EP0323732B1 - Zusammengesetztes Material aus Cellulosefasern und Chitosan und Verfahren zu seiner Herstellung - Google Patents

Zusammengesetztes Material aus Cellulosefasern und Chitosan und Verfahren zu seiner Herstellung Download PDF

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Publication number
EP0323732B1
EP0323732B1 EP88312124A EP88312124A EP0323732B1 EP 0323732 B1 EP0323732 B1 EP 0323732B1 EP 88312124 A EP88312124 A EP 88312124A EP 88312124 A EP88312124 A EP 88312124A EP 0323732 B1 EP0323732 B1 EP 0323732B1
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EP
European Patent Office
Prior art keywords
chitosan
sheet
cellulose fibres
fatty acid
composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP88312124A
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English (en)
French (fr)
Other versions
EP0323732A2 (de
EP0323732A3 (de
Inventor
Jun Hosokawa
Masahi Nishiyama
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Institute of Advanced Industrial Science and Technology AIST
Original Assignee
Agency of Industrial Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agency of Industrial Science and Technology filed Critical Agency of Industrial Science and Technology
Priority to AT88312124T priority Critical patent/ATE78535T1/de
Publication of EP0323732A2 publication Critical patent/EP0323732A2/de
Publication of EP0323732A3 publication Critical patent/EP0323732A3/de
Application granted granted Critical
Publication of EP0323732B1 publication Critical patent/EP0323732B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/10—Packing paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/53—Polyethers; Polyesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added

