KR100631145B1 - Biodegradable Foam Sheet and Method for Preducing the same - Google Patents
Biodegradable Foam Sheet and Method for Preducing the same Download PDFInfo
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- KR100631145B1 KR100631145B1 KR1020040073611A KR20040073611A KR100631145B1 KR 100631145 B1 KR100631145 B1 KR 100631145B1 KR 1020040073611 A KR1020040073611 A KR 1020040073611A KR 20040073611 A KR20040073611 A KR 20040073611A KR 100631145 B1 KR100631145 B1 KR 100631145B1
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- foam
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- foaming
- foamed
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- 239000006260 foam Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims description 5
- 238000005187 foaming Methods 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 239000000155 melt Substances 0.000 claims abstract description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 229920000229 biodegradable polyester Polymers 0.000 claims description 10
- 239000004622 biodegradable polyester Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 239000004604 Blowing Agent Substances 0.000 claims description 8
- 235000013399 edible fruits Nutrition 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000000454 talc Substances 0.000 claims description 6
- 229910052623 talc Inorganic materials 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 7
- 229920003232 aliphatic polyester Polymers 0.000 abstract description 5
- 238000001125 extrusion Methods 0.000 abstract description 5
- 239000004645 polyester resin Substances 0.000 abstract description 4
- -1 Vacuum Forming Substances 0.000 abstract description 3
- 229920006167 biodegradable resin Polymers 0.000 abstract description 3
- 238000007666 vacuum forming Methods 0.000 abstract description 3
- 238000006065 biodegradation reaction Methods 0.000 abstract 1
- 229920000728 polyester Polymers 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 238000003856 thermoforming Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
본 발명은 생분해성 수지로 제조한 저발포쉬트를 이용하여 성형성이 우수한 발포 물품을 제조하는 방법, 보다 상세하게는 성형성이 우수한 생분해성 지방족 폴리에스테르계 발포 쉬트로 제조한 발포 물품의 제조방법에 관한 것이다．The present invention relates to a method for producing a foamed article having excellent moldability using a low foamed sheet made of biodegradable resin, and more particularly to a method for producing a foamed article manufactured from biodegradable aliphatic polyester-based foamed foam sheet having excellent moldability. It is about.
상기 목적을 달성하기 위하여 본 발명의 제조방법은 지방족 폴리에스테르 수지에 발포제，발포조제 등을 첨가하여 용융흐름지수(멜트 인덱스)가 0.3∼30g/10min인 발포재료를 마련한 후 가열, 용융혼합하고 압출하여 발포체 밀도가 0.51 내지 0.9g/㎤(발포배율 2.45 내지 1.38배)인 쉬트형 저발포체로 제조한 후 소정 형상의 금형을 구비한 진공성형기에서 적당한 온도로 가열하에 진공성형하는 것을 특징으로 한다. 이와 같은 본 발명의 제조방법에 따르면, 성형성이 양호하고 성형품의 상태가 우수한 발포 물품이 수득될 수 있다. In order to achieve the above object, the production method of the present invention adds a foaming agent, a foaming aid, and the like to an aliphatic polyester resin to prepare a foaming material having a melt flow index (melt index) of 0.3 to 30 g / 10 min, followed by heating, melt mixing, and extrusion. It is characterized in that the foam density is 0.51 to 0.9g / cm 3 (foaming ratio 2.45 to 1.38 times) to produce a sheet-shaped low foamed body and then vacuum forming under heating to a suitable temperature in a vacuum molding machine having a mold of a predetermined shape. According to such a production method of the present invention, a foamed article having good moldability and excellent state of a molded article can be obtained.
