WO2012026653A1 - Biofilm biodégradable et photodégradable contenant de la balle de riz et du son de riz et son procédé de fabrication - Google Patents

Biofilm biodégradable et photodégradable contenant de la balle de riz et du son de riz et son procédé de fabrication Download PDF

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Publication number
WO2012026653A1
WO2012026653A1 PCT/KR2010/009350 KR2010009350W WO2012026653A1 WO 2012026653 A1 WO2012026653 A1 WO 2012026653A1 KR 2010009350 W KR2010009350 W KR 2010009350W WO 2012026653 A1 WO2012026653 A1 WO 2012026653A1
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WO
WIPO (PCT)
Prior art keywords
biodegradable
photodegradable
biofilm
rice
starch
Prior art date
Application number
PCT/KR2010/009350
Other languages
English (en)
Inventor
Sang-Ik Han
Hang-Won Kang
Ki-Chang Jang
Woo-Duck Seo
Je-Bong Lee
Gi-Hwan Lee
Dong-Soo Park
Jun-Hyun Cho
Soo-Kwon Park
Hung-Gu Hwang
Hak-Dong Lee
Dae-Woo Byun
Kyung-Soon Shin
Woo-Shin Byun
Jun-Hyo Kwon
Original Assignee
Republic Of Korea (Management : Rural Development Administration)
Evergreen Co., Ltd.
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Application filed by Republic Of Korea (Management : Rural Development Administration), Evergreen Co., Ltd. filed Critical Republic Of Korea (Management : Rural Development Administration)
Publication of WO2012026653A1 publication Critical patent/WO2012026653A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—Films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2003/00—Use of starch or derivatives as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0059—Degradable
    • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible
    • 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
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
    • 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
    • C08J2397/00—Characterised by the use of lignin-containing materials
    • C08J2397/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • 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
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00

