JPH0892419A - Biodegradable composite plastic composition - Google Patents
Biodegradable composite plastic compositionInfo
- Publication number
- JPH0892419A JPH0892419A JP23195494A JP23195494A JPH0892419A JP H0892419 A JPH0892419 A JP H0892419A JP 23195494 A JP23195494 A JP 23195494A JP 23195494 A JP23195494 A JP 23195494A JP H0892419 A JPH0892419 A JP H0892419A
- Authority
- JP
- Japan
- Prior art keywords
- starch
- oil
- fat
- biodegradable
- resin
- 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.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、生分解性樹脂に油脂加
工澱粉を複合化させることによって、澱粉配合による物
性低下を防ぎ、生産コストを削減でき、かつ生分解性樹
脂の生分解性を促進することができる、生分解性複合プ
ラスチック組成物に関する。BACKGROUND OF THE INVENTION The present invention prevents the deterioration of physical properties due to the incorporation of starch in the biodegradable resin by compounding the starch with oil and fat processing, can reduce the production cost, and can improve the biodegradability of the biodegradable resin. A biodegradable composite plastic composition that can be accelerated.
【0002】[0002]
【従来の技術】最近、地球環境の保全を図る観点から生
分解性樹脂の開発が活発になってきている。これらの樹
脂は、脂肪族ポリエステル、ポリカプロラクトン、ポリ
乳酸、ポリビニルアルコールなどの化学合成系、ポリヒ
ドロキシブチレート・バリレート共重合体などの微生物
系、アセチルセルロースなどの天然物利用系等に分けら
れている。さらに、これらの樹脂に澱粉を配合してコス
トダウンや生分解性の改善を行うことが提案され、一部
実用化されている。2. Description of the Related Art Recently, the development of biodegradable resins has become active from the viewpoint of protecting the global environment. These resins are divided into chemical synthetic systems such as aliphatic polyester, polycaprolactone, polylactic acid, and polyvinyl alcohol, microbial systems such as polyhydroxybutyrate / vallate copolymer, and natural product utilization systems such as acetylcellulose. There is. Further, it has been proposed that starch is blended with these resins to reduce costs and improve biodegradability, and some of them have been put into practical use.
【0003】例えば、生分解性を有さないポリエチレ
ン、ポリプロピレン等の樹脂と澱粉の複合体は、特公昭
52−21530号や特公昭52−42187号に開示
され、ポリエチレンと澱粉の複合体がエコスター(荻原
工業(株))として市販されている。しかし、この複合
体は、澱粉が分解されて製品の形状は崩れるが、樹脂が
分解されることはなく、そのまま残り、依然として環境
汚染の解決にはならないものであった。また、それ自身
生分解性を有するポリ乳酸と澱粉及び/又は加工澱粉の
複合体が特開平5−39381号公報に開示されてい
る。ポリ乳酸に澱粉及び/又は加工澱粉を複合化させる
ことで分解速度を向上し、かつ樹脂組成物の硬度を調節
して加工性を向上させたものである。ところが、このよ
うに樹脂に澱粉を配合することにより、生分解性等は改
善されるが、強度や伸長率などの機械的性質が大幅に低
下し、脆くなるという問題があった。そのため、実用的
には、澱粉の樹脂に対する添加量も制限されることにも
なっていた。For example, a composite of starch and non-biodegradable resin such as polyethylene or polypropylene and starch is disclosed in JP-B-52-21530 and JP-B-52-42187, and a composite of polyethylene and starch is eco-friendly. It is marketed as Star (Ogihara Industry Co., Ltd.). However, in this complex, the starch was decomposed and the shape of the product was destroyed, but the resin was not decomposed and remained as it was, and it was still not a solution to environmental pollution. Further, a composite of polylactic acid, which itself has biodegradability, and starch and / or modified starch is disclosed in JP-A-5-39381. By compounding polylactic acid with starch and / or modified starch, the decomposition rate is improved and the hardness of the resin composition is adjusted to improve the processability. However, although the biodegradability and the like are improved by blending the starch with the resin as described above, there is a problem in that mechanical properties such as strength and elongation rate are significantly reduced and the resin becomes brittle. Therefore, practically, the amount of starch added to the resin was also limited.
【0004】[0004]
【発明が解決しようとする課題】そこで本発明の目的
は、ポリ乳酸等の生分解性を有する樹脂組成物であっ
て、分解速度が向上し、かつ機械的性質も樹脂単独の場
合と変わらない、優れた生分解性樹脂組成物を提供する
ことにある。本発明者は、油脂加工した澱粉を生分解性
を有する樹脂に複合化させることにより、上記目的を達
成できることを見出した。尚、前記特開平5−3938
1号公報には、ポリ乳酸と加工澱粉との複合化について
も開示がある。しかし、加工澱粉として油脂加工澱粉は
記載も示唆もされていない。さらに、この公報の実施例
に記載された可溶化澱粉やカルボキシメチル化澱粉さら
にはアセチル化澱粉では、油脂加工澱粉を用いた場合の
ように、樹脂の機械的性質を維持することができなかっ
た。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a biodegradable resin composition such as polylactic acid which has an improved decomposition rate and mechanical properties which are the same as those of the resin alone. , To provide an excellent biodegradable resin composition. The present inventor has found that the above object can be achieved by compounding the starch processed with oil and fat with a resin having biodegradability. Incidentally, the above-mentioned JP-A-5-3938.
