulose-based material does not deteriorate or decompose, and each gas Further excellent gas barrier properties and physical properties can be exhibited by the combination of polyketone with excellent barrier properties and a cellulose-based material and the hydrogen bond between the carbonyl group of the polyketone and the hydroxyl of the cellulose-based material.
이하, 본 발명에 따른 일부 실시예들을 참조하여 더욱 상세히 설명하지만, 본 발명의 범주가 그것에 의해 한정되지 않음은 물론이다.Hereinafter, it will be described in more detail with reference to some embodiments according to the present invention, but it goes without saying that the scope of the present invention is not limited thereto.
[제조예][Production Example]
10L의 냉각관과 교반기 및 맨틀이 구비된 Pyrex 재질의 유리 반응기에 에틸렌글리콜디카르복시산 1 kg과 디메틸카보네이트 3 kg을 부가하고, 촉매로서 포타시움 카보네이트 10 g을 추가한 후, 섭씨 120도에서 12시간 반응시켰다. 그런 다음, 반응물을 냉각하고 증류수로 세척한 후, 건조제로서 소디움 설페이트 500 g을 넣고 감압 상태에서 용매를 제거하여, 디메톡시 에틸글리콜 카보네이트 1.2 kg을 합성하였다1 kg of ethylene glycol dicarboxylic acid and 3 kg of dimethyl carbonate were added to a Pyrex glass reactor equipped with a 10 L cooling pipe, stirrer, and mantle, and 10 g of potassium carbonate was added as a catalyst, followed by reaction at 120 degrees Celsius for 12 hours. made it Then, after cooling the reactant and washing with distilled water, 500 g of sodium sulfate was added as a drying agent and the solvent was removed under reduced pressure to synthesize 1.2 kg of dimethoxy ethyl glycol carbonate.
[실시예 1][Example 1]
카르복시메틸 셀룰로오스 2 kg에 증류수 1 kg과 이소프로필알코올 1 kg을 넣고, 섭씨 80도에서 약 3시간 동안 고점도 믹서에 넣고 완전히 용해시킨 후 냉각하여, 고점도의 50% 농도의 하이드록시셀룰로오스 용액을 얻었다. 50% 농도의 하이드록시셀룰로오스 용액 2 kg과 폴리케톤 분말 9 kg을 감압 장치와 승온이 가능한 비유동성 믹서(Henschel Mixer)에 넣고, 상온에서 2시간 동안 혼합하였다. 그런 다음, 섭씨 50도로 승온한 후 감압하여 수분량이 500 ppm 이하로 제거할 수 있도록 12시간 동안 용매를 완전히 제거하여, 카르복시메틸 셀룰로오스(CMC)가 코팅된 폴리케톤 분말 10 kg을 얻었다.1 kg of distilled water and 1 kg of isopropyl alcohol were added to 2 kg of carboxymethyl cellulose, put in a high-viscosity mixer at 80 degrees Celsius for about 3 hours, completely dissolved, and cooled to obtain a high-viscosity 50% concentration hydroxycellulose solution. 2 kg of a 50% concentration hydroxycellulose solution and 9 kg of polyketone powder were placed in a non-fluid mixer (Henschel Mixer) capable of increasing the temperature and a pressure reducing device, and mixed for 2 hours at room temperature. Then, after raising the temperature to 50 degrees Celsius, the pressure was reduced, and the solvent was completely removed for 12 hours so that the moisture content could be removed to 500 ppm or less, thereby obtaining 10 kg of carboxymethyl cellulose (CMC)-coated polyketone powder.
