JP3078478B2 - Composition for biodegradable molded article and method for producing biodegradable molded article - Google Patents
Composition for biodegradable molded article and method for producing biodegradable molded articleInfo
- Publication number
- JP3078478B2 JP3078478B2 JP07203489A JP20348995A JP3078478B2 JP 3078478 B2 JP3078478 B2 JP 3078478B2 JP 07203489 A JP07203489 A JP 07203489A JP 20348995 A JP20348995 A JP 20348995A JP 3078478 B2 JP3078478 B2 JP 3078478B2
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- Prior art keywords
- starch
- parts
- weight
- oxidizing agent
- biodegradable
- 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.)
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、澱粉糊化物を含有
する生分解性生成品用組成物および生分解性生成品の製
造方法に関する。さらに詳しくは澱粉に酸化剤を配合す
ることにより澱粉糊化時に低粘度化させ、成形時の流動
性が改善させれた生分解性成形品用の組成物、および成
形時の流動性を改善して良好な形成加工性を有する生分
解性成形品の製造方法に関する。The present invention relates to a composition for a biodegradable product containing a gelatinized starch and a method for producing the biodegradable product. More specifically, a composition for a biodegradable molded article in which the viscosity is reduced at the time of starch gelatinization by adding an oxidizing agent to the starch to improve the fluidity at the time of molding, and the fluidity at the time of molding are improved. The present invention relates to a method for producing a biodegradable molded product having good processability.
【０００２】[0002]
【従来の技術】澱粉糊化物を生分解性成分として利用す
ることが提案されている。例えば、特開平１−２１７０
０２号（先行技術１という）には、澱粉糊化物を主成分
とする生分解性組成物が開示されている。また、例え
ば、特開平２−１４２２８号（先行技術２という）に
は、澱粉糊化物と生分解性樹脂の複合体である生分解性
組成物が開示されている。2. Description of the Related Art It has been proposed to utilize gelatinized starch as a biodegradable component. For example, JP-A 1-2170
No. 02 (referred to as Prior Art 1) discloses a biodegradable composition containing a gelatinized starch as a main component. For example, Japanese Patent Application Laid-Open No. 2-142228 (hereinafter referred to as Prior Art 2) discloses a biodegradable composition which is a complex of a gelatinized starch and a biodegradable resin.
【０００３】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（先行技術３という）には澱粉グラフト
コポリマーを含む生分解性組成物が開示されている。特
開平３−７０７５２号（先行技術４という）には、アニ
オン性修飾澱粉を含む生分解性組成物が開示されてい
る。特開平３−７４４４５号（先行技術５という）には
カチオン性修飾澱粉を含む生分解性組成物が開示されて
いる。特開平３−７４４４６号（先行技術６という）に
は、ヒドロキシアルキル基、アルキルエーテル基及びエ
ステル基の少なくとも１つを含む様に化学的に改質され
た澱粉を澱粉成分として含む生分解性組成物が開示され
ている。[0003] Biodegradable resin compositions using various modified starches as starches are also known. For example, Japanese Unexamined Patent Publication
-56543 (referred to as prior art 3) discloses a biodegradable composition comprising a starch graft copolymer. JP-A-3-70752 (hereinafter referred to as Prior Art 4) discloses a biodegradable composition containing an anionic modified starch. JP-A-3-74445 (hereinafter referred to as Prior Art 5) discloses a biodegradable composition containing a cationically modified starch. JP-A-3-74446 (referred to as prior art 6) discloses a biodegradable composition containing starch chemically modified to contain at least one of a hydroxyalkyl group, an alkyl ether group and an ester group as a starch component. Is disclosed.