Japanese Unexamined Patent Publication No. 1 discloses a composite of polylactic acid and modified starch. However, neither oil nor fat-modified starch is described or suggested as the modified starch. Furthermore, the solubilized starch, carboxymethylated starch, and acetylated starch described in the examples of this publication were unable to maintain the mechanical properties of the resin as in the case of using the oil-processed starch. .
【0005】[0005]
【課題を解決するための手段】本発明は、油脂加工澱粉
と生分解性樹脂とからなる生分解性複合化プラスチック
組成物に関する。以下に、本発明について詳細に説明す
る。SUMMARY OF THE INVENTION The present invention relates to a biodegradable composite plastic composition comprising a fat-and-oil modified starch and a biodegradable resin. The present invention will be described in detail below.
【0006】本発明で用いられる油脂加工澱粉は従来か
ら公知のものである。例えば、油脂と澱粉を過乾燥して
加工することにより得られる油脂加工澱粉を挙げること
ができる〔特公昭45−32878号〕。この油脂加工
澱粉は、油脂、油脂類縁物質、脂肪酸又はその誘導体の
1種又は2種以上の混合物を澱粉に吸着させ、更にこれ
に熱を加えて熟成することにより得られるものである。
油脂は、植物油でも動物油でもよく、例えば大豆油、菜
種油、亜麻仁油、オリーブ油、豚脂、魚脂等を挙げるこ
とができる。油脂類縁物質は、例えば大豆レシチンのよ
うなリン脂質、モノグリセライド、ジグリセライド等で
ある。脂肪酸とは、油脂の構成成分である脂肪酸であれ
ば特に制限はない。The oil-and-fat processed starch used in the present invention is conventionally known. For example, a fat-and-oil-processed starch obtained by over-drying and processing the fat and oil and starch can be mentioned [JP-B-45-32878]. This oil-and-fat-processed starch is obtained by adsorbing one or a mixture of two or more kinds of oils and fats, oil-and-fat analogues, fatty acids or their derivatives on starch, and further aging it by heating it.
The fats and oils may be vegetable oils or animal oils, and examples thereof include soybean oil, rapeseed oil, linseed oil, olive oil, lard, and fish fat. Examples of the oil and fat analogs are phospholipids such as soybean lecithin, monoglycerides, diglycerides and the like. The fatty acid is not particularly limited as long as it is a fatty acid which is a constituent of fats and oils.
【0007】脂肪酸誘導体は、通常の合成品である脂肪
酸のエステル、アミド及び塩類などであり、脂肪酸のエ
ステルとは、例えばメチールアルコール、エチールアル
コール、アミールアルコール等と脂肪酸類とのエステル
である。脂肪酸のアミドとは、前記脂肪酸類のアミド及
び脂肪酸とアミノ酸類とのアミドである。脂肪酸の塩類
とは、脂肪酸のナトリウム、カリウムなどのアルカリ金
属、カルシウム、マグネシウムなどのアルカリ土類金属
及びアンモニウム等の塩類である。The fatty acid derivatives are esters, amides and salts of fatty acids which are generally synthetic products, and the fatty acid esters are, for example, esters of methyl alcohol, ethyl alcohol, amyl alcohol and the like with fatty acids. . The amides of fatty acids are amides of the above fatty acids and amides of fatty acids and amino acids. The salts of fatty acids are salts of fatty acids such as alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and ammonium.
【0008】さらに、油脂として肝油を用いた油脂加工
澱粉を例示することもできる〔特開昭53−11582
6号〕。肝油を用いた油脂加工澱粉は、油脂の1種であ
る肝油を澱粉粉体に添加し、これを十分に混合吸着させ
ることにより得られる。ここで「肝油」は、タラ肝油、
サメ肝油など魚類肝臓から得られる脂肪油の他、イカ
油、鯨肝油、鰯油等の魚油も包含し、1種又は2種以上
を混合して用いることができる。[0008] Furthermore, oil-and-fat processed starch using liver oil as the oil and fat can be exemplified [JP-A-53-11582].
No. 6]. The oil-and-fat-processed starch using liver oil can be obtained by adding liver oil, which is one of fats and oils, to starch powder, and mixing and adsorbing it sufficiently. Here, "liver oil" means cod liver oil,
In addition to fatty oils obtained from fish livers such as shark liver oils, fish oils such as squid oils, whale liver oils and sardine oils are also included, and one kind or a mixture of two or more kinds can be used.
【0009】また、ヨウ素価130以上の油脂を用いた
油脂加工澱粉を例示することもできる〔特開昭54−1
1247号〕。上記肝油以外に高いヨウ素価を示す油脂
を澱粉に混合吸着させた油脂加工澱粉も本発明において
使用することができる。ヨウ素価130以上の油脂とし
ては、動物油、植物油を問わず使用できる。そのような
油脂としては、サフラワー油(ヨウ素価122〜15
0)、エゴマ油(ヨウ素価162〜208)、アマニ油
(ヨウ素価187〜197)、アサ実油(ヨウ素価14
1〜175)、イワシ油(ヨウ素価163〜195)、
サバ油(ヨウ素価136〜178)などを例示すること
ができる。Further, an oil-and-fat-processed starch using an oil and fat having an iodine value of 130 or more can be exemplified [JP-A-54-1].