[실시예 2][Example 2]
하이드록시에틸셀룰로오스 2 kg을 증류수 1 kg 및 이소프로필알코올 1 kg에 넣고, 섭씨 80도에서 약 3시간 동안 고점도 믹서에 넣고 완전히 용해시킨 후 냉각하여, 고점도의 50% 농도의 하이드록시셀룰로오스 용액을 얻었다. 50% 농도의 하이드록시셀룰로오스 용액 2 kg과 폴리케톤 분말 9 kg을 감압 장치와 승온이 가능한 비유동성 믹서(Henschel Mixer)에 넣고, 상온에서 2시간 동안 혼합하였다. 그런 다음, 섭씨 50도로 승온한 후 감압하여 수분량이 500 ppm 이하로 되도록 12시간 동안 용매를 완전히 제거하여, 하이드록시에틸셀룰로오스(HEC)가 코팅된 폴리케톤 분말 10 kg을 얻었다.2 kg of hydroxyethyl cellulose was added to 1 kg of distilled water and 1 kg of isopropyl alcohol, put in a high-viscosity mixer at 80 degrees Celsius for about 3 hours, completely dissolved, and then cooled to obtain a high-viscosity 50% concentration hydroxycellulose solution. . 2 kg of a 50% concentration hydroxycellulose solution and 9 kg of polyketone powder were placed in a pressure reducing device and a non-fluid mixer (Henschel Mixer) capable of raising the temperature, and mixed at room temperature for 2 hours. Then, after raising the temperature to 50 degrees Celsius, the pressure was reduced and the solvent was completely removed for 12 hours so that the moisture content was less than 500 ppm, thereby obtaining 10 kg of polyketone powder coated with hydroxyethyl cellulose (HEC).
[실시예 3][Example 3]
카르복시메틸 셀룰로오스 1.8 kg과 폴리비닐알코올 200 g을 증류수 1 kg과 이소프로필알코올 1 kg에 넣고, 섭씨 80도에서 약 3시간 동안 고점도 믹서에 넣고 완전히 용해시킨 후 냉각하여, 겔 형태의 카르복시메틸 셀룰로오스와 폴리비닐알코올이 결합된 겔을 얻었다. 카르복시메틸 셀룰로오스와 폴리비닐알코올(CMC-PVA) 겔 2 kg과 폴리케톤 9 kg을 감압 장치와 승온이 가능한 비유동성 믹서(Henschel Mixer)에 넣고, 상온에서 2시간 동안 혼합하였다. 그런 다음, 섭씨 50도로 승온한 후 감압하여 수분량이 500 ppm 이하로 되도록 12시간 동안 물을 완전히 제거하여, 카르복시메틸 셀룰로오스 폴리비닐알코올(CMC-PVA) 겔이 코팅된 폴리케톤 10 kg을 얻었다.1.8 kg of carboxymethyl cellulose and 200 g of polyvinyl alcohol were put into 1 kg of distilled water and 1 kg of isopropyl alcohol, put in a high-viscosity mixer at 80 degrees Celsius for about 3 hours, completely dissolved, and then cooled to obtain gel-type carboxymethyl cellulose and A polyvinyl alcohol bound gel was obtained. 2 kg of carboxymethyl cellulose and polyvinyl alcohol (CMC-PVA) gel and 9 kg of polyketone were placed in a pressure reducing device and a non-fluid mixer (Henschel Mixer) capable of raising the temperature, and mixed at room temperature for 2 hours. Then, after raising the temperature to 50 degrees Celsius, the pressure was reduced and the water was completely removed for 12 hours so that the water content was less than 500 ppm to obtain 10 kg of polyketone coated with carboxymethyl cellulose polyvinyl alcohol (CMC-PVA) gel.
