JPH0565536B2 - - Google Patents
Info
- Publication number
- JPH0565536B2 JPH0565536B2 JP24826790A JP24826790A JPH0565536B2 JP H0565536 B2 JPH0565536 B2 JP H0565536B2 JP 24826790 A JP24826790 A JP 24826790A JP 24826790 A JP24826790 A JP 24826790A JP H0565536 B2 JPH0565536 B2 JP H0565536B2
- Authority
- JP
- Japan
- Prior art keywords
- foam
- chitosan
- starch
- raw material
- present
- 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 - Lifetime
Links
- 239000006260 foam Substances 0.000 claims description 27
- 229920001661 Chitosan Polymers 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 17
- 229920002472 Starch Polymers 0.000 claims description 16
- 239000008107 starch Substances 0.000 claims description 16
- 235000019698 starch Nutrition 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 244000005700 microbiome Species 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002689 soil Substances 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002101 Chitin Polymers 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006248 expandable polystyrene Polymers 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Description
産業上の利用分野
本発明は、生鮮食品用トレーなど使用後速やか
に分解される必要のある種々の発泡体の用途に利
用される。本発明は発泡ポリスチレン等に代わる
発泡体及びその製造方法に関するものであり、更
に詳しく言えば、本発明はキトサン及びデンプン
を複合させた天然多糖からなる発泡複合素材であ
り、人畜に完全に無害で、さらに使用後は土壌中
の微生物によつて完全に分解されうる発泡体及び
その製造方法に関するものである。
従来技術及びその問題点
従来、発泡成形体はポリスチレンが最も一般的
であるが、そのほかポリウレタンやポリエチレン
も用いられている。しかしこのような素材は安全
に燃焼させにくく、また微生物分解性を持たない
ため、使い捨ての用途に用いるには問題が多い。
そこで微生物分解性を持ち、安全に燃焼できる
素材から発泡体を製造する意義は大きいが、現在
その要求を満足させるような発泡体は開発されて
いない。例えば、デンプンのみから発泡体を製造
することが考えられるが、強度的に弱く、使用に
耐えない。またキトサンのみでは発泡しない。
本発明は新規複合発泡体とその製造方法に関す
るものであり、本発明によつて容易に原料を調製
でき、また強度ある発泡体を成形できる。原料に
は食品添加物として認められている天然多糖類の
みを用いるため、人畜に対してまつたく無害であ
り、廃棄後は無公害に分解する発泡ポリスチレン
等に代わる複合発泡体及びその製造方法を提供す
るものである。このような複合発泡体を調製した
例は未だないし、また応用した例もない。
発明が解決しようとする問題点
人間生活において身近に用いられている発泡成
形体のうち、使用期間は短期間で廃棄後速やかに
分解することを望まれる材料は多い。本発明は、
一定期間後に海洋を含む水中あるいは土壌中の微
生物によつて安全に分解され、燃焼もできる新規
な発泡成形体及びその製造の方法を提供するもの
である。
問題点を解決するための手段
本発明者らは、微生物分解性のある成形用素材
について鋭意研究を行つた結果、適切な微生物分
解性をもつデンプン・キトサン系の新規な複合素
材及びその製造方法を見いだし、特許を出願した
（出願番号２−62398、２−121488）。本発明はさ
らにこれを進展させ、発泡体及びその製造法を完
成させるに至つたものである。
本発明の主眼は、デンプン・キトサン系の混合
原料を水蒸気によつて発泡成形させることにあ
る。
デンプン粒を水と加熱するとゲル化する。この
ゲル化デンプンとキトサン塩水溶液とは相溶性が
よく、攪拌によつて均一に混合できる。水分含有
率約70％の高濃度でもニーダーやイクストルーダ
ー等を用いれば容易に均一混合化が可能である。
混合したのち、水蒸気発泡に適した水分量とする
ため、水分含有率60％以下、すなわち固形分濃度
として40％以上になるまで乾燥する。乾燥は送風
あるいは加熱によつて行うが、高温で長時間乾燥
すると着色する場合がある。
水分調整した混合原料は、金型中に密閉し、加
熱して加圧水蒸気を発生させ、急激に圧力を解放
することによつて発泡体を成形させる。このよう
な装置としてイクスパンダー等が知られており、
これらの装置を使用することができる。
具体的にはキトサンをゲル化デンプンに対し５
〜30％となるようキトサン塩水溶液の形で混合
し、十分攪拌する。キトサンとデンプン粒を混合
した後加熱しゲル化を行つても良いが、相溶させ
るために加熱後さらに混合を行うことが望まし
い。混合原料の水分含有率は均一相溶のしやすさ
と次の乾燥工程を考慮して30〜40％程度が好まし
いが、この範囲に限定されない。また、この混合
原料中に填料、グリセリンなどの可塑剤、補強材
等を添加することも妨げるものではない。
この混合物原料を水分含有率60％以下に乾燥
し、金型に充填し易いように粗砕してデンプン・
キトサン系の発泡体原料が完成する。金型に当該
原料を充填し、プレスすると共に密閉下で加熱を
行つて、蒸気を発生させ、発泡体を成形させる。
加熱による蒸気発生及び発泡化には、少なくとも
120℃以上は必要である。本発明で用いる材料の
うち、デンプンについては種々の植物由来のデン
プン粒があるが、いずれも本発明の原料として使
用できる。但しデンプン粒の種類によつてゲル化
温度が異なる。例えばコーンスターチは120℃、
ポテトスターチは80℃程度でゲル化する。
一方キチン質は甲殻類の殻や菌糸体等に含まれ
る含窒素高分子物質であり、このうち脱アセチル
化度が高く、希酸に溶けるものがキトサンと称さ
れているが、本発明にはキトサンを使用する。キ
トサンは由来や分子量によつて特に使用を限定さ
れない。本発明ではキトサンを溶解するため酢酸
や乳酸などの希薄水溶液に溶解して用いるが、装
置の腐食を防ぐ観点から酸の使用量はできるだけ
少ない方が好ましい。
発明の効果
本発明の方法で調製した発泡成形体は人畜に無
害であり、廃棄後は海洋・河川中あるいは土壌中
で容易に微生物分解され、且つ分解された後に有
害物質を生じない。またこの発泡成形体は十分な
強度を有する。このため発泡成形体の種々の用途
に利用でき、使用後無公害に廃棄処理できる。焼
却処理の場合でも、燃焼熱は約4000cal／ｇ（ポリ
エチレンの半分）と低く、有害ガスは生じない。
このことから本発明の素材を発泡成形体として用
いることにより、現在深刻化しているプラスチツ