No. 1247]. In addition to the above-mentioned liver oil, oil-and-fat-modified starch obtained by mixing and adsorbing oil and fat having a high iodine value with starch can also be used in the present invention. As the oil and fat having an iodine value of 130 or more, animal oil or vegetable oil can be used. Such fats and oils include safflower oil (iodine value 122 to 15).
0), perilla oil (iodine value 162 to 208), linseed oil (iodine value 187 to 197), hemp seed oil (iodine value 14)
1-175), sardine oil (iodine number 163-195),
Mackerel oil (iodine value 136-178) etc. can be illustrated.
【0010】さらに、油脂として大豆粕を用いた油脂加
工澱粉を例示することもできる〔特開昭56−7857
2号〕。油脂として大豆粕を用いた油脂加工澱粉は、澱
粉に対して生大豆粉を0.1〜20重量%、好ましくは
0.3〜3重量%の割合で混合し、100℃以下、特に
60〜80℃の温度範囲で3〜6時間加熱することによ
り得ることができる。Further, an oil-and-fat modified starch using soybean meal as an oil and fat can be exemplified [JP-A-56-7857].
No. 2]. The oil-processed starch using soybean meal as the oil is a mixture of raw soybean flour and starch in an amount of 0.1 to 20% by weight, preferably 0.3 to 3% by weight, and 100 ° C or less, particularly 60 to It can be obtained by heating in the temperature range of 80 ° C. for 3 to 6 hours.
【0011】油脂加工澱粉の原料として用いられる原料
澱粉には特に制限はない。例えば、馬鈴薯澱粉、甘薯澱
粉、タピオカ澱粉等の地下澱粉及び、小麦澱粉、コーン
スターチ、サゴ澱粉、米澱粉等の地上澱粉を用いること
ができる。また、その状態も粉体澱粉あるいはスラリー
状、ケーキ状澱粉等いずれであってもよい。澱粉中の油
脂添加量は、澱粉と油脂類の種類により、適宜変化させ
ることができ、例えば、澱粉100重量部当たり、0.
1〜5.0重量部、好ましくは0.5〜2.0重量部の
範囲とすることが適当である。The raw material starch used as the raw material of the oil-and-fat processed starch is not particularly limited. For example, subterranean starch such as potato starch, sweet potato starch, tapioca starch, and above-ground starch such as wheat starch, corn starch, sago starch, rice starch and the like can be used. Further, the state thereof may be any of powdery starch, slurry, cake starch and the like. The amount of fats and oils added to starch can be appropriately changed depending on the types of starch and fats and oils. For example, it is 0.
It is suitable to set the range of 1 to 5.0 parts by weight, preferably 0.5 to 2.0 parts by weight.
【0012】前記油脂類は、澱粉と混合することで澱粉
に吸着させ、さらに必要により加熱熟成することによ
り、油脂加工澱粉とすることができる。例えば、澱粉ケ
ーキ及び粉体の場合には油脂類を水又は有機溶媒に溶解
もしくは分散せしめてスプレーし、澱粉スラリーの場合
は、スラリーに油剤を溶解又は分散させて攪拌すること
により油脂類を澱粉に吸着させることができる。油脂類
の種類によっては、加熱熟成することなしに油脂加工澱
粉として使用し得る。加熱熟成は、例えば、30〜18
0℃の温度で、1時間〜10日の範囲で行うことができ
る。また、加熱熟成と湿式で油脂類を吸着させた澱粉の
乾燥とを同時に行うこともできる。この乾燥は、バンド
ドライヤー、フラッシュドライヤー等の通常澱粉の乾燥
に使われる乾燥機を用い、澱粉の平衡水分にまで乾燥す
ることにより、油脂類を澱粉に均一に混合吸着させるこ
とができる。但し、樹脂と混合する場合には、油脂加工
澱粉の水分は1%以下にするのが適当である。The oils and fats can be processed into oil-and-fat processed starch by admixing the starch and oil with the starch and adsorbing the starch to the starch, and then aging the oil and fat if necessary. For example, in the case of starch cakes and powders, oils and fats are dissolved or dispersed in water or an organic solvent and sprayed, and in the case of starch slurry, the oils and fats are dissolved or dispersed in the slurry and stirred to dissolve the oils and fats into starch. Can be adsorbed on. Depending on the type of fats and oils, it can be used as a fat-and-oil modified starch without aging by heating. The heat aging is, for example, 30 to 18
It can be performed at a temperature of 0 ° C. for 1 hour to 10 days. Further, the heat aging and the drying of the starch having adsorbed the fats and oils by the wet method can be simultaneously performed. The drying can be carried out by using a drier such as a band dryer or a flash dryer which is usually used for drying starch so that the equilibrium water content of the starch is reached, so that fats and oils can be uniformly mixed and adsorbed to the starch. However, when mixed with a resin, the water content of the oil-and-fat-processed starch is appropriately 1% or less.