【０００４】[0004]
【発明が解決しようとする課題】生分解性組成物におい
て、重要な物性は生分解性、強度、伸び等である。しか
し、これらの物性に加えて、成形品に加工する場合の加
熱溶融時の流動性が良好であることも実用上重要であ
る。生分解性組成物を実用するに当たり、従来から成形
品に加工されている合成樹脂、例えば、ポリスチレン等
と同程度の流動性を有することが好ましい。ところが、
これまでは、澱粉系生分解性組成物の開発に当たり、流
動性についてあまり注目されていなかった。The important physical properties of a biodegradable composition are biodegradability, strength, elongation and the like. However, in addition to these physical properties, it is also practically important that the fluidity at the time of heating and melting when processing into a molded article is good. In practical use of the biodegradable composition, it is preferable that the composition has the same fluidity as a synthetic resin conventionally processed into a molded article, for example, polystyrene or the like. However,
Heretofore, in developing starch-based biodegradable compositions, much attention has been paid to fluidity.
【０００５】先行技術１および２に開示された澱粉糊化
物、さらには、先行技術３〜６に記載された加工澱粉に
おいては、加熱溶融時の流動性が不十分であった。その
ため、押し出し成形により、簡単な形状の成形物、例え
ば、シート等を得ることはある程度可能であったが、射
出成形により複雑な形状の物品を成形しようとする場
合、流動性不良により、所望の形状の成形物を得ること
は困難であった。[0005] The gelatinized starch disclosed in Prior Art 1 and 2, and the processed starch described in Prior Art 3 to 6, have insufficient fluidity during heating and melting. For this reason, it was possible to obtain a molded product having a simple shape, for example, a sheet, by extrusion molding to some extent. However, when molding an article having a complicated shape by injection molding, it was difficult to obtain a desired product due to poor fluidity. It was difficult to obtain a shaped article.
【０００６】そこで本発明の第１の目的は、澱粉糊化物
を用いる生分解性組成物であって、加熱溶融時の流動性
が改善され、成形が容易である生分解性成形品用の組成
物を提供することにある。さらに本発明の第２の目的
は、加熱溶融時の流動性が改善され、成形加工を容易に
行える澱粉糊化物を含む生分解性成形品の製造方法を提
供することにある。Accordingly, a first object of the present invention is a biodegradable composition using a gelatinized starch, which has improved fluidity during heating and melting, and is easy to mold. To provide things. Further, a second object of the present invention is to provide a method for producing a biodegradable molded article containing a gelatinized starch, which has improved fluidity during heating and melting and can be easily molded.
【０００７】[0007]
【課題を解決するための手段】本発明は、酸化処理した
澱粉糊化物を含有することを特徴とする生分解性成形品
用組成物に関する。本発明の生分解性成形品用組成物
は、酸化処理した澱粉糊化物からなる態様および酸化処
理した澱粉糊化物と生分解性樹脂とを含む態様を含むも
のである。SUMMARY OF THE INVENTION The present invention relates to a composition for a biodegradable molded article characterized by containing a gelatinized starch which has been oxidized. The composition for a biodegradable molded article of the present invention includes an embodiment comprising an oxidized starch gelatinized product and an embodiment comprising an oxidized starch gelatinized product and a biodegradable resin.
【０００８】さらに本発明は、澱粉を水および酸化剤、
又は水、可塑剤および酸化剤、又は可塑剤および酸化剤
と加熱混合し、得られた混合物を所望の形状に成形する
ことを特徴とする生分解性成形品の製造方法に関する。
さらに本発明は、澱粉を水、酸化剤および生分解性樹
脂、又は水、可塑剤、酸化剤および生分解性樹脂、又は
可塑剤、酸化剤および生分解性樹脂と加熱混合し、得ら
れた混合物を所望の形状に成形することを特徴とする生
分解性成形品の製造方法に関する。[0008] The present invention further provides a starch and water and an oxidizing agent,
Alternatively, the present invention relates to a method for producing a biodegradable molded product, which comprises heating and mixing with water, a plasticizer and an oxidizing agent, or a plasticizer and an oxidizing agent, and molding the resulting mixture into a desired shape.
Further, the present invention is obtained by heating and mixing starch with water, an oxidizing agent and a biodegradable resin, or water, a plasticizer, an oxidizing agent and a biodegradable resin, or a plasticizer, an oxidizing agent and a biodegradable resin. The present invention relates to a method for producing a biodegradable molded product, which comprises molding a mixture into a desired shape.