생분해, 폴리에스테르, 발포쉬트, 발포체, 진공성형, 발포 물품Biodegradation, Polyester, Foam Sheet, Foam, Vacuum Forming, Foam Articles
Description
본 발명은 생분해성 폴리에스테르 수지계 저발포쉬트를 이용하여 성형성이 우수한 발포 물품을 제조하는 방법에 관한 것으로, 더욱 상세하게는 글리콜(glycol)과 디카르복실산(dicarboxylic acids)의 축합중합법에 의하여 얻어진 생분해성 지방족 폴리에스테르 수지에 발포제，발포조제 등을 첨가하여 용융흐름지수(멜트 인덱스)가 0.3∼30g/10min인 발포재료를 마련하여 가열, 용융혼합한 뒤 압출하여 발포체 밀도가 0.51 내지 0.9g/㎤(발포배율 2.45 내지 1.38배)인 쉬트형 저발포체로 제조한 후 가열하여 진공성형하는 것을 특징으로 한다.The present invention relates to a method for producing a foamable article having excellent moldability using a biodegradable polyester resin-based low foaming sheet, and more particularly to a condensation polymerization method of glycol and dicarboxylic acids Foamed material having a melt flow index (melt index) of 0.3 to 30 g / 10 min was added to a biodegradable aliphatic polyester resin, and a foaming agent having a melt flow index (melt index) of 0.3 to 30 g / 10 min. It is made of a sheet-type low foamed body having a g / cm 3 (foaming ratio of 2.45 to 1.38 times) and then heated to vacuum forming.
본 발명의 생분해성 수지 복합물은 밀도가 1.21∼1.25g/cm이고，용융흐름지수(멜트 인덱스)가 0.3∼30g/10min인 지방족 폴리에스테르이다．The biodegradable resin composite of the present invention is an aliphatic polyester having a density of 1.21 to 1.25 g / cm and a melt flow index (melt index) of 0.3 to 30 g / 10 min.
멜트 인덱스가 0.3g/10min 미만이면 압출시 마찰력 때문에 발포제가 분해되는 경우가 발생될 수 있으며，30g/10min 이상이면 특수한 냉각 장치를 사용하여야만 평면성이 양호한 발포쉬트를 얻을 수 있다． 본 발명에 의한 발포쉬트는 T자형 다이 또는 원형다이를 이용하여 압출기에서 발포쉬트 형태로 압출한다． 본 발명에 의하여 제조한 발포쉬트는 단열성， 경량， 생분해성으로 일회용 용기 및 생활용품 등의 넓은 분야에서 저렴하고 용이하게 이용되도록 생분해성 발포 물품을 제공하는데 그 목적이 있다．If the melt index is less than 0.3g / 10min, the foaming agent may be decomposed due to the frictional force during extrusion, and if it is more than 30g / 10min, a special cooling device may be used to obtain a good foam sheet. The foam sheet according to the present invention is extruded in the form of foam sheet from the extruder by using a T-shaped die or a round die. The foam sheet manufactured according to the present invention has a purpose to provide a biodegradable foam article for use inexpensively and easily in a wide range of fields such as disposable containers and household goods with insulation, light weight, and biodegradability.
종래의 발포쉬트 및 발포체는 생분해가 되지 않는 재료로써, 일회용 용기로써 사용후 폐기시에 썩지 않는 문제점과 소각시에 유해가스의 발생으로 인한 환경오염 등의 문제점을 지니고 있다.Conventional foam sheets and foams are materials that are not biodegradable and have problems such as non-rotation upon disposal after use as disposable containers and environmental pollution due to generation of harmful gases during incineration.
본 발명은 상기와 같은 종래의 문제점을 해소하기 위해 발명된 것으로, 단열성을 향상시키고, 용기 외부와의 열전도를 낮추어 용이하게 사용할 수 있을 뿐만 아니라 성형성과 성형 후 성형품의 상태도 우수한 생분해성 발포쉬트를 이용한 발포 물품을 제조하는 방법을 제공하는 데 그 목적이 있다.The present invention has been invented to solve the conventional problems as described above, and can be easily used by improving the thermal insulation and lowering the thermal conductivity with the outside of the container, as well as the biodegradable foam sheet excellent in moldability and state of the molded article after molding It is an object to provide a method for producing a used foamed article.