【0013】本発明の樹脂組成物において用いられる生
分解性樹脂には特に制限はない。それ自身生分解性を有
する樹脂であれば良く、成形性を考慮すると熱可塑性で
あることが適当である。例えば、脂肪族ポリエステル、
ポリカプロラクトン、ポリ乳酸、ポリビニルアルコール
などの化学合成系樹脂、ポリヒドロキシブチレート・バ
リレート共重合体などの微生物系樹脂、アセチルセルロ
ースなどの天然物利用系樹脂等が挙げられる。より具体
的には、生分解性を考慮すると、平均分子量3万〜4万
の範囲の脂肪族ポリエステル、平均分子量4万〜7万の
範囲のポリカプロラクトン、平均分子量8万〜12万の
範囲のポリ乳酸、平均分子量2万〜9万の範囲のポリビ
ニルアルコール、ヒドロキシバリレート分率0〜40モ
ル%のポリヒドロキシブチレート・バリレート共重合
体、酢化度43〜55%のアセチルセルロース、メトキ
シ含率27.5〜31.5%のメチルセルロース、エト
キシ含率47.5〜49.0%のエチルセルロースを用
いることが好ましい。The biodegradable resin used in the resin composition of the present invention is not particularly limited. Any resin that has biodegradability itself may be used, and thermoplastic resin is suitable in consideration of moldability. For example, aliphatic polyester,
Examples thereof include chemically synthesized resins such as polycaprolactone, polylactic acid, and polyvinyl alcohol, microbial resins such as polyhydroxybutyrate / valylate copolymer, and natural product utilization resins such as acetyl cellulose. More specifically, in consideration of biodegradability, an aliphatic polyester having an average molecular weight of 30,000 to 40,000, a polycaprolactone having an average molecular weight of 40,000 to 70,000, and an average molecular weight of 80,000 to 120,000 are used. Polylactic acid, polyvinyl alcohol having an average molecular weight of 20,000 to 90,000, polyhydroxybutyrate / valerate copolymer having a hydroxyvalerate fraction of 0 to 40 mol%, acetyl cellulose having an acetic acidity of 43 to 55%, and methoxy. It is preferable to use methyl cellulose having a rate of 27.5 to 31.5% and ethyl cellulose having an ethoxy content of 47.5 to 49.0%.
【0014】各成分の配合量は、例えば、油脂加工澱粉
を10〜70重量%、好ましくは30〜50重量%、生
分解性樹脂を90〜10重量%、好ましくは70〜50
重量%とすることが適当である。油脂加工澱粉の配合比
率が10重量%以上で澱粉による分解性の促進効果が顕
著になり、また70重量%以下であれば、複合体の成形
も通常の樹脂のみの場合と同様に行うことができる。油
脂加工澱粉と生分解性樹脂とは、例えば、60℃〜22
0℃の範囲の温度にて10〜60分間加熱混練すること
で複合体とすることができる。本発明の複合体は、油脂
加工澱粉を用いている。そのため、複合体を熱圧成形、
インフレ成形、吹き込み成形して得られるフィルムやシ
ートは、未加工の澱粉を用いた場合と比べて機械的性質
の低下が少ない。特に、引っ張り強度は樹脂単独と同程
度に保持され、弾性率は樹脂単独よりも上昇する。The blending amount of each component is, for example, 10 to 70% by weight of oil-and-fat processed starch, preferably 30 to 50% by weight, and 90 to 10% by weight of biodegradable resin, preferably 70 to 50%.
It is appropriate to set it as a weight%. When the blending ratio of the oil-and-fat modified starch is 10% by weight or more, the effect of promoting the degradability by the starch becomes remarkable, and when it is 70% by weight or less, the molding of the composite can be performed in the same manner as in the case of using only a normal resin. it can. The oil-and-fat processed starch and the biodegradable resin are, for example, 60 ° C to 22 ° C.
A composite can be obtained by heating and kneading at a temperature in the range of 0 ° C. for 10 to 60 minutes. The complex of the present invention uses oil-and-fat modified starch. Therefore, the composite is thermoformed,
The film or sheet obtained by inflation molding or blow molding has less deterioration in mechanical properties as compared with the case of using unprocessed starch. In particular, the tensile strength is maintained at the same level as that of the resin alone, and the elastic modulus is higher than that of the resin alone.
