JP2978081B2 - Biodegradable composition - Google Patents
Biodegradable compositionInfo
- Publication number
- JP2978081B2 JP2978081B2 JP7095168A JP9516895A JP2978081B2 JP 2978081 B2 JP2978081 B2 JP 2978081B2 JP 7095168 A JP7095168 A JP 7095168A JP 9516895 A JP9516895 A JP 9516895A JP 2978081 B2 JP2978081 B2 JP 2978081B2
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- starch
- oil
- weight
- fat
- processed
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- Biological Depolymerization Polymers (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、生分解性樹脂と澱粉と
を含む生分解性の組成物に関する。さらに詳しくは、澱
粉として油脂加工澱粉糊化物を用い、澱粉配合による機
械的性質の低下を防ぎつつ、生分解性を向上させた生分
解性複合プラスチック組成物及びその製造方法に関す
る。The present invention relates to a biodegradable composition containing a biodegradable resin and starch. More specifically, the present invention relates to a biodegradable composite plastic composition which uses an oil-and-fat-processed gelatinized starch as a starch, prevents degradation of mechanical properties due to starch blending, and improves biodegradability, and a method for producing the same.
【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、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, biodegradable resins have been actively developed from the viewpoint of preserving the global environment. These resins are chemically synthesized systems such as polycaprolactone, polylactic acid, and polyvinyl alcohol;
They are classified into microbial systems such as valerate copolymers and natural product utilizing systems such as acetylcellulose. Furthermore, it has been proposed to mix starch with these resins to reduce costs and improve biodegradability, and some of them have been put to practical use.
【０００３】樹脂と澱粉とからなる複合体は、例えば、
特開平２−１４２２８号、特開平３−３１３３３号、特
開平４−２４８８５１号、特開平５−３３１３１５号、
特開平６−２０７０４７号等に開示されている。これら
に開示されている複合体では、澱粉を添加することによ
り生分解性は改善されるが、強度や伸長率等の機械的性
質が大幅に低下して脆くなるという問題がある。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
ることになる。[0003] A composite comprising a resin and starch is, for example,
JP-A-2-14228, JP-A-3-31333, JP-A-4-248885, JP-A-5-331315,
It is disclosed in JP-A-6-207047. In the composites disclosed therein, the biodegradability is improved by adding starch, but there is a problem that the mechanical properties such as strength and elongation are significantly reduced and the composite becomes brittle. Therefore, in practice, the amount of starch added to the resin is also limited.
【０００４】また、澱粉として種々の加工澱粉を用いた
生分解性樹脂組成物も知られている。例えば、特開平３
−５６５４３号には澱粉グラフトコポリマー、特開平３
−７０７５２号にはアニオン性修飾澱粉、特開平３−７
４４４５号にはカチオン性修飾澱粉、特開平３−７４４
４６号にはヒドロキシアルキル基及び／又はアルキルエ
ーテル基を含み、及び／又はエステル基を含む様に化学
的に改質されている澱粉を澱粉成分としてそれぞれ用い
た、生分解性組成物が開示されている。しかるに、これ
ら加工澱粉を用いた生分解性組成物においても機械的性
質の低下を充分に抑制することはできなかった。[0004] Biodegradable resin compositions using various modified starches as starches are also known. For example, Japanese Unexamined Patent Publication
No. 5,565,543 discloses a starch graft copolymer.
-70752 discloses an anionic modified starch, disclosed in JP-A-3-7.
No. 4445 discloses cationically modified starch, JP-A-3-744.
No. 46 discloses a biodegradable composition using, as a starch component, a starch containing a hydroxyalkyl group and / or an alkyl ether group and / or chemically modified to contain an ester group. ing. However, even in the biodegradable composition using these modified starches, it was not possible to sufficiently suppress the decrease in mechanical properties.
【０００５】それに対して本発明者らは、澱粉又は加工
澱粉を添加することによる機械的特性の低下を防止し、
かつ生分解性を高めた組成物として、油脂加工澱粉と生
分解性樹脂とを含む生分解性の複合体組成物を開発し、
先に特許出願した〔特願平６−２３１９５４号）。油脂
加工澱粉を含む上記生分解性複合体組成物は、従来の組
成物に比べて機械的特性及び生分解性ともに優れたもの
であった。しかし、実用的には、さらに機械的特性及び
生分解性が向上した生分解性組成物の提供が望まれてい
る。特に、生分解性の向上とコストの低減の観点から、
澱粉の配合比率が高い生分解性組成物の提供が望まれて
いる。On the other hand, the present inventors have prevented the deterioration of the mechanical properties by adding starch or modified starch,
And as a composition with enhanced biodegradability, developed a biodegradable composite composition containing a fat and oil modified starch and a biodegradable resin,
A patent application was filed earlier (Japanese Patent Application No. 6-231954). The biodegradable composite composition containing the oil-and-fat-processed starch was excellent in both mechanical properties and biodegradability as compared with the conventional composition. However, practically, it is desired to provide a biodegradable composition having further improved mechanical properties and biodegradability. In particular, from the viewpoint of improving biodegradability and reducing costs,
It is desired to provide a biodegradable composition having a high starch mixing ratio.
【０００６】[0006]
【発明が解決しようとする課題】そこで本発明の目的
は、樹脂と澱粉とからなる生分解性が改善された複合体
組成物であって、機械的性質が樹脂単独の場合とほぼ同
等であり、かつ生分解性に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、油脂加工した澱粉の
糊化物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。SUMMARY OF THE INVENTION An object of the present invention is to provide a composite composition comprising a resin and starch having improved biodegradability, the mechanical properties of which are substantially the same as those of a resin alone. Another object of the present invention is to provide a biodegradable resin composition having excellent biodegradability. The present inventor has found that the above object can be achieved by complexing a gelatinized product of a starch processed with oil and fat with a resin having biodegradability.