Definitions

  • the present invention relates to a novel composite material based on cellulosic fibres and chitosan. More particularly, the present invention relates to a composite material basically formed of cellulose fibres and chitosan and which is biodegradable, for example, in the soil. The invention also relates to a method for the preparation of such a composite material.
  • the composite material of the invention is useful in a wide variety of applications, mainly but not limited to a sheet form used, for example, as a wrapping sheet for foods, a sheet material for agricultural use, temporary pots for growing young garden trees and seedlings, goods for hydroponics and the like.
  • the services expected for the sheet materials in the above-mentioned applications are mostly of a temporary nature, so that it is desirable that the sheet material can be spontaneously decomposed after use or at the end of the service season without leaving any decomposition products which may cause environmental pollution problems.
  • Such a photodegradable polymer is still not free from the problem of environmental pollution because the decomposition product thereof per se is a potential pollutant of the environment when the amount thereof is relatively large. Moreover, the photodegradable polymer cannot be decomposed when the waste thereof is out of reach of light, for example in the soil.
  • Cellulosic materials including lignocellulose, pectocellulose and bacteria cellulose, are natural products produced by plants and fungi which are readily available. Cellulosic materials are of course absolutely free from the problem of environmental pollution of the soil by waste thereof as is typically evidenced by the fact that cellulosic materials constitute an important constituent of composts. Accordingly, a cellulose-based sheet material is required having a sufficiently high mechanical strength not only in the dry but also in the wet state which is also biodegradable and thus causes no environmental or soil pollution.
  • the present invention provides a composite material which comprises: (a) cellulose fibres shaped in the form of a sheet; (b) chitosan in an amount in the range of from 1% to 99% by weight based on the amount of cellulose fibres; characterised in that the material also comprises (c) a fatty acid containing at least 12 carbon atoms in an amount in the range of from 0.05% to 1.0% by weight based on the amount of the cellulose fibres.
  • the amount of fatty acid as a treatment agent of the sheet material of the cellulose fibres impregnated with chitosan is in the range of from 0.05% to 1% by weight based on the weight of the cellulose fibres.
  • the cellulose fibre and chitosan-based composite sheet material of the invention can be prepared by first forming sheets of the cellulose fibres in a process similar to paper making and then soaking the sheet of cellulose fibres with an aqueous solution of a chitosan salt, followed by drying.
  • the composite sheet material can be prepared by forming sheets from an aqueous slurry of cellulose fibres containing chitosan in the form of a salt.
  • the composite sheet comprising the fatty acid can be prepared by soaking the composite sheet of cellulose fibres and chitosan with a solution of the fatty acid followed by drying.
  • the basic constituents of the inventive composite material are cellulose fibres and chitosan which impregnates a sheet of the cellulose fibres in a limited amount.
  • the cellulose fibres can be obtained from various sources including, mostly, wood and is available in the form of chemical pulp, mechanical pulp and the like.
  • Chitosan is a deacetylation product of chitin which is a nitrogen-containing polymeric compound occurring in large quantities in nature and is a principal constituent of the shells of insects, lobsters, crabs and the like as well as a constituent of certain microorganisms. Chitosan may have different degrees of deacetylation depending on the conditions of the deacetylation treatment of chitin. Chitosan, as such, is insoluble in water but can be solubilized when chitosan is converted into the form of a salt with, for example, acetate ions or chlorine ions.
  • the so-called chitinous substances include chitin and chitosans in general.
  • chitinous substances belong to a class of natural products, various species of microorganisms are known to decompose the chitinous substances. This fact is evidenced by the tests undertaken by the inventors who collected samples of soils from a number of cultivated lands all over the territory of Japan to test the biodegradability of chitosan therein to find microorganisms capable of decomposing chitosan having a relatively high degree of deacetylation.
  • Chitosan has previously been used industrially as a flocculating agent in the technology of waste water disposal. In recent years, investigations have been undertaken for the development of a chitinous substance as a bioadaptable material. Further, an attempt has been made to improve the surface strength of paper with chitosan (see, for example, GB-A-458,813 and "Proceedings of the 2nd International Conference of Chitin and Chitosan", 1982). Also US-A-4 102 738 describes a composite material made from cellulose fibres and chitosan, the chitosan being included to improve crush resistance. No prior art is known, however, of a composite material composed of cellulose fibres and chitosan, which has been surface-treated with a higher fatty acid, i.e. a fatty acid containing at least the carbon atoms.
  • a higher fatty acid i.e. a fatty acid containing at least the carbon atoms.
  • cellulose fibres in a sheet-like form and chitosan shaped in a sheet when alone, cannot retain their strength or form in a hydrous soil. Namely, a sheet of cellulose fibres rapidly disintegrates into discrete fibres in a wet condition and a sheet of chitosan is converted into a gel-like material. It is a discovery that, when cellulose fibres and chitosan form a composite, the composite material can retain its shape and mechanical strength even in a hydrous soil for a length of time and thereafter gradually be decomposed by the microorganisms living in the soil.
  • a composite material composed of cellulose fibres and chitosan alone is water-absorptive, but the composite can be provided with water repellency when it is treated with a higher fatty acid so that the stability of the composite material in the wet condition can be further increased without unduly affecting biodegradability.
  • the treatment of a composite sheet of cellulose fibres and chitosan with a higher fatty acid is performed by bringing the composite sheet into contact with a solution of the fatty acid in a concentration of from 0.1 to 0.5% by weight in a suitable organic solvent, followed by drying.
  • the amount of the higher fatty acid impregnating the composite sheet is in the rage of from 0.05% to 1% by weight or, preferably, in the range of from 0.1% to 0.6% by weight based on the amount of the cellulose fibres.
  • the content of the higher fatty acid has some influence on the biodegradability of the composite sheet in soil.
  • the organic solvent to dissolve the higher fatty acid is not limited, provided that it is inert to chitosan.
  • Methyl alcohol is an example of a suitable organic solvent though not limited thereto.
  • the higher fatty acid is selected from those insoluble in water and having at least 12 carbon atoms per molecule. Stearic and palmitic acids are preferred in respect of the water repellency imparted to the composite sheets treated therewith.
  • the composite sheet of cellulose fibres and chitosan can be prepared in several different ways as described below.
  • cellulose fibres are first treated with an aqueous solution of chitosan and the thus chitosan-treated cellulose fibres are shaped into a sheet-like form.
  • cellulose fibres are slurried in an aqueous medium containing chitosan and sheet-making is performed from this slurry.
  • the average molecular weight and degree of deacetylation of chitosan, as well as the compounding amount thereof with the cellulose fibres, should be selected appropriately in order to control adequately the mechanical properties of the composite material and the biodegradability thereof.
  • the chitosan should have a degree of deacetylation of at least 40% in order to have an adequate sheet-forming power.
  • the chitosan should preferably have an average molecular weight in the range from 2,000 to 500,000.
  • a type of chemical bond is formed between the surface of the cellulose fibres and chitosan so that the composite sheet having biodegradability is imparted with a high mechanical strength whilst still retaining its water-absorptivity.
  • the treatment with a higher fatty acid forms a water-repellent film on the surface of the composite sheet so as to decrease the water-absorptivity of the sheet.
  • a sheet of paper having a basis weight of 50 g/m2 and made from a mechanical pulp was soaked with an aqueous solution of chitosan having an average molecular weight of about 50,000 and a degree of deacetylation of about 99% acidified with acetic acid in different concentrations followed by drying at 105 °C.
  • the contents of chitosan in the thus prepared composite sheets were 1 to 50% by weight based on the cellulose fibres of the paper.
  • the composite sheets were each soaked with 0.1% by weight solution of stearic acid in methyl alcohol followed by drying. The amount of stearic acid picked up by the composite sheet was 0.12% by weight based on the cellulose fibres.
  • Table 1 show that the sheet of cellulose fibres can be imparted with an increased strength even in a wet condition by composite-making with chitosan in an amount of 1% by weight or larger.
  • the biodegradability of the composite sheet is controllable by the amount of chitosan compounded with the cellulose fibres.
  • the composite sheets of cellulose fibres and chitosan were treated with a methyl alcohol solution of stearic acid in varied concentrations of 0.1 to 1.0% by weight and the amount of water absorption of the thus treated sheets was determined to find that the degree of hydrophobicity imparted to the composite sheet remained unchanged when the concentration of the stearic acid solution was increased over 0.5% by weight despite the rapid increase of the amount of stearic acid picked up by the composite sheets. This fact led to a conclusion that the treatment with a higher fatty acid should be performed by using a solution of the fatty acid in a concentration not exceeding 0.5% by weight.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Biological Depolymerization Polymers (AREA)