【0015】[0015]
【発明の効果】本発明によれば、澱粉を軽度かつ安価に
加工して得られる油脂加工澱粉を用いて、生分解性樹脂
との相溶性や界面接着性を向上させ機械的性質の大幅な
低下を防ぐとともに、澱粉の配合率の増加を可能にし、
成形性も良好な生分解性樹脂組成物を得ることができ
る。生分解性樹脂は、汎用の熱可塑性樹脂に比べて高価
であり、将来的にも汎用樹脂並みの価格になることは難
しい。本発明により、安価な澱粉を添加して複合化させ
ることで生分解性のプラスチックの価格を低減でき、ま
た生分解性の促進にもつながり、その応用範囲を汎用樹
脂並みに拡大させることが可能となる。INDUSTRIAL APPLICABILITY According to the present invention, an oil-processed starch obtained by lightly and inexpensively processing starch is used to improve the compatibility with biodegradable resin and the interfacial adhesion and to improve the mechanical properties. While preventing the decrease, it enables to increase the blending ratio of starch,
A biodegradable resin composition having good moldability can be obtained. Biodegradable resins are more expensive than general-purpose thermoplastic resins, and it will be difficult to achieve a price comparable to general-purpose resins in the future. According to the present invention, it is possible to reduce the price of biodegradable plastics by adding inexpensive starch to form a composite, and also to promote biodegradability, so that the range of application can be expanded to that of general-purpose resins. Becomes
【0016】[0016]
【実施例】以下本発明を実施例によりさらに説明する。 実施例1 コーンスターチ100重量部にサフラワー油2重量部を
添加し、ヘンシェルミキサー(三井三池化工機製)を用
いて均一に混合した後、120℃に加熱された箱型乾燥
機にて製品水分が0.3%以下になるまで乾燥し、サフ
ラワー油加工コーンスターチを得た。このサフラワー油
加工コーンスターチと市販脂肪族ポリエステル系生分解
性樹脂〔昭和高分子製ビオノーレ#1000、数平均分
子量3.5万〕を30:70の重量比率で混合した後、
180℃に加温したブラベンダープラストグラフ中で1
5分間混練して複合体を調製した。EXAMPLES The present invention will be further described below with reference to examples. Example 1 2 parts by weight of safflower oil was added to 100 parts by weight of corn starch, and the mixture was uniformly mixed using a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.), and the product moisture was changed by a box dryer heated to 120 ° C. It was dried to 0.3% or less to obtain safflower oil-processed corn starch. After mixing this safflower oil-processed corn starch and a commercially available aliphatic polyester-based biodegradable resin [Bionole # 1000, Showa High Polymer Co., Ltd., number average molecular weight 35,000] at a weight ratio of 30:70,
1 in Brabender plastograph heated to 180 ℃
A composite was prepared by kneading for 5 minutes.
【0017】得られた複合体を試験用卓上プレス(東洋
精機製作所)を用いて、180℃、100kgf/cm
2 熱圧下で成形し、厚さ約0.4mmのシートを得た。
シートより幅5mm、長さ80mmの短冊状試験片を切
り出し引っ張り試験機(オリエンテック)を用いて、機
械的性質を調べた。測定条件としては、100kgfの
ロードセルを用い、スパン長を40mmにし、クロスヘ
ッドスピード5mm/minで行った。この引っ張り試
験結果より各機械的性質を以下の計算式にて算出した。 ・引っ張り強度(kgf/cm2 )=破壊荷重(kg
f)/断面積(cm2 ) ・破壊伸長率(%)={(破壊伸び−スパン長)/スパ
ン長}×100 ・弾性率(kgf/cm2 )=比例源応力/歪み 結果を表1に示す。The composite thus obtained was tested at 180 ° C. and 100 kgf / cm using a test bench press (Toyo Seiki Seisakusho).
2 Formed under heat and pressure to obtain a sheet having a thickness of about 0.4 mm.
A strip-shaped test piece having a width of 5 mm and a length of 80 mm was cut out from the sheet, and the mechanical properties were examined using a tensile tester (Orientec). The measurement conditions were a load cell of 100 kgf, a span length of 40 mm, and a crosshead speed of 5 mm / min. Each mechanical property was calculated from the tensile test results by the following formulas.・ Tensile strength (kgf / cm 2 ) = breaking load (kg
f) / Cross-sectional area (cm 2 ) -Fracture elongation rate (%) = {(Fracture elongation-Span length) / Span length} × 100-Elastic modulus (kgf / cm 2 ) = Proportional source stress / strain Shown in.
【0018】比較例1 サフラワー油加工コーンスターチを水分0.3%以下の
未加工コーンスターチに代えた以外は、実施例1と同様
の調製法で複合体を試作し、同様の試験を行って機械的
性質を調べた。結果を表1に示す。 比較例2 サフラワー油加工コーンスターチを用いずに市販脂肪族
ポリエステル系生分解性樹脂のみでシートを得て、実施
例1と同様にして試験を行って機械的性質を調べた。結
果を表1に示す。Comparative Example 1 A composite was prepared by the same preparation method as in Example 1 except that the cornstarch processed with safflower oil was replaced with an unprocessed cornstarch having a water content of 0.3% or less, and the same test was conducted to perform the test. I investigated the physical properties. The results are shown in Table 1. Comparative Example 2 A sheet was obtained only with a commercially available aliphatic polyester-based biodegradable resin without using safflower oil-treated corn starch, and the same test as in Example 1 was conducted to examine the mechanical properties. The results are shown in Table 1.
【0019】[0019]
【表1】 [Table 1]
【0020】表1に示すように、油脂加工澱粉を用いた
実施例1のシートは、未加工澱粉を用いたシートに比べ
て、引っ張強度や破壊伸長率の低下が少なかった。As shown in Table 1, the sheet of Example 1 in which the oil-and-fat modified starch was used showed less decrease in tensile strength and breaking elongation rate than the sheet in which unprocessed starch was used.