【０００７】[0007]
【課題を解決するための手段】本発明は、油脂加工澱粉
糊化物と生分解性樹脂とを含むことを特徴とする生分解
性組成物に関する。さらに本発明は、油脂加工澱粉と生
分解性樹脂とを水又は水及び可塑剤の存在下で加熱混練
することを特徴とする上記本発明の組成物の製造方法に
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 composition comprising a gelatinized product of a processed fat and oil and a biodegradable resin. Furthermore, the present invention relates to the method for producing the composition of the present invention, wherein the oil-modified starch and the biodegradable resin are heated and kneaded in the presence of water or water and a plasticizer. Hereinafter, the present invention will be described in detail.
【０００８】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。[0008] The processed fats and oils used in the present invention are conventionally known. For example, an oil-and-fat-processed starch obtained by processing an oil and a fat by overdrying can be mentioned (Japanese Patent Publication No. 45-32878). The processed fat or oil is obtained by adsorbing one or more of a mixture of fats and oils, fat-related substances, fatty acids and derivatives thereof on the starch, and applying heat to ripen the starch.
The oils and fats may be vegetable oils or animal oils, such as soybean oil, rapeseed oil, linseed oil, olive oil, lard, fish fat and the like. Fat-related substances are, for example, 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 that is a component of fats and oils.
【０００９】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。Fatty acid derivatives are esters, amides and salts of fatty acids which are ordinary synthetic products, and the esters of fatty acids are, for example, esters of fatty acids with methyl alcohol, ethyl alcohol, amyl alcohol and the like. . The amide of a fatty acid is an amide of the above-mentioned fatty acids and an amide of a fatty acid and an amino acid. The fatty acid salts are salts of fatty acids such as alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, and salts such as ammonium.
【００１０】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。Further, an oil-and-fat-modified starch using liver oil as the oil and fat can be exemplified [Japanese Patent Application Laid-Open No. 53-11582.
No. 6]. An oil-and-fat processed starch using liver oil is obtained by adding liver oil, which is a kind of oil and fat, to starch powder, and mixing and adsorbing the mixture. Here, "liver oil" is cod liver oil,
Fish oils such as squid oil, whale liver oil, sardine oil and the like are included in addition to fatty oils obtained from fish liver such as shark liver oil, and one kind or a mixture of two or more kinds can be used.
【００１１】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 or 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, an oil-and-fat processed starch obtained by mixing and adsorbing an oil or fat having a high iodine value with starch can also be used in the present invention. As an oil having an iodine value of 130 or more, any of animal oil and vegetable oil can be used. Such oils and fats include safflower oil (iodine value 122 to 15).
0), perilla oil (iodine value: 162 to 208), linseed oil (iodine value: 187 to 197), hemp oil (iodine value: 14)
1-175), sardine oil (iodine value 163-195),
Mackerel oil (iodine value 136 to 178) can be exemplified.
【００１２】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-processed starch using soybean meal as an oil and fat can be exemplified [JP-A-56-7857].
No. 2]. Fat-and-oil-processed starch using soybean meal as fat or oil is prepared by mixing raw soybean flour with starch at a ratio of 0.1 to 20% by weight, preferably 0.3 to 3% by weight, and 100 ° C or lower, particularly 60 to 100%. It can be obtained by heating in a temperature range of 80 ° C. for 3 to 6 hours.
【００１３】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 starch used as the raw material of the processed starch is not particularly limited. For example, underground starches such as potato starch, sweet potato starch, tapioca starch, and ground starches such as wheat starch, corn starch, sago starch, and rice starch can be used. The state may be powdered starch, slurry-like or cake-like starch. The amount of fats and oils added to starch can be appropriately changed depending on the types of starch and fats and oils.
It is appropriate that the amount is in the range of 1 to 5.0 parts by weight, preferably 0.5 to 2.0 parts by weight.
【００１４】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、熟成を充分に行うという観点から
は、油脂加工澱粉は１％以下の水分まで乾燥するのが適
当である。The fats and oils are adsorbed on the starch by mixing with the starch and, if necessary, are aged by heating to give a fat-and-oil-processed starch. For example, in the case of starch cakes and powders, fats and oils are dissolved or dispersed in water or an organic solvent and sprayed, and in the case of starch slurries, the fats and oils are dissolved or dispersed in the slurry and stirred to convert the fats and oils into starch. Can be adsorbed. Some types of fats and oils can be used as fats and oils-modified starch without heat aging. Heat aging is, for example, 30 to 18
The reaction can be performed at a temperature of 0 ° C. for a period of 1 hour to 10 days. In addition, heat aging and drying of the starch having the fats and oils adsorbed by the wet method can be performed simultaneously. This drying is carried out by using a dryer commonly used for drying starch, such as a band drier or a flash drier, to dry the starch to the equilibrium moisture, so that the fats and oils can be uniformly mixed and adsorbed on the starch. However, from the viewpoint of sufficiently aging, it is appropriate to dry the fat-and-oil-processed starch to a moisture content of 1% or less.
【００１５】本発明では、上記油脂加工澱粉の糊化物を
用いる。澱粉の糊化とは、一般に、水等の存在下で加熱
すると澱粉粒が不可逆的に膨潤又は溶解し、結晶性及び
複屈折性を失い、粘度が上昇した状態をいう。本発明に
おける澱粉糊化物は、結晶性及び複屈折性を実質的に示
さないものをいう。尚、結晶性及び複屈折性の喪失は、
澱粉粒を偏光顕微鏡で観察し、未糊化澱粉では見られた
形成中心で交差した偏光十字が、見られなくなることで
判定することができる。In the present invention, a gelatinized product of the above-mentioned oil-and-fat processed starch is used. The gelatinization of starch generally refers to a state in which when heated in the presence of water or the like, starch granules irreversibly swell or dissolve, lose crystallinity and birefringence, and increase in viscosity. The gelatinized starch in the present invention refers to one that does not substantially exhibit crystallinity and birefringence. Incidentally, the loss of crystallinity and birefringence,
The starch granules can be observed with a polarizing microscope, and the determination can be made based on the fact that the polarizing cross crossing at the center of formation, which was observed with ungelatinized starch, is no longer seen.