【０００９】生分解性成形品用組成物 本発明の生分解性成形品用組成物は酸化処理した澱粉糊
化物を含有するものである。酸化処理した澱粉糊化物
は、澱粉の酸化処理と糊化とを並行して行うことにより
得ることができる。上記酸化処理と糊化の原料として用
いる澱粉は、特に制限なくいずれの澱粉も用いることが
できる。例えば、馬鈴薯澱粉、コーンスターチ、甘薯澱
粉、タピオカ澱粉、サゴヤシ澱粉、米澱粉、小麦澱粉な
どの未加工澱粉、さらには、各種エステル化澱粉、エー
テル化澱粉等の加工澱粉等を挙げることができる。 Composition for Biodegradable Molded Article The composition for biodegradable molded article of the present invention contains gelatinized starch which has been oxidized. The oxidized starch gelatinized product can be obtained by performing starch oxidizing treatment and gelatinization in parallel. Any starch can be used as a raw material for the oxidation treatment and gelatinization without any particular limitation. For example, raw starches such as potato starch, corn starch, potato starch, tapioca starch, sago palm starch, rice starch, wheat starch, and processed starches such as various esterified starches, etherified starches and the like can be mentioned.
【００１０】澱粉の酸化処理と糊化とは、例えば、澱粉
を水および酸化剤、又は水、可塑剤および酸化剤と加熱
混合することにより行うことができる。酸化剤を共存さ
せることで酸化処理を澱粉糊化と同時に行うことがで
き、得られる組成物の加熱溶融時の流動性を改善するこ
とができる。上記酸化剤としては、例えば、過酸化物を
用いることができる。過酸化物としては、例えば、過硫
酸カリウム、過硫酸アンモニウム、過硫酸ナトリウムか
らなる群から選ばれる過硫酸塩又は過酸化水素を用いる
ことができる。酸化剤の使用量は、澱粉（乾物基準）１
００重量部当たり０．０１〜０．５０重量部の範囲とす
ることが適当である。好ましくは、０．０２〜０．１０
重量部の範囲である。尚、酸化剤の種類および量は、得
られる組成物の流動性を考慮して適宜変化させることが
できる。The oxidation treatment and gelatinization of starch can be carried out, for example, by heating and mixing starch with water and an oxidizing agent or with water, a plasticizer and an oxidizing agent. By coexisting the oxidizing agent, the oxidizing treatment can be performed simultaneously with the starch gelatinization, and the fluidity of the obtained composition at the time of heating and melting can be improved. As the oxidizing agent, for example, a peroxide can be used. As the peroxide, for example, a persulfate or hydrogen peroxide selected from the group consisting of potassium persulfate, ammonium persulfate, and sodium persulfate can be used. The amount of oxidizing agent used is starch (dry matter basis) 1
It is appropriate that the amount is in the range of 0.01 to 0.50 parts by weight per 00 parts by weight. Preferably, 0.02 to 0.10
It is in the range of parts by weight. The type and amount of the oxidizing agent can be appropriately changed in consideration of the fluidity of the obtained composition.
【００１１】上記のように、澱粉を、酸化剤に加えて、
水、可塑剤、又は水および可塑剤の共存下で加熱混合す
ることにより澱粉糊化物が得られる。澱粉の糊化は水単
独又は可塑剤単独の存在下で行うことが出来る。また、
水と可塑剤との存在下でも澱粉を糊化することができ、
この場合水の使用量も低減でき、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
より澱粉糊化物と生分解性樹脂との混合及び成形を容易
に出来ると言う利点もある。As mentioned above, starch is added to an oxidizing agent,
By heating and mixing in the presence of water, a plasticizer, or water and a plasticizer, a starch gelatinized product is obtained. Gelatinization of starch can be performed in the presence of water alone or a plasticizer alone. Also,
Starch can be gelatinized even in the presence of water and a plasticizer,
In this case, the amount of water used can be reduced, which is effective in preventing foaming during molding. Furthermore, there is also an advantage that mixing and molding of the starch gelatinized product and the biodegradable resin can be facilitated by including a plasticizer in the gelatinized product.