【0021】実施例1及び比較例1で調製した複合体、
さらには脂肪族ポリエステル系生分解性樹脂の熱的性質
をフローテスター(島津製作所CFT500C)を用い
て昇温法および定温法により調べた。測定方法として
は、両測定法も長さ2mm、直径1mmのダイを用いた
が、昇温法においては、荷重を10kgfにし5℃/m
in.の昇温速度にて50℃〜200℃の範囲で測定し
た。定温法においては、荷重を5kgfにし190℃の
溶融温度で測定した。尚、昇温法より熱軟化温度および
熱流動化温度を、定温法より、溶融粘度や剪断速度、フ
ローレートを求めた。結果を表2に示すThe composites prepared in Example 1 and Comparative Example 1,
Furthermore, the thermal properties of the aliphatic polyester-based biodegradable resin were examined by a temperature raising method and a constant temperature method using a flow tester (CFT500C manufactured by Shimadzu Corporation). As a measuring method, a die having a length of 2 mm and a diameter of 1 mm was used in both measuring methods, but in the temperature raising method, the load was 5 kg / m at 10 kgf.
in. The heating rate was measured in the range of 50 ° C to 200 ° C. In the constant temperature method, the load was 5 kgf and the measurement was performed at a melting temperature of 190 ° C. The heat softening temperature and the heat fluidizing temperature were determined by the temperature raising method, and the melt viscosity, the shear rate, and the flow rate were determined by the constant temperature method. The results are shown in Table 2.
【0022】[0022]
【表2】 [Table 2]
【0023】表2に示すように、実施例1の複合体の熱
的性質は、樹脂のみからなる比較例2とあまり差がな
く、従来樹脂に用いられていると同様の成形条件にて成
形できることが認められた。As shown in Table 2, the thermal properties of the composite of Example 1 were not significantly different from those of Comparative Example 2 consisting of resin only, and the composite was molded under the same molding conditions as used for conventional resins. It was recognized that it was possible.
【0024】実施例1で調製した複合体の短冊状試験片
を活性汚泥試験、土中埋没試験に供した。比較試料とし
て低密度ポリエチレン(出光興産製)を用いた。結果を
表3に示す。油脂加工澱粉を含む本発明の複合体は、微
生物や酵素によりまず澱粉が優先的に分解され、その結
果多孔質となり脂肪族ポリエステル鎖の生分解を促進す
るものと思われる。The strip-shaped test piece of the composite prepared in Example 1 was subjected to an activated sludge test and a soil burial test. Low-density polyethylene (made by Idemitsu Kosan) was used as a comparative sample. The results are shown in Table 3. It is considered that the complex of the present invention containing the oil-and-fat-processed starch is preferentially decomposed by microorganisms and enzymes, and as a result, becomes porous and accelerates the biodegradation of the aliphatic polyester chain.
【0025】[0025]
【表3】 [Table 3]
【0026】実施例2 約40%の水分を含むタピオカ澱粉ウエットケーキの澱
粉固形分100重量部に大豆粕4重量部を加え、ニーダ
ー(森山製作所製DS1型)で均一に混合した後、90
℃に加温された箱型乾燥機を用いて30分間予備乾燥し
た。その後、120℃に加温された箱型乾燥機を用いて
製品水分が0.3%以下になるように乾燥し、大豆粕加
工タピオカ澱粉を得た。この大豆粕加工タピオカ澱粉と
市販ポリヒドロキシブチレート・バリレート共重合体
〔ゼネカ製バイオポールD410G、ヒドロキシバリレ
ート分率8モル%〕を50:50の重量比率で配合した
後、170℃で15分間混練して複合体を調製した。Example 2 4 parts by weight of soybean meal was added to 100 parts by weight of starch solids in a tapioca starch wet cake containing about 40% water, and uniformly mixed with a kneader (DS1 type manufactured by Moriyama Seisakusho Co., Ltd.).
Preliminary drying was performed for 30 minutes using a box dryer heated to ℃. Then, it was dried to a product moisture of 0.3% or less using a box dryer heated to 120 ° C. to obtain soybean meal-processed tapioca starch. After blending the soybean meal-processed tapioca starch and a commercially available polyhydroxybutyrate-valerate copolymer [Biopol D410G manufactured by Zeneca, hydroxyvalerate fraction 8 mol%] at a weight ratio of 50:50, the mixture is heated at 170 ° C. for 15 minutes. The mixture was kneaded to prepare a composite.
【0027】比較例3 大豆粕加工タピオカ澱粉に代えて水分0.3%以下のタ
ピオカ澱粉を用いた以外は実施例2と同様の調製法で、
複合体を得た。得られた複合体について、実施例2と同
様にして機械的特性について評価した。結果を表4に示
す。Comparative Example 3 The same preparation method as in Example 2 was used except that tapioca starch having a water content of 0.3% or less was used in place of the soybean meal-processed tapioca starch.
A complex was obtained. The resulting composite was evaluated for mechanical properties as in Example 2. The results are shown in Table 4.