【００１６】油脂加工澱粉の糊化物は、油脂加工澱粉と
水又は水と可塑剤とを加熱混合することにより得ること
ができる。油脂加工澱粉の糊化は、水単独の存在下で行
うことができる。また、水と可塑剤との存在下でも、油
脂加工澱粉を糊化することができ、この場合、水の使用
量を低減でき、成形時の発泡防止に有効である。さら
に、糊化物に可塑剤を含有させることにより、油脂加工
澱粉糊化物と生分解性樹脂との混合及び成形を容易にで
きるという利点もある。The gelatinized product of the fat / oil modified starch can be obtained by heating and mixing the fat / oil modified starch and water or water and a plasticizer. Gelatinization of the fat-and-oil-processed starch can be performed in the presence of water alone. In addition, even in the presence of water and a plasticizer, the oil-and-fat-modified starch can be gelatinized. In this case, the amount of water used can be reduced, which is effective in preventing foaming during molding. Further, by adding a plasticizer to the gelatinized product, there is an advantage that mixing and molding of the oil-and-fat processed starch gelatinized product and the biodegradable resin can be facilitated.
【００１７】糊化に用いる可塑剤は、油脂加工澱粉を糊
化でき、かつ糊化物に可塑性を付与できるものであれば
特に制限はなく、例えば、生分解性を有する高沸点可塑
剤を挙げることができる。そのような可塑剤の例として
は、エチレングリコール、プロピレングリコール、グリ
セリン、ソルビトール、ポリエチレングリコール、ポリ
プロピレングリコール等を挙げることができる。The plasticizer used for the gelatinization is not particularly limited as long as it can gelatinize the oil-and-fat processed starch and can impart plasticity to the gelatinized product. Examples thereof include a high boiling plasticizer having biodegradability. Can be. Examples of such plasticizers include ethylene glycol, propylene glycol, glycerin, sorbitol, polyethylene glycol, polypropylene glycol and the like.
【００１８】糊化に水を用いる場合には、油脂加工澱粉
（乾物基準）１００重量部当たり１０〜５０重量部の水
を用いることが、澱粉を充分に糊化させるという観点か
ら適当である。さらに、好ましくは、油脂加工澱粉（乾
物基準）１００重量部当たり１０〜２０重量部の水を用
いることが、澱粉を充分に糊化させるとともに、生分解
性組成物に添加して成形する際の発泡を防止できるとい
う観点から適当である。When water is used for gelatinization, it is appropriate to use 10 to 50 parts by weight of water per 100 parts by weight of the fat and oil-modified starch (based on dry matter) from the viewpoint of sufficiently gelatinizing the starch. Further, it is preferable to use 10 to 20 parts by weight of water per 100 parts by weight of the fat-and-oil-processed starch (dry matter basis) when the starch is sufficiently gelatinized and added to the biodegradable composition for molding. It is appropriate from the viewpoint that foaming can be prevented.
【００１９】また、糊化に水と可塑剤を用いる場合に
は、油脂加工澱粉（乾物基準）１００重量部当たり０．
１〜４０重量部の水及び１〜１００重量部の可塑剤を用
いることが、澱粉を充分に糊化させ、かつ糊化物に充分
な可塑性を付与できるという観点から適当である。さら
に、好ましくは、油脂加工澱粉（乾物基準）１００重量
部当たり０．１〜２０重量部の水及び５〜４０重量部の
可塑剤を用いることが、澱粉を充分に糊化させるととも
に、生分解性組成物に添加して成形する際の発泡を防止
でき、かつ糊化物に適度な可塑性を付与できるという観
点から適当である。When water and a plasticizer are used for gelatinization, the amount of 0.1 g / 100 parts by weight of fat and oil modified starch (dry basis) is used.
The use of 1 to 40 parts by weight of water and 1 to 100 parts by weight of a plasticizer is suitable from the viewpoint that starch can be sufficiently gelatinized and sufficient plasticity can be imparted to the gelatinized product. Further, it is preferable to use 0.1 to 20 parts by weight of water and 5 to 40 parts by weight of a plasticizer per 100 parts by weight of the fat-processed starch (dry matter basis) so that the starch is sufficiently gelatinized and biodegraded. It is suitable from the viewpoint that foaming at the time of molding by being added to the conductive composition can be prevented, and appropriate plasticity can be imparted to the gelatinized product.
【００２０】油脂加工澱粉の糊化のための加熱混合は、
油脂加工澱粉の種類や、可塑剤を用いる場合には可塑剤
の種類、さらには水や可塑剤の添加量により適宜決定で
きるが、例えば６０〜２２０℃で１０〜６０分間行うこ
とが適当である。加熱混合は、例えば、加圧ニーダーや
押出し機等を用いて行うことができる。加熱混合により
得られる糊化物は、例えば、ペレット化しておいて、後
に生分解性樹脂と混合することができる。The heating and mixing for gelatinizing the fat-and-oil-processed starch is as follows:
The type of the oil-and-fat processed starch, and when using a plasticizer, can be appropriately determined by the type of the plasticizer, and furthermore, the amount of water or the plasticizer to be added. . The heating and mixing can be performed using, for example, a pressure kneader or an extruder. The gelatinized product obtained by the heating and mixing can be, for example, pelletized and subsequently mixed with the biodegradable resin.