Claims (10)

  1. Verbundwerkstoff, der umfaßt:
    (a) Cellulosefasern, die in Form eines Bogens geformt sind,
    (b) Chitosan in einer Menge im Bereich von 1 bis 99 Gew-%, bezogen auf die Menge an Cellulosefasern,
    dadurch gekennzeichnet, daß der Werkstoff daneben umfaßt
    (c) eine Fettsäure mit mindestens 12 Kohlenstoffatomen in einer Menge im Bereich von 0,05 bis 1,0 Gew-%, bezogen auf die Menge an Cellulosefasern.
  2. Verbundwerkstoff nach Anspruch 1, worin das Chitosan einen Deacetylisierungsgrad von mindestens 40 % hat.
  3. Verbundwerkstoff nach Anspruch 1 oder Anspruch 2, worin das Chitosan eine mittlere Molekülmasse im Bereich von 2000 bis 500 000 besitzt.
  4. Verbundwerkstoff nach einem der vorhergehenden Ansprüche, worin die Fettsäure eine gesättigte aliphatische Carbonsäure mit 12 bis 18 Kohlenstoffatomen ist.
  5. Verfahren zur Herstellung eines Verbundwerkstoffs nach Anspruch 1, das die folgenden Schritte umfaßt:
    (1) Herstellen eines Bogens von mit Chitosan imprägnierten Cellulosefasern,
    gekennzeichnet durch
    (2) Tränken des Bogens mit einer Lösung einer Fettsäure mit mindestens 12 Kohlenstoffatomen in einem organischen Lösungsmittel, und
    (3) Trocknen des so getränkten Bogens.
  6. Verfahren nach Anspruch 5, worin die Fettsäurelösung eine Konzentration im Bereich von 0,1 bis 0,5 Gew-% an Fettsäure besitzt.
  7. Verfahren nach Anspruch 5 oder Anspruch 6, worin das organische Lösungsmittel Methylalkohol ist.
  8. Verfahren nach einem der Ansprüche 5 bis 7, worin der Bogen aus mit Chitosan imprägnierten Cellulosefasern durch Tränken eines Bogens aus Cellulosefasern mit einer sauren Lösung von Chitosan und Trocknen des Bogens hergestellt wird.
  9. Verfahren nach einem der Ansprüche 5 bis 8, worin die Menge an Chitosan zur Imprägnierung des Bogens aus Cellulosefasern im Bereich von 1 bis 99 Gew-%, bezogen auf die Menge an Cellulosefasern, liegt.
  10. Verfahren nach einem der Ansprüche 5 bis 9, worin das Chitosan eine mittlere Molekülmasse im Bereich von 2000 bis 500 000 besitzt.
EP88312124A 1988-01-06 1988-12-21 Zusammengesetztes Material aus Cellulosefasern und Chitosan und Verfahren zu seiner Herstellung Expired EP0323732B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88312124T ATE78535T1 (de) 1988-01-06 1988-12-21 Zusammengesetztes material aus cellulosefasern und chitosan und verfahren zu seiner herstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP158888 1988-01-06
JP1588/88 1988-01-06