따라서, 상기 목적을 달성하기 위하여 본 발명은 생분해성 발포쉬트를 이용하여 성형성이 우수한 발포 물품을 제조하는 방법으로서, 먼저 용융흐름지수(멜트 인덱스)가 0.3∼30g/10min인 생분해성 폴리에스테르 수지 100중량부를 사용하고, 중탄산 나트륨(중조), 아조디카르본산아미드(ADCA), 아조비스이소부티로니트릴(AIBN) 중에서 선택된 1종 이상의 발포제 및 이산화탄소, 공기, 질소 또는 메탄, 에티렌, 초산아연, 탈크 및 Ca-Zn계 금속비누 중에서 선택된 1종 이상의 발포조제의 혼합물을 상기 생분해성 폴리에스테르 수지 100중량부에 대하여 0.3∼3중량부로 사용하여 혼합 및 펠릿화 한 다음，적당한 온도로 안정화시킨 발포용 압출기에서 가열, 용융, 혼합한 후 압출하여 밀도 0.51 내지 0.9g/㎤(발포배율 2.45 내지 1.38배), 두께 0.1~0.99㎜의 저발포쉬트를 제조하는 단계, 그 다음 금형이 장착된 진공성형기를 이용하여 가열하에 진공성형하여 소정 형상의 발포 물품을 수득하는 공정을 포함하는 것을 특징으로 하는 생분해성 발포 물품의 제조방법을 제공한다.Therefore, in order to achieve the above object, the present invention is a method for producing a foamable article having excellent moldability using a biodegradable foam sheet, firstly, a biodegradable polyester resin having a melt flow index (melt index) of 0.3 to 30 g / 10 min. 100 parts by weight of one or more blowing agents selected from sodium bicarbonate (azo), azodicarboxylic acid amide (ADCA), azobisisobutyronitrile (AIBN) and carbon dioxide, air, nitrogen or methane, ethylene, zinc acetate 0.3 to 3 parts by weight of a mixture of one or more foaming aids selected from talc and Ca-Zn-based metal soaps based on 100 parts by weight of the biodegradable polyester resin, followed by mixing and pelletizing, followed by foaming stabilized at an appropriate temperature. After heating, melting, and mixing in the melt extruder, extrusion is performed to prepare a low foam sheet having a density of 0.51 to 0.9 g / cm 3 (foaming ratio of 2.45 to 1.38 times) and a thickness of 0.1 to 0.99 mm. The method comprising, the following vacuum molding under heating using a vacuum molding machine, the mold is attached to provide a manufacturing method of the biodegradable foamed articles characterized in that it comprises a step for obtaining a foamed article of a desired shape.
구체적 일 양태로, 본 발명은 상기 제조방법에 있어서 발포용 압출기가 실린더 온도 170℃, 다이 온도 100℃로 온도를 충분히 안정시킨 원형 다이 또는 T자형 다이를 구비한 압출기이고, 상기 금형이 과일난좌용 금형 또는 산업포장용 완충재용 금형이며, 진공성형기에서의 가열 온도가 80∼150℃인 것을 특징으로 한다.In a specific aspect, the present invention is an extruder having a circular die or T-shaped die in which the foaming extruder is sufficiently stabilized at a cylinder temperature of 170 ° C., a die temperature of 100 ° C. It is a metal mold | die or a buffer material for industrial packaging, The heating temperature in a vacuum molding machine is 80-150 degreeC, It is characterized by the above-mentioned.
또한, 다른 관점으로서 본 발명은 상기 생분해성 발포 물품의 제조방법에 따라 제조한 과일난좌용 발포용기를 제공한다. In another aspect, the present invention provides a foam container for fruit heating seat prepared according to the method for producing a biodegradable foam article.