【００２１】本発明の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。化学合成系樹脂、微生物系樹脂、天
然物利用系樹脂等のいずれに属する樹脂でも良い。例え
ば、脂肪族ポリエステル（例えば、ポリカプロラクト
ン、ポリ乳酸、ポリヒドロキシブチレート・バリレート
共重合体など）、ポリビニルアルコール、アセチルセル
ロース等を挙げることができる。The biodegradable resin used in the composition of the present invention is not particularly limited. It is sufficient that the resin itself has biodegradability, and thermoplastic resin is appropriate in consideration of moldability. Resins belonging to any of a chemically synthesized resin, a microbial resin, a natural product-based resin and the like may be used. For example, aliphatic polyesters (for example, polycaprolactone, polylactic acid, polyhydroxybutyrate / valerate copolymer, etc.), polyvinyl alcohol, acetylcellulose and the like can be mentioned.
【００２２】より具体的には、生分解性を考慮すると、
平均分子量３万〜４万の範囲のジオールとジカルボン酸
を原料とする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０〜４
０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
挙げることができる。More specifically, considering biodegradability,
Aliphatic polyesters made from diols and dicarboxylic acids having an average molecular weight of 30,000 to 40,000, and an average molecular weight of 40,000 to 7
10,000 polycaprolactone, average molecular weight 80,000-12
Polylactic acid in the range of 10,000, polyvinyl alcohol in the average molecular weight range of 20,000 to 90,000, and hydroxyvalerate fraction of 0 to 4
0 mol% polyhydroxybutyrate / valerate copolymer, acetyl cellulose having an acetylation degree of 43 to 55%, methyl cellulose having a methoxy content of 27.5 to 31.5%, and ethoxy content of 47.5 to 49.0% Ethyl cellulose.
【００２３】また、本発明の組成物においては、油脂加
工澱粉糊化物との相性の良さから、生分解性樹脂が脂肪
族ポリエステルであることが好ましい。生分解性樹脂と
して脂肪族ポリエステルを含む本発明の組成物は、樹脂
のみの場合と比較して、機械的特性がほぼ同等であり、
かつ生分解性は樹脂のみの場合より遙に優れている。脂
肪族ポリエステルとしては、例えば、二塩基酸を含む多
価カルボン酸とジオールを含む多価アルコールの重縮合
物、ヒドロキシ酸の重縮合物、ラクトンの開環重合物等
であって、リパーゼの作用により加水分解されるものを
挙げることができる。具体的には、ポリエチレンアジペ
ート、ポリプロピオンラクトン、ポリカプロラクトン、
ポリ乳酸、ポリ−β−ヒドロキシ酪酸、ポリ−β−ヒド
ロキシブチレート若しくはそれらの共重合体またはその
混合物を挙げることができる。In the composition of the present invention, it is preferable that the biodegradable resin is an aliphatic polyester in view of the good compatibility with the gelatinized product of the processed fat and oil. The composition of the present invention containing an aliphatic polyester as a biodegradable resin has almost the same mechanical properties as compared to the resin alone,
And the biodegradability is far superior to the case of using only the resin. As the aliphatic polyester, for example, a polycondensate of a polyhydric carboxylic acid containing a dibasic acid and a polyhydric alcohol containing a diol, a polycondensate of a hydroxy acid, a ring-opening polymer of a lactone, and the like, the action of lipase Can be mentioned. Specifically, polyethylene adipate, polypropion lactone, polycaprolactone,
Examples include polylactic acid, poly-β-hydroxybutyric acid, poly-β-hydroxybutyrate, a copolymer thereof, or a mixture thereof.
【００２４】本発明の生分解性組成物における各成分の
配合量は、例えば、油脂加工澱粉糊化物（乾物基準）を
１０〜９９重量％、好ましくは５０〜９５重量％、生分
解性樹脂（乾物基準）を９０〜１重量％、好ましくは５
０〜５重量％とすることが適当である。油脂加工澱粉糊
化物の配合比率が１０重量％以上であれば、油脂加工澱
粉糊化物の添加による生分解改善効果が現れ始め、特
に、５０重量％以上になると、澱粉による分解性の促進
効果が顕著になる。また、油脂加工澱粉糊化物の配合比
率が９９重量％以下であれば、成形性等に大きな支障は
なく、特に、９５重量％以下では、通常の樹脂のみの場
合とほぼ同様の成形性を示す。The compounding amount of each component in the biodegradable composition of the present invention is, for example, 10 to 99% by weight, preferably 50 to 95% by weight of a gelatinized product of fat and oil-modified starch (based on dry matter), and a biodegradable resin ( 90-1% by weight (dry matter basis), preferably 5
Suitably, it is 0 to 5% by weight. When the blending ratio of the fat-and-oil-processed starch gelatinized product is 10% by weight or more, the effect of improving biodegradation by adding the fat-and-oil-processed starch gelatinized material starts to appear. Become noticeable. Further, when the blending ratio of the gelatinized oil-and-fat-processed starch is 99% by weight or less, there is no significant problem in moldability and the like. In particular, when it is 95% by weight or less, almost the same moldability as in the case of using only ordinary resin is exhibited. .
【００２５】本発明の組成物は、上記成分に加えて、必
要により、添加剤を適宜加えることもできる。例えば、
植物性タンパク質、パルプ、紫外線安定剤、殺菌剤、除
草剤、肥料、酸化防止剤、界面活性剤、顔料等を挙げる
ことができる。The composition of the present invention may optionally contain additives in addition to the above components, if necessary. For example,
Vegetable proteins, pulp, ultraviolet stabilizers, bactericides, herbicides, fertilizers, antioxidants, surfactants, pigments and the like can be mentioned.