ク廃棄物公害に対する問題の解決になる。
実施例
次に実施例により、本発明の複合素材及びその
製造方法を更に詳細に説明するが、これに限定さ
れるものではない。
実施例 １
コーンスターチ粒に対し20％の蟹殻由来のキト
サンを酢酸水溶液に溶解した後、コーンスターチ
粒と混合した。固形分濃度は30％であつた。十分
混合したのち、オートクレープで120℃、20分間
加熱してデンプン粒のゲル化を行つた。これをさ
らにニーダーで十分混練したのち、取り出して乾
燥し、破砕を行い、発泡体原料とした。発泡体原
料の水分含有量は10〜90％に調整した。
発泡体原料をイクスパンダー型成形機（幸和工
業製：ポン煎餅焼成機）を用いて発泡成形し、厚
さ５mm、直径100mmの円盤型成形サンプルを得た。
この発泡体原料の水分量と、成形したサンプルの
試験片（長さ20×幅15×厚さ５mm）の強度、発泡
成形の形態、及び、土中に埋めて２カ月後の分解
状態の関係を表１に示す。
INDUSTRIAL APPLICATIONS The present invention finds use in a variety of foam applications that require rapid decomposition after use, such as trays for fresh food. The present invention relates to a foam that can replace foamed polystyrene, etc., and a method for producing the same.More specifically, the present invention relates to a foamed composite material made of a natural polysaccharide combined with chitosan and starch, and is completely harmless to humans and animals. The present invention also relates to a foam that can be completely decomposed by microorganisms in soil after use, and a method for producing the same. Prior art and its problems Conventionally, polystyrene has been the most common foam molded product, but polyurethane and polyethylene have also been used. However, such materials are difficult to burn safely and are not biodegradable by microorganisms, so there are many problems in using them for disposable purposes. Therefore, it is of great significance to manufacture foams from materials that are biodegradable and can be safely combusted, but currently no foams have been developed that satisfy these requirements. For example, it is conceivable to produce foam only from starch, but it is weak in strength and cannot be used. Furthermore, chitosan alone does not foam. The present invention relates to a novel composite foam and a method for producing the same. According to the present invention, raw materials can be easily prepared and a strong foam can be molded. Because we use only natural polysaccharides that are approved as food additives as raw materials, we are developing a composite foam and its manufacturing method that can replace expanded polystyrene, etc., which is completely harmless to humans and animals, and which decomposes without causing any pollution after disposal. This is what we provide. There is no example of preparing such a composite foam, and there is no example of its application. Problems to be Solved by the Invention Among the foamed molded products commonly used in human life, many materials are used for a short period of time and are desired to be quickly decomposed after disposal. The present invention
The object of the present invention is to provide a novel foam molded article that can be safely decomposed by microorganisms in water or soil including the ocean after a certain period of time, and can also be combusted, and a method for producing the same. Means for Solving the Problems As a result of intensive research into molding materials that are biodegradable by microorganisms, the present inventors have developed a novel composite material based on starch and chitosan that is appropriately biodegradable and a method for producing the same. and filed a patent application (application numbers 2-62398, 2-121488). The present invention has further developed this and has completed a foam and a method for producing the same. The main objective of the present invention is to foam-mold a starch/chitosan-based mixed raw material using steam. When starch granules are heated with water, they gel. This gelled starch and chitosan salt aqueous solution have good compatibility and can be mixed uniformly by stirring. Even at high concentrations with a water content of about 70%, it is possible to easily mix them uniformly using a kneader, extruder, etc.