또 다른 관점으로서, 본 발명은 상기 생분해성 발포 물품의 제조방법에 따라 제조한 산업포장용 완충재를 제공한다.As another aspect, the present invention provides a cushioning material for industrial packaging prepared according to the method for producing a biodegradable foamed article.
이하, 본 발명을 보다 상세히 설명하면 다음과 같다. Hereinafter, the present invention will be described in more detail.
본 발명에서 사용되는 생분해성 폴리에스테르 수지는 글리콜(glycol)과 디카르복실산(dicarboxylic acids) 그리고, 반응촉매의 축합중합에 의하여 합성된 것으로서, 수지의 특성을 제어하기 위해 고무성분을 첨가할 수도 있으며, 공중합체를 사용하는 것도 가능하다.The biodegradable polyester resin used in the present invention is synthesized by condensation polymerization of glycol, dicarboxylic acids, and reaction catalysts, and rubber components may be added to control the properties of the resin. It is also possible to use a copolymer.
상기 생분해성 폴리에스테르의 분자량은 2만∼15만이다. 용융흐름지수(멜트 인덱스)는 0.3∼30g/10min이다． 멜트 인덱스가 0.3g/10min 미만이면 압출시 마찰력 때문에 발포제가 분해되는 경우가 발생될 수 있고， 흐름성이 나빠져서 진공 열성형에 적합한 발포체를 얻기 어렵다. 30g/10min이상이면 특수한 냉각 장치를 사용하여야만 평면성이 양호한 발포쉬트를 얻을 수 있으며， 수득되는 발포체가 불균일하고, 외관이 나빠지며, 기포의 분포도 불균일 해진다. The molecular weight of the biodegradable polyester is 20,000 to 150,000. Melt flow index (melt index) is 0.3-30g / 10min. If the melt index is less than 0.3g / 10min, the foaming agent may decompose due to the frictional force during extrusion, and the flowability deteriorates, making it difficult to obtain a foam suitable for vacuum thermoforming. If it is more than 30g / 10min, a special cooling device can be used to obtain a foam sheet with good flatness, resulting in uneven foam, poor appearance, and uneven bubble distribution.
발포제는 무기발포제, 휘발성 발포제, 분해형 발포제 모두를 사용할 수 있으며, 용도에 따라서 무기발포제나 휘발성 발포제를 사용하는 것이 바람직하다.The foaming agent can be used both an inorganic foaming agent, a volatile foaming agent and a decomposition type foaming agent, it is preferable to use an inorganic foaming agent or a volatile foaming agent depending on the application.
무기 발포제로는 중탄산 나트륨(중조)를 사용할 수 있으며, 유기 및 휘발성 발포제로는 아조디카르본산아미드(ADCA), 아조비스이소부티로니트릴(AIBN) 등의 지방족 탄화수소를 사용할 수 있다. Sodium bicarbonate (heavy bath) may be used as the inorganic blowing agent, and aliphatic hydrocarbons such as azodicarboxylic acid amide (ADCA) and azobisisobutyronitrile (AIBN) may be used as the organic and volatile blowing agents.
본 발명에서는 이와 같은 발포제와 함께 발포조제를 사용하는 바, 발포조제는 발포분해 촉진 및 발포의 핵이 되는 것으로서, 물리 발포제에 의한 고발포에는 이산화 탄소, 공기, 질소 또는 메탄, 에티렌 등의 가스상 핵제 등을 발포조제로 사용할 수 있으며, 유기 발포제에 의한 중·저 발포에는 초산아연, 탈크 또는 Ca-Zn계 금속비누 등의 고체 분말을 발포조제로서 사용할 수 있다. In the present invention, when the foaming aid is used together with such a foaming agent, the foaming aid is a nucleus for promoting foaming decomposition and foaming, and the high foaming by the physical foaming agent is a gas phase such as carbon dioxide, air, nitrogen or methane, ethylene, etc. Nucleating agents and the like can be used as foaming aids, and solid powders such as zinc acetate, talc or Ca-Zn-based metal soaps can be used as foaming aids for medium and low foaming with organic foaming agents.