【００２６】本発明の組成物は、油脂加工澱粉糊化物と
生分解性樹脂とを、生分解性樹脂の溶融温度以上で加熱
混練することにより製造することができる。例えば、６
０℃〜２２０℃の範囲の温度にて１０〜６０分間、油脂
加工澱粉糊化物と生分解性樹脂とを加熱混練することで
得ることができる。油脂加工澱粉糊化物は、前述のよう
に予めペレット状としておき、このペレットと、生分解
性樹脂のペレットとを加熱混練し、さらに射出成形機又
は押出成形機等を用いて成形することができる。The composition of the present invention can be produced by heating and kneading the gelatinized oil-and-fat-modified starch and the biodegradable resin at a temperature not lower than the melting temperature of the biodegradable resin. For example, 6
It can be obtained by heating and kneading the gelatinized fat and oil-processed starch and the biodegradable resin at a temperature in the range of 0 ° C to 220 ° C for 10 to 60 minutes. The oil-and-fat processed starch gelatinized material is previously pelletized as described above, and the pellet and the biodegradable resin pellet are heated and kneaded, and further molded using an injection molding machine or an extrusion molding machine or the like. .
【００２７】また、本発明の組成物は、油脂加工澱粉と
生分解性樹脂とを水又は水及び可塑剤の存在下、生分解
性樹脂の溶融温度以上で加熱混練することによっても製
造することができる。その際の油脂加工澱粉と水の比率
は、糊化物の製造と同様に、油脂加工澱粉（乾物基準）
１００重量部当たり、水１０〜５０重量部とすることが
適当である。また、油脂加工澱粉と水と可塑剤との比率
は、油脂加工澱粉（乾物基準）１００重量部当たり、水
０．１〜４０重量部及び可塑剤１〜１００重量部とする
ことが適当である。The composition of the present invention can also be produced by heating and kneading a fat and oil-modified starch and a biodegradable resin in the presence of water or water and a plasticizer at a temperature not lower than the melting temperature of the biodegradable resin. Can be. In this case, the ratio of the fat-and-oil-processed starch to water is the same as in the case of the gelatinized product, and the oil-and-fat-modified starch (dry matter basis)
It is appropriate to use 10 to 50 parts by weight of water per 100 parts by weight. Also, the ratio of the oil-and-fat processed starch, water and plasticizer is preferably 0.1 to 40 parts by weight of water and 1 to 100 parts by weight of the plasticizer per 100 parts by weight of oil-and-fat processed starch (dry matter basis). .
【００２８】本発明の組成物は、樹脂製品の加工に用い
られる常法により成形することができる。成形品の形状
や用途等には特に制限はない。例えば、シート、フィル
ム、容器等に成形できる。また、ペレットに成形し、更
に二次加工用に供することもできる。The composition of the present invention can be formed by a conventional method used for processing resin products. There is no particular limitation on the shape and use of the molded product. For example, it can be formed into a sheet, film, container or the like. Further, it can be formed into pellets and further provided for secondary processing.
【００２９】本発明の組成物は、油脂加工澱粉糊化物を
用いている。そのため、この組成物を熱圧成形、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 composition of the present invention uses an oil-and-fat-processed starch gelatinized product. Therefore, the film or sheet obtained by hot-pressing, inflation forming, or blow-molding the composition has less decrease 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.
【００３０】[0030]
【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糊化物を用いて、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。従来の生分解性樹脂は、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樹脂組成物の価格を低減で
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。According to the present invention, the use of fat- and starch-processed starch obtained by processing starch lightly and inexpensively improves compatibility with biodegradable resins and interfacial adhesion, and improves mechanical properties. It is possible to obtain a biodegradable resin composition which prevents a significant decrease, increases the blending ratio of starch, and has good moldability. Conventional biodegradable resins are more expensive than general-purpose thermoplastic resins, and it is difficult to reach a price comparable to general-purpose resins in the future. According to the present invention, the cost of the biodegradable resin composition can be reduced by adding an inexpensive starch to form a complex, which also leads to the promotion of biodegradability, and its application range can be expanded to the level of general-purpose resins. It becomes possible.
【００３１】[0031]
【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（水分１．０％になったもの）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〕を乾物基
準で６０：４０の重量比率で混合し、さらにグリセリン
を澱粉（乾物基準）１００重量部に対して４０重量部混
合した後、二軸押出機（東洋精機製）を用いて混練ゾー
ン温度１３０℃にて混練し、直径約３ｍｍの棒状に押し
出したものを２〜３ｍｍに切断してペレットを得た。The present invention will be further described with reference to the following 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.). It was dried to 0.3% or less to obtain safflower oil-processed corn starch. This safflower oil-processed corn starch (water having a water content of 1.0%) and a commercially available aliphatic polyester-based biodegradable resin (Bionore # 1000, manufactured by Showa Polymer Co., number average molecular weight: 35,000) were dried on a dry matter basis to 60: After mixing at a weight ratio of 40 and further mixing 40 parts by weight of glycerin with respect to 100 parts by weight of starch (based on dry matter), the mixture was kneaded using a twin-screw extruder (manufactured by Toyo Seiki) at a kneading zone temperature of 130 ° C. The pellet extruded into a rod having a diameter of about 3 mm was cut into 2-3 mm to obtain a pellet.