【００１２】糊化に用いられる可塑剤は澱粉を糊化出
来、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
げることが出来る。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 gelatinization is not particularly limited as long as it can gelatinize starch and can impart plasticity to the gelatinized product, and examples thereof include a high-boiling plasticizer having biodegradability. Examples of such plasticizers include ethylene glycol, propylene glycol, glycerin, sorbitol, polyethylene glycol, polypropylene glycol and the like.
【００１３】糊化に水を用いる場合には、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 starch (dry matter basis) from the viewpoint of sufficiently gelatinizing the starch. More preferably, 10 to 20 parts by weight of water is used per 100 parts by weight of starch (based on dry matter), from the viewpoint of sufficiently gelatinizing the starch and preventing foaming when added to the biodegradable composition and molded. Appropriate.
【００１４】また、糊化に水と可塑剤を用いる場合に
は、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、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, 0.1 to 40 parts by weight of starch (based on dry matter) is used.
It is appropriate to use 1 part by weight of water and 1 to 100 parts by weight of a plasticizer from the viewpoint that starch can be sufficiently gelatinized and sufficient plasticity can be imparted to the gelatinized product. More preferably, 0.1 to 100 parts by weight of starch (based on dry matter) is used.
The use of 20 parts by weight of water and 5 to 40 parts by weight of a plasticizer can sufficiently gelatinize the starch, prevent foaming when added to the biodegradable composition and molding, and provide a gelatinized material. It is appropriate from the viewpoint that appropriate plasticity can be imparted.
【００１５】また、糊化に可塑剤のみを用いる場合に
は、澱粉（乾物基準）１００重量部当たり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、澱粉（乾物基準）１
００重量部当たり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、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 only a plasticizer is used for gelatinization, it is preferable to use 1 to 100 parts by weight of a plasticizer per 100 parts by weight of starch (based on dry matter) to sufficiently gelatinize the starch,
It is also suitable from the viewpoint that sufficient plasticity can be imparted to the gelatinized product. Further preferably, starch (on a dry matter basis)
The use of 5 to 40 parts by weight of a plasticizer per 100 parts by weight is appropriate from the viewpoint that the starch can be sufficiently gelatinized and that the gelatinized product can be imparted with appropriate plasticity.
【００１６】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。[0016] The gelatinization of starch generally means 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 starch gelatinized product in the present invention refers to one that does not substantially exhibit crystallinity and birefringence. The loss of crystallinity and birefringence can be determined by observing the starch granules with a polarizing microscope and observing the presence of a polarizing cross crossing at the center of formation of ungelatinized starch.
【００１７】澱粉の酸化処理および糊化のための加熱混
合は、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。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
出し機を用いて行うことができる。加熱混合により、酸
化処理した澱粉糊化物からなる、本発明の生分解性成形
品用組成物を得ることができる。得られる組成物は、例
えばペレット化しておき、生分解性成形品の製造の際に
このペレットを使用することができる。The heating and mixing for oxidizing and gelatinizing the starch can be appropriately determined depending on the type of starch, the type of plasticizer when a plasticizer is used, and the amounts of water and plasticizer added. For example, it is appropriate to carry out at 60 to 220 ° C. for 10 to 60 minutes. The heating and mixing can be performed using, for example, a pressure kneader or an extruder. By heating and mixing, the composition for a biodegradable molded article of the present invention, which is made of an oxidized starch gelatinized product, can be obtained. The obtained composition is pelletized, for example, and the pellet can be used in the production of a biodegradable molded article.
【００１８】また、酸化処理した澱粉糊化物と生分解性
樹脂とを含む本発明の生分解性成形品用組成物は、例え
ば、ペレット状の上記酸化処理した澱粉糊化物と生分解
性樹脂と混合することにより得ることが出来る。本発明
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 composition for a biodegradable molded article of the present invention containing an oxidized starch gelatinized product and a biodegradable resin is, for example, a pellet-like oxidized starch gelatinized product and a biodegradable resin. It can be obtained by mixing. The biodegradable resin used in 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.