After mixing, the materials are dried until the moisture content is 60% or less, that is, the solid content concentration is 40% or more, in order to obtain a moisture content suitable for steam foaming. Drying is done by blowing air or heating, but if it is dried at high temperatures for a long time, it may become discolored. The mixed raw material whose moisture content has been adjusted is sealed in a mold, heated to generate pressurized steam, and the pressure is rapidly released to form a foam. Expanders and other devices are known as such devices.
These devices can be used. Specifically, chitosan was compared to gelatinized starch by 5%.
Mix in the form of an aqueous chitosan salt solution to a concentration of ~30% and stir thoroughly. Although chitosan and starch granules may be mixed and then heated to form a gel, it is desirable to further mix the mixture after heating in order to make them compatible. The moisture content of the mixed raw materials is preferably about 30 to 40% in consideration of the ease of homogeneous compatibility and the subsequent drying process, but is not limited to this range. Further, it is not prohibited to add fillers, plasticizers such as glycerin, reinforcing materials, etc. to this mixed raw material. This mixed raw material is dried to a moisture content of 60% or less, and crushed to make it easier to fill into molds.
Chitosan-based foam raw material is completed. The mold is filled with the raw material, pressed and heated under closed conditions to generate steam and mold the foam.
For steam generation and foaming due to heating, at least
A temperature of 120℃ or higher is required. Among the materials used in the present invention, there are starch granules derived from various plants, and any of them can be used as a raw material in the present invention. However, the gelation temperature differs depending on the type of starch granules. For example, corn starch is 120℃,
Potato starch gels at around 80℃. On the other hand, chitin is a nitrogen-containing polymeric substance contained in crustacean shells and mycelia, among which chitosan has a high degree of deacetylation and is soluble in dilute acids. Use chitosan. The use of chitosan is not particularly limited by its origin or molecular weight. In the present invention, chitosan is dissolved in a dilute aqueous solution such as acetic acid or lactic acid, but it is preferable that the amount of acid used be as small as possible from the viewpoint of preventing corrosion of the equipment. Effects of the Invention The foam molded article prepared by the method of the present invention is harmless to humans and animals, and after being disposed of, it is easily decomposed by microorganisms in the ocean, rivers, or soil, and does not produce harmful substances after being decomposed. Moreover, this foamed molded product has sufficient strength. Therefore, the foamed molded product can be used for various purposes and can be disposed of without pollution after use. Even when incinerated, the heat of combustion is as low as approximately 4,000 cal/g (half that of polyethylene), and no harmful gases are produced.