그밖에 무기발포제 및 휘발성 발포제의 이형 발포제를 병행하여 사용할 수도 있다. In addition, the release foaming agent of an inorganic foaming agent and a volatile foaming agent can also be used together.
저발포의 경우 특히 바람직한 발포제는 중탄산 나트륨(중조)을 사용하는 것이며, 발포제와 발포조제의 혼합량은 생분해성 폴리에스테르 수지 100중량부에 대하여 0.3∼3중량부인 것이 바람직하다. 중∼고발포의 경우 특히 바람직하게는 부탄, 펜탄, 헥산 중에서 선택된 1종 이상의 탄화수소 발포제와 발포조제를 생분해성 폴리에스테르 수지 100중량부에 대하여 30∼100중량부로 사용하는 것이다.In the case of low foaming, a particularly preferred blowing agent is sodium bicarbonate (heavy bath), and the mixing amount of the blowing agent and the blowing aid is preferably 0.3 to 3 parts by weight based on 100 parts by weight of the biodegradable polyester resin. In the case of medium to high foaming, one or more hydrocarbon blowing agents selected from butane, pentane and hexane are preferably used in an amount of 30 to 100 parts by weight based on 100 parts by weight of the biodegradable polyester resin.
본 발명의 발포체는 밀도 0.51 내지 0.9g/㎤(발포배율 2.45 내지 1.38배)가 되도록 발포성형을 한다. 열성형용 저발포체의 경우 바람직하게는 0.51~0.8g/㎤이며, 더욱 바람직하게는 0.6~0.7g/㎤이다The foam of the present invention is foamed so as to have a density of 0.51 to 0.9 g / cm 3 (foam ratio 2.45 to 1.38 times). The low foaming material for thermoforming is preferably 0.51 to 0.8 g / cm 3, more preferably 0.6 to 0.7 g / cm 3.
또한, 폴리에스테르 수지를 원활하게 발포시키기 위해 필요에 따라 용융혼합중에 기포 조정제를 첨가할 수 있다. 기포 조정제로는 무기분말로 탈크, 탄산칼슘, 실리카 등을 사용할 수 있으며, 다가 카르복실산의 산성염, 탄산나트륨, 탄산수소 나트륨의 혼합물 등을 사용할 수 있다. 첨가량은 생분해성 폴리에스테르 수지 100중량부에 대하여 0.01∼1.0중량부인 것이 바람직하다. In addition, in order to make foaming of a polyester resin smoothly, a bubble adjuster can be added as needed during melt mixing. As the bubble regulator, talc, calcium carbonate, silica, or the like can be used as the inorganic powder, and an acid salt of polyhydric carboxylic acid, a mixture of sodium carbonate, sodium hydrogen carbonate and the like can be used. It is preferable that addition amount is 0.01-1.0 weight part with respect to 100 weight part of biodegradable polyester resin.
또한 필요에 따라서 난연제, 열안정제, 착색제, 고무성분, 산화방지제 등과 같은 통상적인 공지의 첨가제를 첨가할 수 있다.In addition, conventionally known additives such as flame retardants, heat stabilizers, colorants, rubber components, antioxidants and the like may be added as necessary.
이같은 사용비로 펠릿화한 것을, 압출기 내에서 가열, 용융, 혼합한 후 압출 하면 생분해성 발포쉬트를 얻을 수 있다. The pelletized at such a usage ratio is extruded after heating, melting and mixing in an extruder to obtain a biodegradable foam sheet.