【００３２】得られたペレットを試験用卓上プレス（東
洋精機製作所）を用いて、加圧温度１５０℃、加重１０
０ｋｇｆ／ｃｍ2 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、１０
０ｋｇｆ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 obtained pellets were pressed using a test table press (Toyo Seiki Seisakusho) at a pressurization temperature of 150 ° C. and a load of 10
The sheet was molded under 0 kgf / cm 2 to obtain a sheet having a thickness of about 0.4 mm. A rectangular 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 10
Using a 0 kgf load cell, the span length was set to 40 mm, and the crosshead speed was 5 mm / min. From the results of the tensile test, each mechanical property was calculated by the following formula.・ Tensile strength (kgf / cm 2 ) = Breaking load (kg
f) / cross-sectional area (cm 2 ) ・ Elongation at break (%) = {(elongation at break−span length) / span length} × 100 ・ Elastic modulus (kgf / cm 2 ) = proportional source stress / strain Table 1 shows the results. Shown in
【００３３】比較例１ サフラワー油加工コーンスターチを水分１．０％の未加
工コーンスターチの糊化物に代えた以外は、実施例１と
同様の調製法でペレットを作製し、さらにこのペレット
から熱圧シートを作製し、次いで短冊状試験片を作製
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。Comparative Example 1 Pellets were prepared in the same manner as in Example 1, except that the safflower oil-processed corn starch was replaced with unprocessed gelatinized corn starch having a moisture content of 1.0%. A sheet was prepared, then a strip-shaped test piece was prepared, and a similar test was performed to examine mechanical properties. Table 1 shows the results.
【００３４】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 2 A sheet was obtained only from a commercially available aliphatic polyester-based biodegradable resin without using safflower oil-processed corn starch, and a test was conducted in the same manner as in Example 1 to examine mechanical properties. Table 1 shows the results.
【００３５】表１に示す様に油脂加工澱粉を用いた実施
例１は樹脂のみを用いた比較例２とほぼ同等の機械的特
性を有しており、未加工澱粉を用いた比較例１に比べて
優れた機械的特性を有することがわかる。As shown in Table 1, Example 1 using an oil-modified starch has almost the same mechanical properties as Comparative Example 2 using only a resin. It can be seen that it has excellent mechanical properties.
【００３６】[0036]
【表１】 [Table 1]
【００３７】実施例１で調製した短冊状試験片（５ｍｍ
×８０ｍｍ）を標準活性汚泥曝気槽にさらした活性汚泥
試験、地表下１５ｃｍに埋没させた土中埋没試験に供し
た。比較試料として比較例２と低密度ポリエチレン（出
光興産製）で調製した短冊状試験片を用いた。結果を表
２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 prepared in Example 1 (5 mm
× 80 mm) was subjected to an activated sludge test exposed to a standard activated sludge aeration tank, and a soil burial test buried 15 cm below the ground surface. As a comparative sample, a strip-shaped test piece prepared from Comparative Example 2 and low-density polyethylene (manufactured by Idemitsu Kosan) was used. Table 2 shows the results. It is believed that the complex of the present invention containing the oil-and-fat modified starch is such that the starch is first preferentially degraded by microorganisms and enzymes, and as a result becomes porous, thereby promoting the biodegradation of the aliphatic polyester chain.
【００３８】[0038]
【表２】 [Table 2]
【００３９】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％〕を乾物基準で５０：５０の重量比率
で配合し、さらに澱粉（乾物基準）１００重量部当たり
１５重量部の水及び２０重量部のグリセリンを混合した
後、二軸押出機（東洋精機製）を用いて混練ゾーン温度
１７０℃にて混練し、直径約３ｍｍの棒状に押し出した
ものを２〜３ｍｍに切断してペレットを得た。このペレ
ットから加圧温度を１８０℃とした以外は実施例１と同
様に短冊状試験片を作製し、機械的特性を試験した。結
果を表３に示す。Example 2 4 parts by weight of soybean meal was added to 100 parts by weight of a starch solid content of a tapioca starch wet cake containing about 40% of water, and the mixture was uniformly mixed with a kneader (Moriyama Seisakusho type DS1).
Preliminary drying was carried out for 30 minutes using a box dryer heated to ° C. Thereafter, the product was dried using a box drier heated to 120 ° C. so that the product moisture was 0.3% or less, to obtain a processed soybean meal tapioca starch. This soybean meal processed tapioca starch and a commercially available polyhydroxybutyrate / valerate copolymer [Biopol D410G manufactured by Zeneca, hydroxyvalerate fraction 8 mol%] are blended at a weight ratio of 50:50 on a dry matter basis, and further starch ( After mixing 15 parts by weight of water and 20 parts by weight of glycerin per 100 parts by weight, using a twin screw extruder (manufactured by Toyo Seiki Co., Ltd.), kneading was performed at a kneading zone temperature of 170 ° C. to obtain a rod having a diameter of about 3 mm. Was extruded to obtain a pellet. A strip-shaped test piece was prepared from this pellet in the same manner as in Example 1 except that the pressing temperature was set to 180 ° C., and the mechanical properties were tested. Table 3 shows the results.
【００４０】比較例３ 大豆粕加工タピオカ澱粉に代えて水分１３％のタピオカ
澱粉（澱粉乾物基準１００重量部当たり１５重量部の
水）を用いた以外は実施例２と同様の調製法で、ペレッ
トを得、さらに短冊状試験片を作製した。この短冊状試
験片について、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３に示す。Comparative Example 3 A pellet was prepared in the same manner as in Example 2 except that tapioca starch having a water content of 13% (15 parts by weight of water per 100 parts by weight of starch dry matter) was used in place of the processed soybean meal tapioca starch. And a strip-shaped test piece was prepared. This strip-shaped test piece was evaluated for mechanical properties in the same manner as in Example 2. Table 3 shows the results.
【００４１】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。シートの評価方法
も、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３に示す。Comparative Example 4 A sample was obtained in the same manner as in Example 2 except that a soybean meal processed tapioca starch was not used and only a copolymer of commercially available polyhydroxybutyrate and valerate was used. The sheet was evaluated in the same manner as in Example 1 except that the pressing temperature was set to 180 ° C. Table 3 shows the results.
