WO1996016116A1 - Composition de resine biodegradable - Google Patents

Composition de resine biodegradable Download PDF

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Publication number
WO1996016116A1
WO1996016116A1 PCT/JP1995/002342 JP9502342W WO9616116A1 WO 1996016116 A1 WO1996016116 A1 WO 1996016116A1 JP 9502342 W JP9502342 W JP 9502342W WO 9616116 A1 WO9616116 A1 WO 9616116A1
Authority
WO
WIPO (PCT)
Prior art keywords
starch
cellulose
esterified
acid
resin composition
Prior art date
Application number
PCT/JP1995/002342
Other languages
English (en)
Japanese (ja)
Inventor
Akihiko Kawakita
Ramani Narayan
Original Assignee
Evercorn, Inc.
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 Evercorn, Inc. filed Critical Evercorn, Inc.
Publication of WO1996016116A1 publication Critical patent/WO1996016116A1/fr

Links

Classifications

    • 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
    • C08L1/08—Cellulose derivatives
    • C08L1/10—Esters of organic acids, i.e. acylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C08L3/06—Esters
    • 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

Definitions

  • the present invention relates to a biodegradable resin composition having water resistance.
  • starch-based biodegradable resin compositions have excellent biodegradability (starch has a slower biodegradable condition and a faster decomposition rate than cellulose), but has high water resistance. It was not enough, and this was one of the reasons that the applicable products (uses) were limited.
  • an object of the present invention is to provide a biodegradable resin composition capable of significantly improving the water resistance of a resin molded article while maintaining good starch biodegradability. I do.
  • the biodegradable resin composition of the present invention comprises an esterified starch, It is a characteristic requirement that it contains three components, ie, lulose and an ester-type plasticizer, as essential components. Brief description of the drawing>
  • Raw starch such as corn, corn, wheat, scallop, cassava, tapio, rice, legumes, kudzu peravi, lotus starch, etc.
  • a physically modified starch obtained by converting them into alpha ( ⁇ ) enzymatically modified starch such as enzymatic degradation, chemically modified starch obtained by acid treatment, hypochlorous acid treatment, etherification, etc. can be used.
  • high-amylose starch with an amylose content of 50% or more is used for final resin molded products and films (hereinafter referred to simply as “resin molded products”). . ), It can be suitably used because of its excellent strength.
  • esterified acid of the esterified starch the following various organic acids and inorganic acids can be suitably used.
  • Saturated fatty acids such as acetic acid, propionic acid, drank acid, valeric acid, cabronic acid, cabrylic acid, cabric acid, lauric acid, myristic acid, palmitic acid and stearic acid, and acrylic acid, crotonic acid, Unsaturated fatty acids such as tonic acid, oleic acid, erucic acid and sorbic acid 2 Aliphatic saturated and unsaturated dicarboxylic acids such as malonic acid, succinic acid, alkenyl succinic acid, maleic acid and fumaric acid.
  • Inorganic acids such as phosphoric acid, urea phosphoric acid, etc.
  • lower saturated fatty acids such as acetic acid and brobionic acid can be suitably used because of their excellent strength when formed into a final resin molded product.
  • Esterified starch has a degree of substitution (DS) of 0.4 or more (total substitution DS3)
  • those having a DS of 1.0 to 2.8 are used. If D S is less than 0.4, it is difficult to impart water resistance to the resin molded product, and the compatibility with other resins when blended is poor.
  • the starch is dissolved by heating in dimethyl sulfoxide and reacted with an acid anhydride in the presence of an alkali catalyst to obtain a desired esterified starch.
  • esterified acid of the esterified cellulose those used for the above-mentioned esterified starch can be used.
  • lower saturated fatty acids such as acetic acid, propionic acid, butyric acid, and their mixed acids are superior in strength to the final resin molded product as in the case of esterified starch. It can be suitably used.