【００１９】本発明の生分解性成形品用組成物には、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。添加剤としては、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出来る。The composition for a biodegradable molded article of the present invention may optionally contain additives in addition to the above-mentioned components. Examples of the additives include vegetable protein, pulp, ultraviolet stabilizer, fungicide, herbicide, fertilizer, antioxidant, surfactant, pigment and the like.
【００２０】生分解性成形品の製造方法 本発明の生分解性成形品の製造方法は、生分解性成形品
が酸化処理した澱粉糊化物のみからなる場合は、上記生
分解性成形品用組成物の場合と同様に、澱粉を水および
酸化剤、又は水、可塑剤および酸化剤、又は可塑剤およ
び酸化剤と加熱混合した後、得られる混合物を所望の形
状に成形することにより行うことができる。成形品への
成形は、例えば、射出成形や押出成形等を用いて行うこ
とができる。また、酸化処理した澱粉糊化物と生分解性
樹脂を含む生分解性成形品の製造は、澱粉を水、酸化剤
および生分解性樹脂、又は水、可塑剤、酸化剤および生
分解性樹脂、又は可塑剤、酸化剤および生分解性樹脂と
加熱混合し、得られた混合物を所望の形状に成形するこ
とにより行うことができる。成形品への成形は、上記と
同様に、例えば、射出成形や押出成形等を用いて行うこ
とができる。 Process for Producing a Biodegradable Molded Product The process for producing a biodegradable molded product of the present invention is characterized in that, when the biodegradable molded product comprises only oxidized starch gelatinized product, As in the case of the product, the starch is heated and mixed with water and an oxidizing agent, or with water, a plasticizer and an oxidizing agent, or a plasticizer and an oxidizing agent, and then the resulting mixture is formed into a desired shape. it can. The molding into a molded article can be performed using, for example, injection molding, extrusion molding, or the like. In addition, in the production of a biodegradable molded article containing an oxidized starch gelatinized product and a biodegradable resin, the starch is treated with water, an oxidizing agent and a biodegradable resin, or water, a plasticizer, an oxidizing agent and a biodegradable resin, Alternatively, it can be carried out by heating and mixing with a plasticizer, an oxidizing agent and a biodegradable resin, and molding the resulting mixture into a desired shape. Molding into a molded article can be performed using, for example, injection molding, extrusion molding, or the like, similarly to the above.
【００２１】いずれの場合も、澱粉、酸化剤、可塑剤、
生分解性樹脂としては、生分解性成形品用組成物の場合
と同様のものを用いることができる。また、澱粉に対す
る酸化剤、可塑剤および水の使用量についても、生分解
性成形品用組成物の場合と同様にすることができる。成
形品の形状には特に制限はなく、生分解性を利用できる
いずれの用途の成形品、例えば、洗剤等の容器、使い捨
て食器等を挙げることができる。In each case, starch, oxidizing agent, plasticizer,
As the biodegradable resin, the same one as in the case of the composition for a biodegradable molded article can be used. In addition, the amounts of the oxidizing agent, the plasticizer, and the water used for the starch can be the same as in the case of the composition for a biodegradable molded article. The shape of the molded article is not particularly limited, and examples include molded articles for any use that can utilize biodegradability, such as containers for detergents, disposable tableware, and the like.
【００２２】[0022]
【発明の効果】本発明によれば、澱粉糊化物を用いる生
分解性組成物であって、加熱溶融時の流動性が改善さ
れ、成形が容易である生分解性成形品用の組成物を提供
することができる。特に、本発明の生分解性成形品用組
成物は射出成形によっても成形することができる。さら
に本発明によれば、加熱溶融時の流動性が改善され、成
形加工を容易に行える澱粉糊化物を含む生分解性成形品
の製造方法を提供することができる。本発明の製造方法
では、射出成形によっても成形することができる。According to the present invention, there is provided a biodegradable composition using a gelatinized product of starch, which has improved fluidity during heating and melting and is easy to mold. Can be provided. In particular, the composition for a biodegradable molded article of the present invention can be molded by injection molding. Further, according to the present invention, it is possible to provide a method for producing a biodegradable molded article containing a gelatinized starch product, which has improved fluidity during heating and melting and facilitates molding. In the production method of the present invention, molding can also be performed by injection molding.