이와 같이 얻은 발포쉬트를 소정 형상의 금형이 장착된 진공성형기를 이용하여 가열하에, 예컨대 80~150℃ 온도하에 성형함으로써 본 발명의 생분해성 발포쉬트로 제조된 성형성이 양호하고 성형품에 두께가 두껍거나 얇은 상태가 없는 생분해성 발포 물품를 얻을 수 있다. 이러한 발포 물품의 예로는 과일난좌용 발포용기 또는 산업포장용 완충재 등이 있다. The foam sheet thus obtained is molded under heating using a vacuum molding machine equipped with a mold having a predetermined shape, for example, at a temperature of 80 to 150 ° C., thereby making the moldability formed by the biodegradable foam sheet of the present invention good and having a thick thickness on the molded article. A biodegradable foamed article can be obtained that is free or thin. Examples of such foamed articles include fruit containers and foamed containers for industrial or industrial packaging.
이와 같이 제조된 발포 물품, 특히 과일난좌용 발포용기는 금형에 의한 성형성이 양호하고, 성형품에 두께나 얇은 부분도 없는 우수한 상태를 보이는 바(실시예 참조) 포장재 산업 분야에 널리 사용될 것으로 사료된다. The foamed articles manufactured in this way, in particular, foam containers for fruit stools, have good moldability by mold and have excellent thickness or thin parts (see examples). .
이하, 본 발명을 실시예를 통해 보다 상세히 설명하고자 하며, 본 실시예에 의해 본 발명이 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples, and the present invention is not limited by the Examples.
실시예 1 내지 2Examples 1-2
다음 표 1에 나타낸 사용비율로 각 성분을 혼합하여 펠릿화한 것을 압출기내에서 가열, 용융, 혼합한 후, 실린더 온도는 170℃, 다이 온도는 100℃로 충분히 안정화시킨 압출기에서 T자형다이(실시예1), 원형다이(실시예2)를 사용하여 두께1.5㎜∼5㎜, 폭 120㎝의 발포쉬트를 수득하였다. 수득한 발포쉬트를 원적외선 히터 가열로를 통하여 연화시키고, 연화된 발포쉬트를 과일난자용 금형이 장착된 진공성형기를 통해 80∼150℃ 온도하에 통과시켜 과일난좌용 발포용기를 성형하고, 각 성형 조건으로부터 수득된 발포용기 성형체에 대해 하기의 기준으로 성형성을 평가하여, 그 결과를 다음 표 1에 나타내었다.After mixing, pelletizing and mixing each component in the use ratios shown in Table 1 in the extruder, the T-shaped dies were carried out in an extruder in which the cylinder temperature was 170 ° C and the die temperature was sufficiently stabilized at 100 ° C. Example 1) Using a circular die (Example 2), a foam sheet having a thickness of 1.5 mm to 5 mm and a width of 120 cm was obtained. The obtained foam sheet was softened through a far-infrared heater heating furnace, and the softened foam sheet was passed through a vacuum molding machine equipped with a fruit egg mold at a temperature of 80 to 150 ° C. to form a foam container for fruit egg seat, and each molding condition The foamability obtained from the foamed container molded body was evaluated by the following criteria, the results are shown in Table 1 below.
(성형성의 평가)(Evaluation of gender)
○ : 금형에 의한 성형성이 양호하고, 성형품에 두께가 두껍거나 얇은 부분도 없는 우수한 상태 (Circle): Excellent moldability by a metal mold | die, and the outstanding state in which the molded article is not thick or thin part.
△ : 금형에 의한 성형성이 양호하고, 성형품의 상태가 양호한 상태 (Triangle | delta): The shape | formability by a metal mold | die is favorable, and the state of a molded article is favorable.
× : 금형에 의한 성형성이 불량하고, 성형품의 상태가 나쁘며, 셀파괴가 일어난 상태 X: The moldability was poor, the state of the molded article was bad, and the cell destruction occurred.