【0028】比較例4 大豆粕加工タピオカ澱粉を用いず、市販ポリヒドロキシ
ブチレートとバリレートとの共重合体のみを用いた他は
実施例2と同様にして試料を得た。但し、シートの評価
方法は、加圧温度を180℃とした以外は実施例1と同
じ方法で行った。結果を表4に示す。Comparative Example 4 A sample was obtained in the same manner as in Example 2 except that the soybean meal-processed tapioca starch was not used and only the copolymer of commercially available polyhydroxybutyrate and valilate was used. However, the evaluation method of the sheet was the same as in Example 1 except that the pressing temperature was 180 ° C. The results are shown in Table 4.
【0029】結果を表4に示すように、本発明の複合体
組成物である実施例2は、未加工澱粉を用いた比較例3
に比べて優れた機械的特性を有することが分かる。さら
に、本発明の複合体組成物である実施例2は、樹脂のみ
の比較例4とほぼ同等の機械的特性を有することが分か
る。As shown in Table 4, the composite composition of the present invention, Example 2, is a comparative example 3 using unmodified starch.
It has excellent mechanical properties as compared with. Further, it can be seen that Example 2 which is the composite composition of the present invention has substantially the same mechanical properties as Comparative Example 4 in which only the resin is used.
【0030】[0030]
【表4】 [Table 4]
【0031】実施例3 コーンスターチ100重量部に大豆油2重量部を添加し
て、スーパーミキサー(川田製作所製)を用いて均一に
混合した後、箱型乾燥機を用いて製品水分が0.3%以
下になるように過乾燥し、大豆油加工コーンスターチを
得た。この大豆油加工コーンスターチと分子量4万のポ
リカプロラクトン〔ダイセル化学製、プラクセルH4〕
を40:60の比率で配合した後、100℃に加温した
スクリュー径20mm、L/D25の二軸押出機を用い
て均質な直径3mmの円柱ペレットを得た。シートの作
製は、加圧温度を100℃とした以外は、実施例1と同
様にして行った。得られたシートの機械的特性を実施例
1と同様にして求め、結果を表5に示す。得られたシー
トを地表下15cmの土中に埋没したところ、2ヵ月後
にはシートの形状が見られなくなった。Example 3 To 100 parts by weight of corn starch, 2 parts by weight of soybean oil was added and uniformly mixed using a super mixer (manufactured by Kawada Seisakusho Co., Ltd.). To obtain a soybean oil-processed cornstarch, the cornstarch was overdried so that the cornstarch content was not more than%. This soybean oil-processed cornstarch and polycaprolactone having a molecular weight of 40,000 [Placcel H4 manufactured by Daicel Chemical]
Was blended in a ratio of 40:60, and then a uniform cylindrical pellet having a diameter of 3 mm was obtained using a twin screw extruder having a screw diameter of 20 mm and L / D25 heated to 100 ° C. The sheet was manufactured in the same manner as in Example 1 except that the pressing temperature was 100 ° C. The mechanical properties of the obtained sheet were determined in the same manner as in Example 1, and the results are shown in Table 5. When the obtained sheet was buried in the soil 15 cm below the surface of the earth, the shape of the sheet disappeared after 2 months.
【0032】比較例5 大豆油加工コーンスターチに代えてコーンスターチを用
いた以外は実施例3と同様の調製法で、複合体を得た。
機械的特性の結果を表5に示す。 比較例6 大豆油加工コーンスターチを用いず、ポリカプロラクト
ン樹脂のみでシートを作製した以外は実施例3と同様の
方法でシートを得た。得られたシートの機械的特性の結
果を表5に示す。Comparative Example 5 A composite was obtained by the same preparation method as in Example 3 except that cornstarch was used instead of cornstarch processed with soybean oil.
The results of mechanical properties are shown in Table 5. Comparative Example 6 A sheet was obtained in the same manner as in Example 3 except that the soybean oil-processed corn starch was not used and the sheet was produced only with the polycaprolactone resin. The results of mechanical properties of the obtained sheet are shown in Table 5.
【0033】[0033]
【表5】 [Table 5]
【0034】実施例4 トウモロコシ澱粉100重量部にアマニ油を1重量部添
加して、プレーンミキサー(宝工機製)を用いて均一に
混合した後、100℃に加温された箱型乾燥機を用いて
製品水分が0.3%以下になるように乾燥し、アマニ油
加工トウモロコシ澱粉を得た。このアマニ油加工トウモ
ロコシ澱粉と平均分子量12万のポリ乳酸〔島津製作所
製〕を30:70の比率で配合した後、180℃に加温
したラポプラストミル(東洋精機製作所製)を用いて均
質な直径3mmの円柱ぺレットを得た。シートの作製
は、加圧温度を180℃とした以外は、実施例1と同様
にして行った。得られたシートの機械的特性を実施例1
と同様にして求め、結果を表6に示す。Example 4 1 part by weight of linseed oil was added to 100 parts by weight of corn starch, and the mixture was uniformly mixed using a plain mixer (manufactured by Takara Machine Co., Ltd.), and then a box type dryer heated to 100 ° C. was used. It was dried so that the product water content was 0.3% or less, and linseed oil-processed corn starch was obtained. This linseed oil-processed corn starch and polylactic acid having an average molecular weight of 120,000 (manufactured by Shimadzu Corporation) were mixed at a ratio of 30:70, and then homogenized using a Lapoplast mill (manufactured by Toyo Seiki Seisakusho) heated to 180 ° C. A cylindrical pellet having a diameter of 3 mm was obtained. The sheet was manufactured in the same manner as in Example 1 except that the pressing temperature was 180 ° C. The mechanical properties of the obtained sheet are shown in Example 1.