[실시예 4][Example 4]
나노 셀룰로오스(sappi사 CNF) 2 kg을 증류수 1 kg과 이소프로필알코올 1 kg에 넣고 분산제로서 실리콘 분산제(BYK-349) 2 g을 넣은 후, 섭씨 80도에서 약 3시간 동안 고점도 믹서에 넣고 완전히 분산시킨 뒤 냉각하여, 나노 셀룰로오스 분산액을 제조하였다. 제조된 분산액 2 kg과 폴리케톤 9 kg을 감압 장치와 승온이 가능한 비유동성 믹서(Henschel Mixer)에 넣고, 상온에서 2시간 동안 혼합하였다. 섭씨 50도로 승온한 후 감압하여 수분량이 500 ppm 이하로 되도록 12시간 동안 물을 완전히 제거하여, 나노 셀룰로오스가 코팅된 폴리케톤 10 kg을 얻었다.Put 2 kg of nanocellulose (sappi's CNF) into 1 kg of distilled water and 1 kg of isopropyl alcohol, add 2 g of silicone dispersant (BYK-349) as a dispersing agent, and then put it in a high-viscosity mixer at 80 degrees Celsius for about 3 hours to completely disperse After cooling, a nano-cellulose dispersion was prepared. 2 kg of the prepared dispersion and 9 kg of polyketone were placed in a pressure reducing device and a non-fluid mixer (Henschel Mixer) capable of raising the temperature, and mixed at room temperature for 2 hours. After raising the temperature to 50 degrees Celsius, the pressure was reduced and water was completely removed for 12 hours so that the moisture content was less than 500 ppm, thereby obtaining 10 kg of polyketone coated with nanocellulose.
[실시예 5][Example 5]
실시예 4에서 제조된 나노 셀룰로오스가 코팅된 폴리케톤 10 kg, 제조예에서 제조된 디메톡시 에틸글리콜 카보네이트 500 g, 및 프로필렌 카보네이트 100 g을 이축 압출기에 넣고 압출(압출온도: 섭씨 190도, 토출조건: 2kg/hr에서 200rpm)하여 펠렛을 제조한 후, 필름 압출 성형기(T-die)를 이용해서 섭씨 200도 가공온도에서 50 ㎛ 두께의 필름을 제조하였다.10 kg of polyketone coated with nanocellulose prepared in Example 4, 500 g of dimethoxy ethyl glycol carbonate prepared in Preparation Example, and 100 g of propylene carbonate were put into a twin screw extruder and extruded (extrusion temperature: 190 degrees Celsius, discharge conditions) : 200rpm at 2kg/hr) to prepare pellets, and then use a film extrusion molding machine (T-die) to prepare a film having a thickness of 50 μm at a processing temperature of 200 degrees Celsius.
[실시예 6][Example 6]
실시예 1에서 제조된 카르복시메틸 셀룰로오스(CMC)가 코팅된 폴리케톤 10 kg, 제조예에서 제조된 디메톡시 에틸글리콜 카보네이트 500 g, 및 프로필렌 카보네이트 100 g을 이축 압출기에 넣고 압출(압출온도: 섭씨 190도, 토출조건: 2kg/hr에서 200rpm)하여 펠렛을 제조한 후, 필름 압출 성형기(T-die)를 이용해서 섭씨 200도 가공온도에서 50 ㎛ 두께의 필름을 제조하였다.10 kg of polyketone coated with carboxymethyl cellulose (CMC) prepared in Example 1, 500 g of dimethoxy ethyl glycol carbonate prepared in Preparation Example, and 100 g of propylene carbonate were put into a twin screw extruder and extruded (extrusion temperature: 190 degrees Celsius) Also, discharge conditions: 2kg/hr at 200 rpm) to prepare pellets, and then use a film extrusion molding machine (T-die) to prepare a film with a thickness of 50 μm at a processing temperature of 200 degrees Celsius.
[실시예 7][Example 7]
실시예 3에서 제조된 하이드록시에틸셀룰로오스(HEC)가 코팅된 폴리케톤 10 kg, 제조예에서 제조된 디메톡시 에틸글리콜 카보네이트 500 g, 및 프로필렌 카보네이트 100 g을 이축 압출기에 넣고 압출(압출온도: 섭씨 190도, 토출조건: 2kg/hr에서 200rpm)하여 펠렛을 제조한 후, 필름 압출 성형기(T-die)를 이용해서 섭씨 200도 가공온도에서 50 ㎛ 두께의 필름을 제조하였다.10 kg of polyketone coated with hydroxyethyl cellulose (HEC) prepared in Example 3, 500 g of dimethoxy ethyl glycol carbonate prepared in Preparation Example, and 100 g of propylene carbonate were put into a twin screw extruder and extruded (extrusion temperature: Celsius) 190 degrees, discharge condition: 2 kg / hr at 200 rpm) to prepare pellets, and then use a film extrusion molding machine (T-die) to prepare a film with a thickness of 50 μm at a processing temperature of 200 degrees Celsius.