Publications (3)

Publication Number Publication Date
EP0323732A2 EP0323732A2 (de) 1989-07-12
EP0323732A3 EP0323732A3 (de) 1991-04-03
EP0323732B1 true EP0323732B1 (de) 1992-07-22

Family

ID=11505673

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88312124A Expired EP0323732B1 (de) 1988-01-06 1988-12-21 Zusammengesetztes Material aus Cellulosefasern und Chitosan und Verfahren zu seiner Herstellung

Country Status (5)

Country Link
EP (1) EP0323732B1 (de)
JP (1) JPH026689A (de)
AT (1) ATE78535T1 (de)
CA (1) CA1330916C (de)
DE (1) DE3873061T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591169A (zh) * 2019-09-30 2019-12-20 台州学院 一种用于食品包装的甘蔗纤维/壳聚糖复合膜及其制备方法

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0686548B2 (ja) * 1989-04-21 1994-11-02 工業技術院長 新規な吸水性複合素材及びその製造方法
US5306550A (en) * 1990-06-29 1994-04-26 Director-General Of Agency Of Industrial Science And Technology Biodegradable composition and shaped article obtained therefrom
DE4121085A1 (de) * 1990-06-29 1992-01-02 Agency Ind Science Techn Biologisch abbaubare zusammensetzung, daraus ausgeformter gegenstand und verfahren zur herstellung von biologisch abbaubarem material
JPH0628890B2 (ja) * 1990-08-22 1994-04-20 工業技術院長 天然多糖類から成るフィルム又はシートの製造方法
JPH04120142A (ja) * 1990-09-11 1992-04-21 Agency Of Ind Science & Technol 生物分解性複合素材及びその製造方法
EP0578107B1 (de) * 1992-07-09 1997-08-20 Dierig Holding Ag Vliesstoff aus natürlichen Fasern und Verwendungen dafür
KR20010079260A (ko) * 2001-06-28 2001-08-22 손태원 고배향 키토산 단섬유
WO2005118952A1 (en) * 2004-06-01 2005-12-15 Pulp And Paper Research Institute Of Canada Papermaking additive
PL2223941T3 (pl) * 2009-02-27 2019-04-30 Rohm & Haas Szybkoutwardzalna kompozycja węglowodanowa
CN103882764A (zh) * 2014-03-12 2014-06-25 金红叶纸业集团有限公司 湿用成膜组合物及其制造方法
CN112980209B (zh) * 2021-04-22 2021-12-24 湖南省杨林木业有限公司 一种抑菌防霉木胶板及其制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5116528A (ja) * 1974-07-31 1976-02-09 Nissan Motor Toransumitsushonkontoroorurinkeeji
JPS5335008A (en) * 1976-09-14 1978-04-01 Susumu Kashiwara Paper strength enhancing method
US4102738A (en) * 1977-01-17 1978-07-25 American Cyanamid Company Use of chitosan in corrugating medium
JPS60134097A (ja) * 1983-12-19 1985-07-17 株式会社協立有機工業研究所 抄紙方法
JP2571919B2 (ja) * 1986-10-07 1997-01-16 日本ピー・エム・シー株式会社 製紙方法
JPH01174699A (ja) * 1987-12-28 1989-07-11 Osaka Godo Kk ケーシング用材料の製造法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110591169A (zh) * 2019-09-30 2019-12-20 台州学院 一种用于食品包装的甘蔗纤维/壳聚糖复合膜及其制备方法
CN110591169B (zh) * 2019-09-30 2022-04-05 台州学院 一种用于食品包装的甘蔗纤维/壳聚糖复合膜及其制备方法

Also Published As

Publication number Publication date
EP0323732A2 (de) 1989-07-12
JPH026689A (ja) 1990-01-10
DE3873061T2 (de) 1992-12-03
DE3873061D1 (de) 1992-08-27
EP0323732A3 (de) 1991-04-03
CA1330916C (en) 1994-07-26
ATE78535T1 (de) 1992-08-15

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