  • esterified cellulose those having a DSO of 4 or more, preferably DS 1.0 to 2.8 are used. If the DS is less than 0.4, it is difficult to impart water resistance to the resin molded product.
  • ester-type plasticizer one or more of the following examples can be selected and used.
  • phthalic acid esters or polyhydric alcohol esters are preferred because of their particularly good miscibility with both esterified starch and esterified cellulose.
  • This ester-type plasticizer is used for plasticizing the resin composition at a relatively low temperature during molding, thereby making it difficult for the resin composition to deteriorate due to heat and providing good moldability. is there.
  • the reason why the ester type is used as the plasticizer is to ensure compatibility with both the esterified starch and the esterified cellulose.
  • Phthalates such as dimethyl phthalate, getyl phthalate, dibutyl phthalate, di-octyl phthalate, and ethyl phthalylethyl glycolate;
  • Aliphatic base esters such as butyl oleate, glyceryl monooleate, butyl adipate, di-n-hexyl adipate,
  • Polyhydric alcohol esters such as fatty acid mono-di-triglyceride such as triacetin, diacetyl glycerin, triglycol-nitroglycerin, and glycerin monostearate;
  • Xylate esters such as methyl diacetyl ricinolate and triethyl acetyl citrate
  • Phosphoric acid esters such as tributyl triphosphate and triphenyl phosphinate
  • (a) / (b) 40 to 60/80/20 (weight ratio), and (c) 30 to 100 parts by weight of (a) + (b). To 60 parts by weight.
  • esterified cellulose If the amount of esterified cellulose is too small, it is difficult to ensure water resistance of the resin molded product. If the amount of esterified cellulose is excessive, it is difficult to impart the excellent biodegradability of starch to the resin molded product.
  • the resin composition must be heated to a relatively high temperature in order to plasticize the resin during the molding process, which may cause thermal deterioration of the resin composition. It is difficult to secure the strength of the steel.
  • esterified starch knead esterified cellulose and ester-type plasticizer to prepare a master batch, and then knead with esterified starch. Is preferred.
  • a known kneading machine such as an oven roller, a nieg, and an extruder can be used.
  • the composition of the present invention may further contain, if necessary, a filler, a heat stabilizer, an antioxidant, a coloring agent, an antistatic agent, an ultraviolet absorber and the like.
  • the resin composition of the present invention may be used as a molding material for injection molding, extrusion molding, blow molding, vacuum molding, force render molding, foam molding, powder molding, etc., similarly to general-purpose thermoplastic resins. Can be.
  • Applicable products include packaging materials (films, sheets, bottles, boxes, can carriers), agricultural materials (agricultural films, binding tapes), and consumer materials (diaper backsheets, shopping bags, garbage). bag ), And kitchen materials (cups, trays, plates, knives, forks, and sbooons). Examples>
  • the esterified cellulose and the plasticizer were mixed according to the formulation shown in Table 1 using a kneader “Laboblast Mill Type C” (manufactured by Toyo Seiki Co., Ltd.) at 175 ° C and 50 rpm. Kneaded for 15 minutes. The kneaded material was formed into a sheet by heating at 170 ° C. and then cut into strips. The flake pellet and the esterified starch were kneaded for 15 minutes at a prescribed mixing ratio at 165 ° C. ⁇ 50 rpm using the above-mentioned lab blast mill, and then heated at 150 ° C. with a hot press. The sheet was lmm thick. This sheet was cut into a 5 x 5 cm mouth to prepare a test piece.
  • test specimen was immersed in distilled water for 24 hours in a constant temperature and constant temperature room at 23 ° C and 50% RH, and the weight was calculated according to the following equation based on the weight before and after water absorption.
  • Soluble component ratio (%) (M 1 -M 3) 100 / M 1 (6) Measurement results:

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)
  • Biological Depolymerization Polymers (AREA)

Abstract

Une composition de résine biodégradable résistante à l'eau comprend un amidon estérifié (a) présentant un degré de substitution (DS) de 0,4 ou plus, une cellulose estérifiée (b) présentant un degré de substitution de 0,4 ou plus, et un plastifiant à esters (c) en tant qu'ingrédients essentiels. La composition peut fournir une résine moulée présentant une résistance à l'eau supérieure tout en conservant intacte la bonne biodégradabilité de l'amidon.
PCT/JP1995/002342 1994-11-22 1995-11-16 Composition de resine biodegradable WO1996016116A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP28830294A JPH08143710A (ja) 1994-11-22 1994-11-22 生分解性樹脂組成物
JP6/288302 1994-11-22

Publications (1)

Publication Number Publication Date
WO1996016116A1 true WO1996016116A1 (fr) 1996-05-30

Family

ID=17728416

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1995/002342 WO1996016116A1 (fr) 1994-11-22 1995-11-16 Composition de resine biodegradable

Country Status (2)

Country Link
JP (1) JPH08143710A (fr)
WO (1) WO1996016116A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19706642A1 (de) * 1997-02-20 1998-08-27 Apack Verpackungen Gmbh Verfahren zur Herstellung eines Formkörpers aus biologisch abbaubarem Material
US5912177A (en) * 1994-06-29 1999-06-15 Common Services Agency Stem cell immobilization
EP1113022A1 (fr) * 2000-01-02 2001-07-04 Japan Corn Starch Co., Ltd. Blocs biodégradables pour des modèles
WO2002024753A3 (fr) * 2000-09-25 2002-06-20 Univ Nebraska Compositions a base de polysaccharide expanse resistantes a l'eau et procedes de fabrication de ces compositions
US6833097B2 (en) 2000-01-03 2004-12-21 Japan Corn Starch Co. Ltd. Biodegradable block for models
CN109715721A (zh) * 2016-12-15 2019-05-03 富士施乐株式会社 树脂组合物和树脂成型体

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003211573B2 (en) 2002-02-21 2008-05-22 Nissei Company, Ltd. Biodegradable molding
JP4610187B2 (ja) * 2003-12-26 2011-01-12 ダイセル化学工業株式会社 セルロースエステル系樹脂組成物
JP2007002142A (ja) * 2005-06-24 2007-01-11 Tokyo Univ Of Agriculture & Technology 生分解性プラスチック、および該プラスチックから得られる生分解性プラスチック製品
JP4618649B2 (ja) * 2006-11-28 2011-01-26 リケンテクノス株式会社 アセチルセルロース樹脂組成物
CN108368306A (zh) * 2015-12-22 2018-08-03 罗地亚阿塞托有限公司 包含乙酸纤维素的新增塑组合物
JP6573006B2 (ja) * 2018-07-06 2019-09-11 富士ゼロックス株式会社 樹脂組成物及び樹脂成形体

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06207047A (ja) * 1991-11-14 1994-07-26 Ivan Tomka 高い耐水性を有する、生物学的に分解可能な成形材料ないしはポリマーブレンド及びその製造方法並びに成形材料ないしは押出成形体
JPH06329832A (ja) * 1993-04-28 1994-11-29 Hoechst Celanese Corp 繊維、フィルム、及びプラスチック材料を製造するのに用いられる、セルロースアセテートとスターチアセテートとから成るポリマーブレンド物及び該ブレンド物を調製する方法
JPH07102114A (ja) * 1993-10-04 1995-04-18 Teijin Ltd 生分解性組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06207047A (ja) * 1991-11-14 1994-07-26 Ivan Tomka 高い耐水性を有する、生物学的に分解可能な成形材料ないしはポリマーブレンド及びその製造方法並びに成形材料ないしは押出成形体
JPH06329832A (ja) * 1993-04-28 1994-11-29 Hoechst Celanese Corp 繊維、フィルム、及びプラスチック材料を製造するのに用いられる、セルロースアセテートとスターチアセテートとから成るポリマーブレンド物及び該ブレンド物を調製する方法
JPH07102114A (ja) * 1993-10-04 1995-04-18 Teijin Ltd 生分解性組成物

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5912177A (en) * 1994-06-29 1999-06-15 Common Services Agency Stem cell immobilization
DE19706642A1 (de) * 1997-02-20 1998-08-27 Apack Verpackungen Gmbh Verfahren zur Herstellung eines Formkörpers aus biologisch abbaubarem Material
EP1113022A1 (fr) * 2000-01-02 2001-07-04 Japan Corn Starch Co., Ltd. Blocs biodégradables pour des modèles
JP2001192401A (ja) * 2000-01-02 2001-07-17 Nippon Koonsutaac Kk 生分解性のモデル用ブロック材
JP4601111B2 (ja) * 2000-01-02 2010-12-22 日本コーンスターチ株式会社 生分解性のモデルの製作方法
US6833097B2 (en) 2000-01-03 2004-12-21 Japan Corn Starch Co. Ltd. Biodegradable block for models
WO2002024753A3 (fr) * 2000-09-25 2002-06-20 Univ Nebraska Compositions a base de polysaccharide expanse resistantes a l'eau et procedes de fabrication de ces compositions
CN109715721A (zh) * 2016-12-15 2019-05-03 富士施乐株式会社 树脂组合物和树脂成型体
US11174373B2 (en) 2016-12-15 2021-11-16 Fujifilm Business Innovation Corp. Resin composition and resin molded body

Also Published As

Publication number Publication date
JPH08143710A (ja) 1996-06-04

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