이상에서 상술한 바와 같이, 본 발명은 글리콜(glycol)과 디카르복실산(dicarboxylic acids), 반응촉매의 축합중합법에 의하여 얻어진 생분해성 수지를 사용하여 여기에 발포제， 발포조제와 산화방지제를 이축 압출기에서 혼합하고 발포용 압출기에서 압출하여 얻은 생분해성 발포쉬트를, 소정 형상의 금형이 장착된 진공성형기에서 가열하에 진공성형함으로써 성형성이 양호하고 성형품의 상태도 우수한 발포 물품을 수득하는 방법에 관한 것으로서，이와 같은 본 발명의 제조 방법에 의하면 발포배율이 충분히 높고 두께가 충분히 두꺼운 발포쉬트를 얻을 수 있으며， 열성형에 적합하고， 생분해성 지방족 폴리에스테르 수지 본래의 특성을 충분히 유지하면서도 독립 기포율이 좋고 발포쉬트 표면의 표면도 우수한 발포체를 제공할 수 있으며，일회용 용기, 포장재 및 생활용품 등 다방면에서 이용가능한 환경 친화적인 생분해성 폴리에스테르 발포쉬트로 성형된 발포 물품을 저렴하고 용이하게 수득할 수 있다. As described above, the present invention uses a biodegradable resin obtained by the condensation polymerization method of glycol, dicarboxylic acids, and reaction catalysts, to which a blowing agent, a foaming aid and an antioxidant The biodegradable foam sheet obtained by mixing in an extruder and extruded in a foam extruder is vacuum-molded under heating in a vacuum molding machine equipped with a mold of a predetermined shape to obtain a foamed article having good moldability and excellent state of the molded article. According to the manufacturing method of the present invention, a foam sheet having a sufficiently high foaming ratio and a sufficient thickness can be obtained, which is suitable for thermoforming, biodegradable aliphatic polyester resins, while maintaining the original characteristics, while maintaining sufficient independence. Good foam sheet surface Also it may provide a good foam can be inexpensive and easily obtain a foamed molded article as a disposable container, packaging and personal care, environmental friendly biodegradable polyester available in many areas the foamed sheet.
본 발명은 특정의 한 예를 상술한 바와 같이 설명하였지만, 본 발명은 그에 한정되는 것이 아니라 이하의 특허청구 범위에 의하여 마련되는 본 발명의 목적이나 분야를 벗어나지 않는 한도 내에서 본 발명이 다양하게 개조 및 변화될 수 있다는 것은 당 업계에서 통상의 지식을 가진 자는 용이하게 알 수 있다.
While the present invention has been described with reference to one specific example, the present invention is not limited thereto and various modifications of the present invention can be made without departing from the object or the scope of the present invention provided by the following claims. And it can be easily understood by those skilled in the art that it can be changed.
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| KR1020040073611A KR100631145B1 (en) | 2004-09-15 | 2004-09-15 | Biodegradable Foam Sheet and Method for Preducing the same |
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| KR1020040073611A KR100631145B1 (en) | 2004-09-15 | 2004-09-15 | Biodegradable Foam Sheet and Method for Preducing the same |
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| JP6265597B2 (en) * | 2009-09-25 | 2018-01-24 | アーケマ・インコーポレイテッド | Biodegradable foam with improved dimensional stability |
| KR101328753B1 (en) | 2010-12-30 | 2013-11-13 | (주)엘지하우시스 | Eco-friendly forming sheet |
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| JP2003253028A (en) | 2002-02-27 | 2003-09-10 | Toray Ind Inc | Crosslinked polyester resin foam, laminated sheet therefrom and molded article using the sheet |
| JP2004231766A (en) | 2003-01-30 | 2004-08-19 | Mitsui Chemicals Inc | Aliphatic polyester composition sheet and aliphatic polyester composition forming obtained therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003253028A (en) | 2002-02-27 | 2003-09-10 | Toray Ind Inc | Crosslinked polyester resin foam, laminated sheet therefrom and molded article using the sheet |
| JP2004231766A (en) | 2003-01-30 | 2004-08-19 | Mitsui Chemicals Inc | Aliphatic polyester composition sheet and aliphatic polyester composition forming obtained therefrom |
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