【００４２】表３に示すように、本発明の組成物である
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
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 3, it can be seen that Example 2 which is a composition of the present invention has excellent mechanical properties as compared with Comparative Example 3 using raw starch. Further, it can be seen that Example 2 which is the composition of the present invention has almost the same mechanical properties as Comparative Example 4 using only the resin.
【００４３】[0043]
【表３】 [Table 3]
【００４４】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。得られた大豆油加工コーンスターチ（乾物基準）
１００重量部に対して水２０重量部及びエチレングリコ
ール１５重量部を配合し、二軸押出機（東洋精機製）を
用いて混練ゾーン温度１３０℃にて混練し、直径約３ｍ
ｍの棒状に押し出したものを２〜３ｍｍに切断して大豆
油加工コーンスターチ糊化物ペレットを得た。Example 3 2 parts by weight of soybean oil was added to 100 parts by weight of corn starch, and the mixture was uniformly mixed using a super mixer (manufactured by Kawada Seisakusho). % To obtain a soybean oil-processed corn starch. The resulting soybean oil-processed corn starch (dry matter basis)
20 parts by weight of water and 15 parts by weight of ethylene glycol are blended with 100 parts by weight, and kneaded at a kneading zone temperature of 130 ° C. using a twin-screw extruder (manufactured by Toyo Seiki), and the diameter is about 3 m.
The extruded rod was cut into 2-3 mm pieces to obtain gelatinized corn starch pellets processed with soybean oil.
【００４５】得られた大豆油加工コーンスターチ糊化物
ペレットと分子量７万のポリカプロラクトン〔ダイセル
化学製、プラクセルＨ７〕を乾物基準で７０：３０の比
率で配合した後、二軸押出機（東洋精機製）を用いて混
練ゾーン温度１３０℃にて混練し、直径約３ｍｍの棒状
に押し出したものを２〜３ｍｍに切断して本発明の組成
物のペレットを得た。得られたペレットからのシートの
作製は、加圧温度を１３０℃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４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。The resulting soybean oil-processed corn starch gelatinized pellets and a polycaprolactone having a molecular weight of 70,000 [Daicel Chemical Co., Ltd., Praxel H7] were blended at a ratio of 70:30 on a dry matter basis, and then a twin-screw extruder (Toyo Seiki Co., Ltd. ), And kneaded at a kneading zone temperature of 130 ° C., extruded into a rod having a diameter of about 3 mm, and cut into 2-3 mm to obtain pellets of the composition of the present invention. Production of a sheet from the obtained pellets was performed in the same manner as in Example 1 except that the pressing temperature was 130 ° 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 4. When the obtained sheet was buried in soil 15 cm below the surface of the ground, the shape of the sheet could not be seen after two months.
【００４６】比較例５ 大豆油加工コーンスターチに代えて未加工コーンスター
チを用いて作製した未加工コーンスターチの糊化物のペ
レットを用いた以外は実施例３と同様の調製法でシート
を得た。機械的特性の結果を表５に示す。Comparative Example 5 A sheet was obtained by the same preparation method as in Example 3, except that gelatinized pellets of raw corn starch prepared using raw corn starch instead of soybean oil-processed corn starch were used. Table 5 shows the results of the mechanical properties.
【００４７】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４に示す。Comparative Example 6 A sheet was obtained in the same manner as in Example 3 except that a sheet was prepared using only polycaprolactone resin without using soybean oil-processed corn starch. Table 4 shows the results of the mechanical properties of the obtained sheet.
【００４８】表４に示すように油脂加工澱粉を用いた実
施例３は樹脂のみを用いた比較例６に比べて破壊伸長率
がやや劣るものの引張強度は同等であり、未加工澱粉を
用いた比較例５に比べて優れた機械的特性を有している
ことが分かる。As shown in Table 4, in Example 3 using an oil-modified starch, the elongation at break was slightly inferior to that in Comparative Example 6 using only the resin, but the tensile strength was the same, and the unmodified starch was used. It can be seen that it has excellent mechanical properties as compared with Comparative Example 5.
【００４９】[0049]
【表４】 [Table 4]
【００５０】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（水分１％）と平均分子量１２万のポリ乳酸
〔島津製作所製〕を乾物基準で７０：３０の比率で配合
し、これにプロピレングリコールを澱粉（乾物基準）１
００重量部に対して３０重量部混合した後、１８０℃に
加温したラボプラストミル（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５に示す。Example 4 One part by weight of linseed oil was added to 100 parts by weight of corn starch and uniformly mixed using a plain mixer (manufactured by Takara Koki Co., Ltd.), and then a box-shaped dryer heated to 100 ° C. The dried product was dried to a moisture content of 0.3% or less to obtain linseed oil-processed corn starch. This linseed oil-processed corn starch (water content: 1%) and polylactic acid having an average molecular weight of 120,000 (manufactured by Shimadzu Corporation) are blended at a ratio of 70:30 on a dry matter basis, and propylene glycol is added to the starch (dry matter basis).
After mixing 30 parts by weight with respect to 00 parts by weight, a uniform cylindrical pellet having a diameter of 3 mm was obtained using a Labo Plastomill (manufactured by Toyo Seiki Seisakusho) heated to 180 ° C. The production of the sheet was performed in the same manner as in Example 1 except that the pressing temperature was set to 180 ° 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.
【００５１】比較例７ マアニ油加工トウモロコシ澱粉に代えて未加工トウモロ
コシ澱粉を用いた以外は実施例４と同様の調製法でシー
トを得た。機械的特性の結果を表５に示す。Comparative Example 7 A sheet was obtained by the same preparation method as in Example 4 except that unprocessed corn starch was used instead of the maani oil-processed corn starch. Table 5 shows the results of the mechanical properties.
【００５２】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５に示す。Comparative Example 8 A sheet was obtained in the same manner as in Example 4 except that a sheet was prepared only with a polylactic acid resin without using linseed oil-processed corn starch. Table 5 shows the results of the mechanical properties.