[실시예 8][Example 8]
실시예 4에서 제조된 카르복시메틸 셀룰로오스와 폴리비닐알코올이(CMC-PVA) 코팅된 폴리케톤 10 kg, 제조예에서 제조된 디메톡시 에틸글리콜 카보네이트 500 g, 및 프로필렌 카보네이트 100 g을 이축 압출기에 넣고 압출(압출온도: 섭씨 190도, 토출조건: 2kg/hr에서 200rpm)하여 펠렛을 제조한 후, 필름 압출 성형기(T-die)를 이용해서 섭씨 200도 가공온도에서 50 ㎛ 두께의 필름을 제조하였다10 kg of polyketone coated with carboxymethyl cellulose and polyvinyl alcohol (CMC-PVA) prepared in Example 4, 500 g of dimethoxy ethyl glycol carbonate prepared in Preparation Example, and 100 g of propylene carbonate were put into a twin screw extruder and extruded. (Extrusion temperature: 190 degrees Celsius, discharge conditions: 200 rpm at 2 kg/hr) to prepare pellets, and then use a film extrusion molding machine (T-die) to prepare a film with a thickness of 50 μm at a processing temperature of 200 degrees Celsius.
[비교예 1][Comparative Example 1]
폴리케톤 10 kg을 필름 압출 성형기(T-die)를 이용해서 섭씨 240도의 가공온도에서 50 ㎛ 두께의 필름을 제조하였다.A film having a thickness of 50 μm was prepared from 10 kg of polyketone using a film extrusion molding machine (T-die) at a processing temperature of 240 degrees Celsius.
[비교예 2][Comparative Example 2]
폴리케톤 10 kg을 필름 압출 성형기(T-die)를 이용해서 섭씨 240도의 가공온도에서 100 ㎛ 두께의 필름을 제조하였다.A film having a thickness of 100 μm was prepared from 10 kg of polyketone using a film extrusion molding machine (T-die) at a processing temperature of 240 degrees Celsius.
[실험예][Experimental example]
산소 투과도 측정Oxygen permeability measurement
실시예 5 내지 8과 비교예 1 및 2에서 각각 제조된 필름들에 대해 산소투과도 측정기(MOCON, Model OX-Tran)을 사용하여 산소투과도를 측정 하였고, 그 결과를 하기 표 1에 나타내었다.Oxygen permeability was measured using an oxygen permeability meter (MOCON, Model OX-Tran) for the films prepared in Examples 5 to 8 and Comparative Examples 1 and 2, respectively, and the results are shown in Table 1 below.
상기 표 1에서 보는 바와 같이, 나노 셀룰로오스, 카르복시메틸 셀룰로오스, 하이드록시에틸 셀룰로오스, 카르복시메틸 셀룰로오스-폴리비닐 알코올이 포함된 폴리케톤 필름의 산소 투과도가 폴리케톤 단일 수지로 제조된 필름보다 우수한 것을 알 수 있다. 특히, 나노 셀룰로오스(실시예 6)나 카르복시메틸 셀룰로오스-폴리비닐알코올(실시예 9)이 포함된 폴리케톤 필름이 가장 우수한 것으로 확인되었다. As shown in Table 1, the oxygen permeability of the polyketone film containing nano-cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose-polyvinyl alcohol is superior to that of a film made of polyketone single resin. have. In particular, the polyketone film containing nano-cellulose (Example 6) or carboxymethyl cellulose-polyvinyl alcohol (Example 9) was confirmed to be the most excellent.