Definitions

  • the present invention relates to a biodegradable, photodegradable biofilm comprising rice hull and rice bran, and a method of its preparation.
  • the biodegradable, photodegradable biofilm of the present invention enables to retain a suitable strength to protect crops during their growth. Further, it has biodegradable, photodegradable properties, thus capable of reducing the cost normally required for collecting the leftover films used for covering field during cultivation and the handling cost thereof.
  • Japanese Patent Application Publication No. Hei 8-311243 discloses a method for manufacturing a container by using a biodegradable foaming composition comprising a natural biodegradable polymer material such as starch and plant fiber, and aliphatic polyester and other additives.
  • Japanese Patent Application Publication No. Hei 7-97545 discloses a method for manufacturing a container manufactured by using a starch-containing biodegradable material by coating the surface of the container with a coating agent, wherein polylactic acid is dissolved in halogenated hydrocarbon.
  • Korean Patent No. 10-0574547 discloses a method for manufacturing a container manufactured by using a natural biodegradable polymer material such as pulp fiber powder, starch or the like, by coating the inner surface of the container with a coating agent comprising a natural biodegradable polymer material, acrylate copolymer, and a solvent.
  • Korean Patent No. 10-0830901 discloses a method for improving decomposition and preservation by gas phase depositioning a mixture on the biodegradable film. This method is focused on the improvement of film with regard to their decomposition and blocking of moisture.
  • field normally retain covering effect of soil due to the films covered thereon and thus it is necessary to take a preventive measure against the growth of weeds.
  • biodegradable property of the protective films is required. Therefore, there is an urgent need for the development of a method which can resolve the above problems.
  • Korean Patent No. 10-0368738 discloses a bio/photodegradable film to be used for covering field crops during the cultivation, which comprises starch, an oxidizing agent and photodegradation controller, and polyethylene and aliphatic polymer as matrix resin.
  • starch starch
  • oxidizing agent and photodegradation controller polyethylene and aliphatic polymer as matrix resin.
  • polyethylene which is used for processability of a film, it was hard to achieve the complete decomposition of the film.
  • the present invention has been made in an effort to solve the above problems by discovering that a biodegradable and photodegradable film, which enables to retain a suitable strength to undergo growth environment for field crops and be completely degraded after a certain period of time, can be manufactured by using rice hull and rice bran, which are very commonly seen in Korea.
  • an object of the present invention is to provide a method for manufacturing a biodegradable and photodegradable biofilm which has a suitable strength to protect field crops during the cultivation and is biodegradable as well as photo-degradable thereby reducing cost for collecting used biofilms and their treatment.
  • the present invention relates to a biodegradable, photodegradable biofilm comprising 20 ⁇ 50 wt% of rice hull, 5 ⁇ 15 wt% of rice bran, 1 ⁇ 15 wt% of starch, 0 ⁇ 5 wt% of titanium dioxide and 20 ⁇ 60 wt% of biodegradable polyester.
  • the present invention also relates to a method of manufacturing biodegradable, photodegradable biofilm comprising:
  • biodegradable, photodegradable biofilm of the present invention comprises rice hull, rice bran and starch which are readily available in the market. Further, biodegradable, photodegradable biofilm of the present invention, when used as a protective film for covering field crops during their cultivation, enables to maintain sufficient strength to protect them, and in six months later, when they are to be discarded after being used-up upon harvest of the crops, they start to proceed themselves with a slow biodegradation thus eliminating the worries for environmental contamination and the release of environmental hormones therefrom, while reducing the general cost which otherwise might have occurred to collect the used protective films and handling them thereafter.
  • FIG. 1 shows a picture of biodegradable, photodegradable biofilms comprising rice hull and rice bran manufactured according to the present invention.
  • FIG. 2 is a graph showing the result of tension test of the biodegradable, photodegradable biofilms manufactured according to Examples 1 ⁇ 3 of the present invention.
  • FIG. 3 is a graph showing the result of tension test of commercial protective films.
  • the biodegradable, photodegradable biofilm of the present invention comprising rice hull, rice bran and starch can retain suitable strength to protect field crops during their growth period to be covered therewith, and can slowly start to attend to its self biodegradation in soil around the time when the crop cultivation is completed, thus being freed from the worries of environmental contamination and cost and labor for handling the used biofilms.
  • the rice hull used for the manufacture of the biofilm gives strength to the biodegradable, photodegradable biofilm, and is used in the form of powder with a predeterminded particle size in order to promote easy decomposition of the biofilm during crop cultivation being protected with the film. More specifically, the rice hull is preferably to have a particle size capable of being sieved through 120 ⁇ 250 mesh sieve. In general, the smaller the particle size the greater the hardness of the biofilm. However, if the particle size of the rice hull powder is larger than the hole size of 120 mesh sieve, it will deteriorate processability and makes the surface of the biofilm rough.
  • rice hull powder is smaller than the hole size of 250 mesh sieve it will considerably increase the manufacturing cost due to the requirement of excess pulverization while the advantages in effect may not be obvious. Therefore, it is recommended that rice hull with at least two different kinds of particle size are used together to produce good quality biofilm in terms of hardness and softness.
  • Rice hull is used in the amount of 20 ⁇ 50 wt% relative to the total composition of the biofilm. If the amount of the rice hull is less than 20 wt% it will deteriorate biodegradability of the biofilm thus not being suitable to be used as a protective film for field crops. In contrast, if the amount is greater than 50 wt% it will worsen the processability thus it may cause any unexpected problems during the biofilm manufacturing process.
  • Rice bran is used to render biodegradability and softness to the biofilm.