Therefore, by using the material of the present invention as a foamed molded article, the problem of plastic waste pollution, which is currently becoming more serious, can be solved. Examples Next, the composite material of the present invention and the method for producing the same will be explained in more detail with reference to Examples, but the invention is not limited thereto. Example 1 Chitosan derived from crab shells was dissolved in an acetic acid aqueous solution in an amount of 20% based on corn starch particles, and then mixed with corn starch particles. The solid content concentration was 30%. After thorough mixing, the starch granules were gelled by heating in an autoclave at 120°C for 20 minutes. This was further thoroughly kneaded in a kneader, then taken out, dried, and crushed to obtain a foam raw material. The moisture content of the foam raw material was adjusted to 10-90%. The foam raw material was foam-molded using an expander-type molding machine (manufactured by Kowa Kogyo: Pon cracker baking machine) to obtain a disk-shaped molded sample with a thickness of 5 mm and a diameter of 100 mm.
The relationship between the moisture content of this foam raw material, the strength of the molded sample test piece (length 20 x width 15 x thickness 5 mm), the form of foam molding, and the state of decomposition two months after burying it in the soil. are shown in Table 1.
【表】
実施例 ２
実施例１と同様の条件でサンプル成形を行つ
た。但し、デンプン粒だけのゲル化を先に行い、
これにキトサンの酢酸水溶液を混練した。キトサ
ン量はデンプンの０〜40％とし、発泡体原料の水
分量は30％に調整した。得られた発泡体サンプル
の性質を表２に示す。[Table] Example 2 Sample molding was performed under the same conditions as in Example 1. However, only the starch granules are gelled first,
This was kneaded with an aqueous solution of chitosan in acetic acid. The amount of chitosan was adjusted to 0 to 40% of the starch, and the moisture content of the foam raw material was adjusted to 30%. The properties of the foam samples obtained are shown in Table 2.
Claims (1)
泡させて成る微生物分解発泡体。 ２ 加熱ゲル化させたデンプン粒とキトサン塩水
溶液を混合相溶し、水分含有率を60％以下に調製
した原料を加圧加熱によつて可塑化し、水蒸気発
泡成形させる特許請求の範囲第１項記載の微生物
分解性発泡体の製造方法。 ３ デンプンに対するキトサンの量を５〜30％と
することを特徴とする特許請求の範囲第２項記載
の微生物分解性発泡体の製造方法。[Claims] 1. A microbially decomposed foam made by steam foaming raw materials consisting of starch and chitosan. 2. Starch granules that have been heated and gelled are mixed and dissolved with an aqueous chitosan salt solution, and the water content is adjusted to 60% or less, and the raw material is plasticized by heating under pressure and then steam-foamed. A method of manufacturing the microbially degradable foam described. 3. The method for producing a microbially degradable foam according to claim 2, characterized in that the amount of chitosan based on starch is 5 to 30%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24826790A JPH04126734A (en) | 1990-09-17 | 1990-09-17 | Starch/chitosan-based microbiologically degradable expanded material and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24826790A JPH04126734A (en) | 1990-09-17 | 1990-09-17 | Starch/chitosan-based microbiologically degradable expanded material and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04126734A JPH04126734A (en) | 1992-04-27 |
| JPH0565536B2 true JPH0565536B2 (en) | 1993-09-17 |
Family
ID=17175591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24826790A Granted JPH04126734A (en) | 1990-09-17 | 1990-09-17 | Starch/chitosan-based microbiologically degradable expanded material and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04126734A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1423435A1 (en) * | 2001-09-04 | 2004-06-02 | Heppe GmbH Biotechnologische Systeme und Materialien | Substances made of modified polysaccharides and method for the production thereof |
| JP2007238825A (en) * | 2006-03-10 | 2007-09-20 | Aicello Chemical Co Ltd | Chitosan-based shaped article treated with steam and its manufacturing method |
| CN105254931A (en) * | 2015-11-20 | 2016-01-20 | 保龄宝生物股份有限公司 | Development of novel product for improving properties of crosslinked-acetylated starch particles by introducing chitosan |
-
1990
- 1990-09-17 JP JP24826790A patent/JPH04126734A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04126734A (en) | 1992-04-27 |
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