본 발명이 속한 분야에서 통상의 지식을 가진 자라면, 상기 내용을 바탕으로, 본 발명의 범주 내에서 다양한 응용 및 변형을 수행하는 것이 가능할 것이다.Those skilled in the art to which the present invention pertains will be able to perform various applications and modifications within the scope of the present invention based on the above information.
Claims (9)
(2)
(3)
상기 식에서,
R1 및 R3은 서로 독립적으로 OH, OCH3, OCH2OH, O(CH2)nCH3, O(CH2)nCH2OH, OC6H5, OC6H4OH, O(CH2)nC6H5, O(CH2)nC6H4OH, O(CH2)nC6H4CH2OH, OC6H11, OC6H10OH, OC6H10CH2OH, O(CH2)nC6H11, O(CH2)nC6H10OH 또는 O(CH2)nC6H10CH2OH이고, 여기서, n은 1 내지 20의 자연수이며;
R2는 (CH2)m, [(CH2)m-C6H4]p, [(CH2)m-C6H10]q, [(CH2)a-X-(CH2)b]s, [(CH2)a-X-(CH2)b-Y-(CH2)c]t 또는 [(CH2)aC(CH3)2(CH2)a'-X-(CH2)bC(CH3)2(CH2)b']s 이고;
여기서,
m은 1 내지 20의 자연수이며;
X 및 Y는 서로 독립적으로 C6H4, C6H10, O, CO2, OCO2, O2C 또는 NH이고;
a, a', b, b' 및 c는 서로 독립적으로 1 내지 20의 자연수이며;
p, q, s 및 t는 서로 독립적으로 1 내지 5의 자연수이고,
R4 및 R6는 서로 독립적으로 H, CH3, CH2OH, (CH2)nCH3, (CH2)nCH2OH, C6H5, C6H4OH, (CH2)nC6H5, (CH2)nC6H4OH, (CH2)nC6H4CH2OH, C6H11, C6H10OH, C6H10CH2OH, (CH2)nC6H11, (CH2)nC6H10OH, (CH2)nC6H10CH2OH, (CH2)nOCO2(CH2)n'H 또는 (CH2)nOCO2(CH2)n'OH 이고, 여기서, n 및 n'는 1 내지 20의 자연수이며;
R5는 (CH2)m 이고, 여기서, m은 1 내지 20의 자연수이며,
상기에서 CH2, (CH2)n, (CH2)m, C6H5, C6H4, C6H11 및 C6H10-은 치환 구조 또는 미치환 구조이며, 치환 구조인 경우에 하나 이상의 수소가 C1-C5 알킬기로 치환되어 있다.The resin composite according to claim 1, wherein the polyketone plasticizer is at least one selected from the following Chemical Formulas 3 and 4:
(2)
(3)
In the above formula,
R 1 and R 3 are independently of each other OH, OCH 3 , OCH 2 OH, O(CH 2 ) n CH 3 , O(CH 2 ) n CH 2 OH, OC 6 H 5 , OC 6 H 4 OH, O( CH 2 ) n C 6 H 5 , O(CH 2 ) n C 6 H 4 OH, O(CH 2 ) n C 6 H 4 CH 2 OH, OC 6 H 11 , OC 6 H 10 OH, OC 6 H 10 CH 2 OH, O(CH 2 ) n C 6 H 11 , O(CH 2 ) n C 6 H 10 OH or O(CH 2 ) n C 6 H 10 CH 2 OH, where n is from 1 to 20; is a natural number;
R 2 is (CH 2 ) m , [(CH 2 ) m -C 6 H 4 ] p , [(CH 2 ) m -C 6 H 10 ] q , [(CH 2 ) a -X-(CH 2 ) b ] s , [(CH 2 ) a -X-(CH 2 ) b -Y-(CH 2 ) c ] t or [(CH 2 ) a C(CH 3 ) 2 (CH 2 ) a' -X- (CH 2 ) b C(CH 3 ) 2 (CH 2 ) b′ ] s ;
here,
m is a natural number from 1 to 20;
X and Y are independently of each other C 6 H 4 , C 6 H 10 , O, CO 2 , OCO 2 , O 2 C or NH;
a, a', b, b' and c are each independently a natural number from 1 to 20;
p, q, s and t are independently of each other a natural number from 1 to 5,