【００２３】本発明による流動性の改善は、少量の酸化
剤を用い、糊化と並行して行える（追加の工程が不要で
ある）ことから、安いコストで行うことができる。澱粉
や澱粉糊化物に比べて高価である生分解性樹脂に複合化
させる場合、流動性が改善されることから、澱粉糊化物
（酸化処理した）の配合率を増加させることができ、そ
の結果、生分解性樹脂成形品の価格を低減することがで
きる。本発明の酸化処理した澱粉糊化物は流動性が改善
され、その結果、種々の複合組成物に対して高率で配合
することができる。その結果、複合組成物の生分解性を
促進でき（澱粉糊化物の有する生分解性は生分解性樹脂
より高いから）、生分解性複合組成物の応用範囲を汎用
樹脂並みに拡大させることが可能となる。The improvement of the fluidity according to the present invention can be carried out at low cost because a small amount of an oxidizing agent can be used in parallel with the gelatinization (an additional step is not required). When complexed with a biodegradable resin that is more expensive than starch or gelatinized starch, the flowability is improved, and the compounding ratio of gelatinized starch (oxidized) can be increased. In addition, the price of the biodegradable resin molded product can be reduced. The oxidized starch gelatinized product of the present invention has improved fluidity, and as a result, can be blended with various composite compositions at a high rate. As a result, the biodegradability of the composite composition can be promoted (because the biodegradability of the starch gelatinized product is higher than that of the biodegradable resin), and the application range of the biodegradable composite composition can be expanded to the level of general-purpose resins. It becomes possible.
【００２４】[0024]
【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１〜３ コーンスターチ（乾物基準）１００重量部当、水１５重
量部、グリセリン２０重量部に、過硫酸アンモニウム
０．０２重量部、０．０６重量部、または０．１０重量
部を加えた。これら混合物を堅型ミキサー（関東混合機
工業製関東ミキサー）にて低速、中速、高速にて各１分
間ずつ混合した。上記混合物を一軸押し出し機（プラス
トグラフ）を用いて下記条件にて直径約４ｍｍの棒状に
押し出し加工した。その後ハサミで長さ約０．５〜１ｃ
ｍのペレット状にカットした。The present invention will be further described with reference to the following examples. Examples 1 to 3 To 100 parts by weight of corn starch (based on dry matter), 15 parts by weight of water, and 20 parts by weight of glycerin, 0.02 parts by weight, 0.06 parts by weight, or 0.10 parts by weight of ammonium persulfate was added. These mixtures were mixed for 1 minute each at a low speed, a medium speed, and a high speed using a rigid mixer (Kanto mixer manufactured by Kanto Blender Co., Ltd.). The mixture was extruded into a rod having a diameter of about 4 mm using a uniaxial extruder (plastograph) under the following conditions. Then use scissors about 0.5-1c in length
m in the form of pellets.
【００２５】 スクリュー Ｌ／Ｄ２５（一軸） 回転数 ６０r.p.m ダイ ６φ 温度 ZONE１：ZONE２：ZONE３＝５０℃：１３
０℃：５０℃Screw L / D25 (uniaxial) Rotational speed 60 rpm Die 6φ Temperature ZONE1: ZONE2: ZONE3 = 50 ° C.:13
0 ° C: 50 ° C
【００２６】比較例１ 過硫酸カリウムを添加しなかった以外は、実施例１と同
様にしてペレット状組成物を得た。 比較例２ 市販のポリスチレンレット（旭化成（株）製スタイロン
６００）を用いた。Comparative Example 1 A pellet composition was obtained in the same manner as in Example 1 except that potassium persulfate was not added. Comparative Example 2 A commercially available polystyrene ret (Stylon 600 manufactured by Asahi Kasei Corporation) was used.