  • the molecular structure of rice bran is more densed than that of rice hull, and thus it gives a better softness than the rice hull.
  • Rice bran is also used in the form of powder with a predeterminded particle size as is the case with rice hull, in the range of 120 ⁇ 200 mesh sieve hole size. In general, the lower the particle size the better the biodegradability of the biofilm. If the particle size of the rice hull powder is bigger than the hole size of 120 mesh sieve it may deteriorate processability of manuafacturing the biofilm.
  • Rice bran is used in the amount of 5 ⁇ 15 wt% relative to the total composition of the biofilm. If the amount of the rice bran is less than 5 wt% it will deteriorate biodegradability of the biofilm. In contrast, if the amount is greater than 15 wt% it will worsen the processability.
  • the starch used in the present invention serves as a binder, and it is preferred to use undenatured starch.
  • the undenatured starch is a negative ionic natural starch which does not require any physical or chemical treatment. Therefore, it can make the manufacturing process simple and reduce the manufacturing cost.
  • Examples of the undenatured starch include corn, glutinous corn, potato, tapioca, sweet potato, rice, glutinous rice, wheat, barley, and other seeds and cuts comprising less than 40 wt% of amylase.
  • the above undenatured starch is normally charged with 500 meq or higher negative charge and thus tends to aggregate together, which weakens the bonding energy among molecules thereby deteriorating overall strength and water-resistance.
  • rice hull and rice bran are used in powder form, as described previously, thus preventing aggregation of starch molecules thereby improving the overall mechanical properties of the film such as tensile strength, resistance or the like.
  • the amount of starch to be used in the present invention is 1 ⁇ 15 wt%. If the amount is below 5% it may decrease adhesion thus not being suitable to be used as a binder. In contrast, if it is used more than 15 wt% it will result in reducing the amount of rice hull and rice bran thus deteriorating the mechanical strength of the film.
  • Titanium dioxide(TiO 2 ) one of the major constituents of the present invention, is typically used as an emusifiable concentrate or involved in crystal formation in a crystalline oil and smoothen the glaze surface. In the present invention, it is used to render photodegradability on films.
  • the amount of titanium dioxide to be used in the present invention is 0 ⁇ 5 wt% relative to the total film composition. If it is used more than 5 wt% it may cause problems in terms of productivity, softness and strength.
  • Biodegradable polyester is used in the present invention to give elasticity and tensile strength to the film.
  • the biodegradable polyester to be used in the present invention is at least one selected from the group consisting of polylactide, polyglycolic acid, poly hydroxy butyric acid, polycaprolactone, polybutylene succinate adipate polymer, terpolymer of terephthalic acid and adipic acid and 1,4-butanediol, polyhydroxyalkanoate and polycaprolactone.
  • the biodegradable polyester is preferably used in the amount of 20 ⁇ 60 wt% relative to the total film composition. If the amount used is less than 20 wt% it will deteriorate biodegradability. In contrast, if the amount exceeds 60 wt% it may cause problems of softness, milling and increase in manufacturing cost.
  • calcium carbonate(CaCO 3 ) may be further added in order to expedite degradation upon necessity.
  • Calcium carbonate is preferably added in the range of 0.5 ⁇ 30 wt% relative to the total film composition. If its content is less than 0.5 wt% it may not be able to attain the intended effect of degradation. In contrast, if its content is greater than 30 wt% it may result in deterioration of the softness of the biofilm and too early degradation not suitable for crop cultivation of the biofilm. Therefore, it is preferred that calcium carbonate is used in the range of 30 wt% or less.
  • additives such as processing agent, releasing agent, preservative, inorganic filler, white agent, drying agent, heat stabilizer, and fluorescent agent may be added as necessary within the scope that the addition may not damage the object of the present invention.
  • the present invention also relates to a method of manufacturing a biodegradable, photodegradable biofilm. The method is described herein below.
  • rice hull and rice bran are pulverized using a conventional pulverizer to be suitable for the biodegradable, photodegradable biofilm to be prepared.
  • the pulverized rice hull and rice bran are added into a mixer along with starch and titanium dioxide, subjected to milling for 20 ⁇ 30 minutes to obtain a mixture for molding.
  • the mixture is then extruded for molding along with biodegradable polyester at 120 ⁇ 190°C to form a film with a thickness of 0.03 ⁇ 1.0 mm.
  • the biodegradable, photodegradable biofilm prepared according to a composition of the present invention has the advantages as a protective film. First, it can reduce the growth of weeds by covering the field with the film during their cultivation. Second, due to the biodegradable, photodegradable properties of the film, it starts to be degraded in soil after a certain length time thus eliminating the worries of release of environmental hormones as well as environmental contamination. Further, due to biodegradation nature, it can contribute to the reduction of costs associated in the collecting of used protective films and their treatment thereafter.
  • LDPE low density polyethylene
  • Example 1 Example 2 Example 3 rice hull (sieved through 200 ⁇ 250 mesh sieve) (wt%) -000 15 10 rice hull (sieved through 150 ⁇ 200 mesh sieve)(wt%) - 15 20 rice hull (sieved through 120 ⁇ 150 mesh sieve) (wt%) 30 - - rice bran (sieved through 120 ⁇ 150 mesh sieve) (wt%) 10 5 10 Starch (wt%) 5 10 10 titanium dioxide (wt%) 3 3 3 3 polylactide (wt%) 52 52 47
  • the intensity for secondary breakpoint of the films manufactured in Examples 1 ⁇ 3 were in the range of 15 ⁇ 20N, with the tensile force being maintained at 50% strain, thus showing excellent mechanical strength and tensile force.
  • the maximum tension force was 280 ⁇ 320%.
  • the agricultural film of Comparative Film under the pressure of 6 N or higher of force, increased its tensile force to 300%, even up to 600% maximally, thus showing that it is extendable under a small force and not readily breakable.
  • the biodegradable, photodegradable biofilm of the present invention has a suitable strength to be used as a protective film capable of replacing the conventional low density polyethylene film thereby resolving the issues of environmental contamination, release of environmental hormones, cost for collecting and treating the used films.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