R 4 and R 6 are independently of each other H, CH 3 , CH 2 OH, (CH 2 ) n CH 3 , (CH 2 ) n CH 2 OH, C 6 H 5 , C 6 H 4 OH, (CH 2 ) n C 6 H 5 , (CH 2 ) n C 6 H 4 OH, (CH 2 ) n C 6 H 4 CH 2 OH, C 6 H 11 , C 6 H 10 OH, C 6 H 10 CH 2 OH, ( CH 2 ) n C 6 H 11 , (CH 2 ) n C 6 H 10 OH, (CH 2 ) n C 6 H 10 CH 2 OH, (CH 2 ) n OCO 2 (CH 2 ) n' H or (CH 2 ) n OCO 2 (CH 2 ) n' OH, where n and n' are natural numbers from 1 to 20;
R 5 is (CH 2 ) m , where m is a natural number from 1 to 20;
In the above, CH 2 , (CH 2 ) n , (CH 2 ) m , C 6 H 5 , C 6 H 4 , C 6 H 11 and C 6 H 10- are substituted structures or unsubstituted structures, and in the case of substituted structures, at least one hydrogen is It is substituted with a C 1 -C 5 alkyl group.
(a) 셀룰로오스 또는 셀룰로오스 유도체를 용매에 용해시켜 셀룰로오스 용액을 제조하는 과정;
(b) 상기 셀룰로오스 용액과 폴리케톤 분말을 혼합하여 혼합물을 제조하는 과정;
(c) 상기 혼합물에서 용매를 제거하여 셀룰로오스 또는 셀룰로오스 유도체가 코팅된 폴리케톤 분말을 제조하는 과정; 및
(d) 상기 셀룰로오스 또는 셀룰로오스 유도체가 코팅된 폴리케톤 분말과 폴리케톤 가소제를 혼합한 후 혼합물을 용융하는 과정;
을 포함하는 것을 특징으로 하는 수지 복합체 제조방법.A method for producing the resin composite according to any one of claims 1 to 5,
(a) preparing a cellulose solution by dissolving cellulose or a cellulose derivative in a solvent;
(b) preparing a mixture by mixing the cellulose solution and polyketone powder;
(c) preparing a polyketone powder coated with cellulose or a cellulose derivative by removing the solvent from the mixture; and
(d) mixing the cellulose or cellulose derivative-coated polyketone powder with a polyketone plasticizer and then melting the mixture;
A method for producing a resin composite comprising a.
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KR20060043450A (en) * | 2004-03-09 | 2006-05-15 | 셀가드 인코포레이티드 | Method of making a composite microporous membrane |
KR20160119881A (en) * | 2014-11-28 | 2016-10-17 | 주식회사 씨케이바이오텍 | Coating composition for disinfectant tablet, and preparation method of coated disinfectant tablet using the same |
KR101777294B1 (en) * | 2016-02-04 | 2017-09-13 | 주식회사 효성 | Polyketone composition |
KR102093026B1 (en) * | 2018-06-27 | 2020-03-24 | 최하영 | Polyketone Composition Containing Plasticizer |
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KR20160119881A (en) * | 2014-11-28 | 2016-10-17 | 주식회사 씨케이바이오텍 | Coating composition for disinfectant tablet, and preparation method of coated disinfectant tablet using the same |
KR101777294B1 (en) * | 2016-02-04 | 2017-09-13 | 주식회사 효성 | Polyketone composition |
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