【００２７】[0027]
【表１】 [Table 1]
【００２８】実施例１〜３および比較例１〜２で調製し
たペレットの熱流動性をフローテスター（島津製作所製
ＣＦＴ５００Ｃ）を用いて昇温法により調べた。測定方
法としては、長さ２ｃｍ、直径１ｍｍのダイを用い、荷
重を５０ｋｇｆにし、５℃／ｍｉｎの昇温速度にて５０
℃〜２００℃の範囲で測定した。各温度における溶融粘
度の結果を図１に、フローレート（剪断速度）の結果を
図２に示す。即ち、ごく少量の酸化剤を添加した実施例
１〜３は、酸化剤を添加していない比較例１に比べて溶
融粘度が低下して、流動性が改善され、それらは比較例
２のごとき汎用ポリスチレンと同等であることが認めら
れた。The thermal fluidity of the pellets prepared in Examples 1 to 3 and Comparative Examples 1 and 2 was examined by a temperature rising method using a flow tester (CFT500C manufactured by Shimadzu Corporation). As a measuring method, a die having a length of 2 cm and a diameter of 1 mm was used, the load was set to 50 kgf, and the temperature was increased at a rate of 5 ° C./min.
It measured in the range of ° C-200 ° C. FIG. 1 shows the results of the melt viscosity at each temperature, and FIG. 2 shows the results of the flow rate (shear rate). That is, in Examples 1 to 3 in which only a small amount of the oxidizing agent was added, the melt viscosity was reduced and the fluidity was improved as compared with Comparative Example 1 in which the oxidizing agent was not added. It was found to be equivalent to general purpose polystyrene.
【００２９】実施例４ コーンスターチ（乾物基準）１００重量部当、水２０重
量部、ポリエチレングリコール１５重量部、過硫酸カリ
ウム０．０４重量部をヘンシェルミキサー（三井三池化
工機製）にとり、６００r.p.m ５分間攪拌し混合した。
これを下記押出機、条件にてペレット化した。 押出機名 東洋精機（株）製ラボプラストミル 型式 ２軸押出機２Ｄ２５Ｓ スクリュー Ｌ／Ｄ＝２５（２軸） 温度 ZONE 1:ZONE 2:ZONE 3:ZONE 4 ＝50℃：60
℃： 120℃： 100℃ ダイ ３φ ペレッタイザー 東洋精機（株）製コールドカットペレ
ッタイザーPETEC 型Example 4 100 parts by weight of corn starch (based on dry matter), 20 parts by weight of water, 15 parts by weight of polyethylene glycol, and 0.04 parts by weight of potassium persulfate were placed in a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) and the mixture was mixed at 600 rpm. Stir and mix for minutes.
This was pelletized using the following extruder and conditions. Extruder name Toyo Seiki Co., Ltd. Labo Plastomill Model Twin screw extruder 2D25S Screw L / D = 25 (two screws) Temperature ZONE 1: ZONE 2: ZONE 3: ZONE 4 = 50 ° C: 60
° C: 120 ° C: 100 ° C Die 3φ Pelletizer Cold cut pelletizer made by Toyo Seiki Co., Ltd. PETEC type
【００３０】上記条件で得た澱粉ペレットを日精樹脂工
学（株）製射出成形機、植木鉢成形金型を用いて下記条
件にて射出成形し、成形品を得た。 加熱筒設定温度 ノズル 150℃ 前部 155℃ 中間部
145℃ 後部 120℃ 金型表面温度 ２０℃ 射出時間 ３秒The starch pellets obtained under the above conditions were injection-molded under the following conditions using an injection molding machine manufactured by Nissei Resin Engineering Co., Ltd. and a flowerpot molding die to obtain a molded product. Heating cylinder set temperature Nozzle 150 ° C Front 155 ° C Middle
145 ° C Rear 120 ° C Mold surface temperature 20 ° C Injection time 3 seconds
【００３１】比較例３ 過硫酸カリウム添加を添加しなかった以外は実施例４と
同様にしてペレットおよび成形品を得た。Comparative Example 3 Pellets and molded articles were obtained in the same manner as in Example 4 except that potassium persulfate was not added.