【００５３】表５に示すように油脂加工澱粉を用いた実
施例４は樹脂のみを用いた比較例８とほぼ同等の機械的
特性を有しており、未加工澱粉を用いた比較例７よりも
優れた機械的特性を有していることが分かる。As shown in Table 5, Example 4 using the oil-modified starch had almost the same mechanical properties as Comparative Example 8 using only the resin, and Comparative Example 7 using the unmodified starch. It can also be seen that they also have excellent mechanical properties.
【００５４】[0054]
【表５】 [Table 5]
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平７−62220（ＪＰ，Ａ) 特開 平６−271696（ＪＰ，Ａ) 特開 平８−188671（ＪＰ，Ａ) 特開 平８−92419（ＪＰ，Ａ) 特開 平６−49276（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C08L 3/04 - 3/10 C08L 1/12 C08L 29/04 C08L 67/00 - 67/04 C08L 101/00 - 101/14 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-7-6220 (JP, A) JP-A-6-271696 (JP, A) JP-A-8-188861 (JP, A) JP-A 8- 92419 (JP, A) JP-A-6-49276 (JP, A) (58) Fields investigated (Int. Cl. 6 , DB name) C08L 3/04-3/10 C08L 1/12 C08L 29/04 C08L 67/00-67/04 C08L 101/00-101/14
Claims (9)
含むことを特徴とする生分解性組成物。1. A biodegradable composition comprising an oil-and-fat processed starch gelatinized product 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 fat- and oil-processed starch is obtained by adsorbing one or more compounds selected from the group consisting of fats and oils, related substances of fats and oils, fatty acids and fatty acid derivatives on the starch, and then aging the starch. The composition of claim 1.
ポリビニルアルコール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,
3. The composition according to claim 1, which is a resin selected from the group consisting of polyvinyl alcohol and acetyl cellulose.
ン、ポリ乳酸及びポリヒドロキシブチレート・バリレー
ト共重合体からなる群から選ばれる樹脂である請求項３
記載の組成物。4. The resin according to claim 3, wherein the aliphatic polyester is a resin selected from the group consisting of polycaprolactone, polylactic acid, and a polyhydroxybutyrate-valerate copolymer.
A composition as described.
又は水及び可塑剤の存在下で糊化させたものである請求
項１〜４のいずれか１項に記載の組成物。5. The composition according to any one of claims 1 to 4, wherein the fat and oil-modified starch is gelatinized in the presence of water or water and a plasticizer.
量が１０〜９９重量％の範囲であり、生分解性樹脂（乾
物基準）の配合量が９０〜１重量％の範囲である請求項
１〜５のいずれか１項に記載の組成物。6. The amount of the gelatinized starch (based on dry matter) processed by the fat and oil is in the range of 10 to 99% by weight, and the amount of the biodegradable resin (based on dry matter) is in the range of 90 to 1% by weight. Item 6. The composition according to any one of Items 1 to 5.
水及び可塑剤の存在下で加熱混練することを特徴とする
請求項１記載の組成物の製造方法。7. The method for producing a composition according to claim 1, wherein the oil-modified starch and the biodegradable resin are heated and kneaded in the presence of water or water and a plasticizer.
準での重量比が１０：９０〜９９：１の範囲であり、油
脂加工澱粉（乾物基準）１００重量部当たり１０〜５０
重量部の水を存在させる請求項７記載の製造方法。8. The weight ratio of the oil-modified starch to the biodegradable resin on a dry matter basis is in the range of 10:90 to 99: 1, and 10 to 50 per 100 parts by weight of the oil-modified starch (dry matter).
The method according to claim 7, wherein water is present in parts by weight.
準での重量比が１０：９０〜９９：１の範囲であり、油
脂加工澱粉（乾物基準）１００重量部当たり０．１〜４
０重量部の水及び１〜１００重量部の可塑剤を存在させ
る請求項７記載の製造方法。9. The weight ratio of the oil-modified starch to the biodegradable resin on a dry matter basis is in the range of 10:90 to 99: 1, and 0.1 to 4 per 100 parts by weight of the oil-modified starch (dry matter).
The method according to claim 7, wherein 0 parts by weight of water and 1 to 100 parts by weight of a plasticizer are present.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7095168A JP2978081B2 (en) | 1995-04-20 | 1995-04-20 | Biodegradable 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 |
|---|---|---|---|
| JP7095168A JP2978081B2 (en) | 1995-04-20 | 1995-04-20 | Biodegradable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08283458A JPH08283458A (en) | 1996-10-29 |
| JP2978081B2 true JP2978081B2 (en) | 1999-11-15 |
Family
ID=14130240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7095168A Expired - Fee Related JP2978081B2 (en) | 1994-09-28 | 1995-04-20 | Biodegradable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2978081B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220087744A (en) * | 2020-12-18 | 2022-06-27 | 대상 주식회사 | Binder for fish farming feed and fish farming feed composition comrising the same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100503763B1 (en) * | 1998-01-23 | 2005-10-27 | 주식회사 새 한 | Biodecomposable resin composition |
| KR100564345B1 (en) | 1998-08-11 | 2006-03-27 | 도시노부 요시하라 | Composition for molding biodegradable plastic, biodegradable plastic obtained therefrom, method of molding the same, and use of biodegradable plastic |
-
1995
- 1995-04-20 JP JP7095168A patent/JP2978081B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220087744A (en) * | 2020-12-18 | 2022-06-27 | 대상 주식회사 | Binder for fish farming feed and fish farming feed composition comrising the same |
| KR102567365B1 (en) | 2020-12-18 | 2023-08-18 | 대상 주식회사 | Binder for fish farming feed and fish farming feed composition comrising the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08283458A (en) | 1996-10-29 |
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