The results are shown in Table 6.
【0035】比較例7 マアニ油加工トウモロコシ澱粉に代えてトウモロコシ澱
粉を用いた以外は実施例4と同様の調製法で、複合体を
得た。機械的特性の結果を表6に示す。 比較例8 アマニ油加工トウモロコシ澱粉を用いず、ポリ乳酸樹脂
のみでシートを作製した以外は実施例4と同様の方法で
シートを得た。機械的特性の結果を表6に示す。Comparative Example 7 A composite was obtained by the same preparation method as in Example 4 except that corn starch was used instead of maani oil-processed corn starch. The results of mechanical properties are shown in Table 6. Comparative Example 8 A sheet was obtained in the same manner as in Example 4 except that a sheet made of only a polylactic acid resin was used without using linseed oil-processed corn starch. The results of mechanical properties are shown in Table 6.
【0036】[0036]
【表6】 [Table 6]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C08L 101/00 ZAB ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Office reference number FI technical display location C08L 101/00 ZAB
Claims (4)
生分解性複合化プラスチック組成物。1. A biodegradable composite plastic composition comprising a fat-and-oil modified starch and a biodegradable resin.
縁物質、脂肪酸及び脂肪酸誘導体からなる群から選ばれ
る1種又は2種以上の化合物を吸着させ、次いで熟成す
ることにより得られる請求項1記載の組成物。2. The processed fat-and-oil starch is obtained by adsorbing one or more compounds selected from the group consisting of fats and oils, analogs of fats and oils, fatty acids and fatty acid derivatives, and aging. The composition according to 1.
ポリカプロラクトン、ポリ乳酸、ポリビニルアルコー
ル、ポリヒドロキシブチレート・バリレート共重合体及
びアセチルセルロースからなる群から選ばれる樹脂であ
る請求項1又は2記載の組成物。3. The biodegradable resin is an aliphatic polyester,
The composition according to claim 1 or 2, which is a resin selected from the group consisting of polycaprolactone, polylactic acid, polyvinyl alcohol, polyhydroxybutyrate-valerate copolymer, and acetylcellulose.
%の範囲であり、生分解性樹脂の配合量が80〜30重
量%の範囲である請求項1〜3のいずれか1項に記載の
組成物。4. The blended amount of the oil-and-fat modified starch is in the range of 20 to 70% by weight, and the blended amount of the biodegradable resin is in the range of 80 to 30% by weight. The composition as described.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP6231954A JP2981129B2 (en) | 1994-09-28 | 1994-09-28 | Biodegradable composite plastic composition |
EP95114621A EP0704495A3 (en) | 1994-09-28 | 1995-09-18 | Biodegradable compositions |
US08/531,653 US5691403A (en) | 1994-09-28 | 1995-09-21 | Biodegradable compositions |
FI954581A FI954581A (en) | 1994-09-28 | 1995-09-27 | Biodegradable compositions |
KR1019950032185A KR960010741A (en) | 1994-09-28 | 1995-09-27 | Biodegradable Composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP6231954A JP2981129B2 (en) | 1994-09-28 | 1994-09-28 | Biodegradable composite plastic composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0892419A true JPH0892419A (en) | 1996-04-09 |
JP2981129B2 JP2981129B2 (en) | 1999-11-22 |
Family
ID=16931669
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JP6231954A Expired - Fee Related JP2981129B2 (en) | 1994-09-28 | 1994-09-28 | Biodegradable composite plastic composition |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005015504A (en) * | 2003-06-23 | 2005-01-20 | Teijin Ltd | Polylactic acid resin composition containing phospholipid, and molded article |
KR100458292B1 (en) * | 1997-03-21 | 2005-04-06 | 주식회사 엘지화학 | Biodegradable Resin Composition |
CN102161780A (en) * | 2011-06-01 | 2011-08-24 | 刘立文 | Calcium sulfate-corn starch-polylactic acid composite material and preparation method thereof |
-
1994
- 1994-09-28 JP JP6231954A patent/JP2981129B2/en not_active Expired - Fee Related
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100458292B1 (en) * | 1997-03-21 | 2005-04-06 | 주식회사 엘지화학 | Biodegradable Resin Composition |
JP2005015504A (en) * | 2003-06-23 | 2005-01-20 | Teijin Ltd | Polylactic acid resin composition containing phospholipid, and molded article |
CN102161780A (en) * | 2011-06-01 | 2011-08-24 | 刘立文 | Calcium sulfate-corn starch-polylactic acid composite material and preparation method thereof |
Also Published As
Publication number | Publication date |
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JP2981129B2 (en) | 1999-11-22 |
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