La présente invention porte sur un biofilm biodégradable et photodégradable comprenant de la balle de riz et du son de riz et sur un procédé pour sa préparation. Plus particulièrement, la présente invention porte sur un biofilm biodégradable et photodégradable comprenant de la balle de riz et du son de riz, de l'amidon, du dioxyde de titane et un polyester biodégradable, qui permet de conserver une résistance appropriée pour protéger des cultures pendant leur croissance, ce qui permet ainsi de réduire le coût normalement requis pour la collecte de films utilisés pour recouvrir un champ pendant la culture qui restent et leur coût de manipulation.
PCT/KR2010/009350 2010-08-24 2010-12-27 Biofilm biodégradable et photodégradable contenant de la balle de riz et du son de riz et son procédé de fabrication WO2012026653A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020100082172A KR101062012B1 (ko) 2010-08-24 2010-08-24 왕겨 및 쌀겨를 함유한 생분해성, 광분해성 바이오 필름 및 이의 제조방법
KR10-2010-0082172 2010-08-24

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WO2012026653A1 true WO2012026653A1 (fr) 2012-03-01

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015085168A1 (fr) * 2013-12-05 2015-06-11 Earnest Stuart Biomasse broyée finement
CN112980090A (zh) * 2021-04-22 2021-06-18 王明霞 一种生态降解塑料地膜及其制备方法
CN113061277A (zh) * 2021-04-27 2021-07-02 杭州圣立新材料有限公司 一种生物可降解智能透水保湿膜及其制备方法和应用
CN113400690A (zh) * 2021-08-06 2021-09-17 甘肃华瑞农业股份有限公司 一种可降解农用地膜的制成装置及其加工方法
CN113897040A (zh) * 2019-07-09 2022-01-07 中山市金群瑞科技有限公司 一种高机械强度可降解食品包装材料的制备方法

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KR101414398B1 (ko) * 2012-07-18 2014-07-01 김응서 왕겨를 이용한 올레핀 표면 장식용 시트 제조 방법
KR101286485B1 (ko) 2013-02-25 2013-07-16 주식회사 웰데코 다기능 무늬시트의 제조방법
CN105504363A (zh) * 2016-01-07 2016-04-20 东莞市酬勤包装制品有限公司 淀粉/植物纤维复合生物降解聚酯吹膜级树脂及制备方法
KR200490545Y1 (ko) * 2017-08-01 2019-11-28 김병용 아이스크림 막대
KR102572348B1 (ko) 2022-11-25 2023-08-30 주식회사 아포트레 커피박을 이용한 친환경 플라스틱 펠릿 및 이의 제조방법

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JP2005131790A (ja) * 2002-03-05 2005-05-26 Mikazuki Napurasu Kigyo Kumiai 生分解性繊維質成形体の製造方法
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015085168A1 (fr) * 2013-12-05 2015-06-11 Earnest Stuart Biomasse broyée finement
CN113897040A (zh) * 2019-07-09 2022-01-07 中山市金群瑞科技有限公司 一种高机械强度可降解食品包装材料的制备方法
CN112980090A (zh) * 2021-04-22 2021-06-18 王明霞 一种生态降解塑料地膜及其制备方法
CN112980090B (zh) * 2021-04-22 2023-05-09 格域新材料科技(江苏)有限公司 一种生态降解塑料地膜及其制备方法
CN113061277A (zh) * 2021-04-27 2021-07-02 杭州圣立新材料有限公司 一种生物可降解智能透水保湿膜及其制备方法和应用
CN113400690A (zh) * 2021-08-06 2021-09-17 甘肃华瑞农业股份有限公司 一种可降解农用地膜的制成装置及其加工方法
CN113400690B (zh) * 2021-08-06 2022-09-13 甘肃华瑞农业股份有限公司 一种可降解农用地膜的制成装置及其加工方法

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