【００３２】[0032]
【表２】 [Table 2]
【００３３】実施例５ 実施例４で得たペレット５０重量部と、ダイセル化学工
業株式会社製ポリカプロラクトン（プラクセルＨ７）５
０重量部とを混合し、日精樹脂工学（株）製射出成形
機、植木鉢成形金型を用いて下記条件にて射出成形試験
を行い成形品を得た。 加熱筒設定温度 ノズル 150℃、前部 155℃、中間部
145℃、後部 120℃ 金型表面温度 ２０℃ 射出時間 ３秒Example 5 50 parts by weight of the pellets obtained in Example 4 and polycaprolactone (Placcel H7) 5 manufactured by Daicel Chemical Industries, Ltd.
And 0 parts by weight, and subjected to an injection molding test under the following conditions using an injection molding machine and a flowerpot molding die manufactured by Nissei Plastics Engineering Co., Ltd. to obtain a molded product. Heating cylinder set temperature Nozzle 150 ° C, front 155 ° C, middle
145 ° C, rear 120 ° C Mold surface temperature 20 ° C Injection time 3 seconds
【００３４】比較例４ 過硫酸カリウム添加を添加しなかった以外は実施例５と
同様にして成形品を得た。Comparative Example 4 A molded product was obtained in the same manner as in Example 5 except that potassium persulfate was not added.
【００３５】[0035]
【表３】 [Table 3]
【図１】 実施例１〜３および比較例１および２の各組
成物の各温度における溶融粘度を示す。FIG. 1 shows the melt viscosity at each temperature of each composition of Examples 1 to 3 and Comparative Examples 1 and 2.
【図２】 実施例１〜３および比較例１および２の各組
成物の各温度におけるフローレート（剪断速度）を示
す。FIG. 2 shows a flow rate (shear rate) at each temperature of each composition of Examples 1 to 3 and Comparative Examples 1 and 2.
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Claims (12)
を含有することを特徴とする生分解性成形品用組成物。1. A composition for a biodegradable molded article, comprising a gelatinized oxidized starch and a biodegradable resin.
処理と糊化とを並行して行って得たものである請求項１
記載の組成物。2. The starch gelatinized product subjected to the oxidation treatment is obtained by performing the starch oxidation treatment and the gelatinization in parallel.
A composition as described.
び酸化剤、又は水、可塑剤および酸化剤、又は可塑剤お
よび酸化剤と加熱混合することにより行う請求項２記載
の組成物。3. The composition according to claim 2, wherein the starch is oxidized and gelatinized by heating and mixing the starch with water and an oxidizing agent, or with water, a plasticizing agent and an oxidizing agent, or a plasticizing agent and an oxidizing agent. .
組成物。4. The composition according to claim 3, wherein the oxidizing agent is a peroxide.
モニウム、過硫酸ナトリウムからなる群から選ばれる過
硫酸塩又は過酸化水素である請求項４記載の組成物。5. The composition according to claim 4, wherein the peroxide is a persulfate or hydrogen peroxide selected from the group consisting of potassium persulfate, ammonium persulfate, and sodium persulfate.
０１〜０．５０重量部の酸化剤を用いる請求項２〜５の
いずれか１項に記載の組成物。6. An amount of 0.1% by weight per 100 parts by weight of starch (based on dry matter).
6. The composition according to claim 2, wherein the oxidizing agent is used in an amount of from 0.01 to 0.50 parts by weight.
〜５０重量部の水、又は澱粉(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、又と澱粉(乾物基準)１００重量部当たり１〜１０
０重量部の可塑剤を用いる請求項２〜６のいずれか１項
に記載の組成物。7. 10 parts per 100 parts by weight of starch (based on dry matter)
0.1 to 40 parts by weight of water and 1 to 100 parts by weight of plasticizer per 100 parts by weight of water or starch (based on dry matter) or 1 to 10 parts by weight per 100 parts by weight of starch (based on dry matter)
The composition according to any one of claims 2 to 6, wherein 0 parts by weight of a plasticizer is used.
又は水、可塑剤、酸化剤および生分解性樹脂、又は可塑
剤、酸化剤および生分解性樹脂、と加熱混合し、得られ
た混合物を所望の形状に成形することを特徴とする生分
解性成形品の製造方法。8. The method of claim 1, wherein the starch is water, an oxidizing agent and a biodegradable resin.
Or biodegradable characterized by heating and mixing with water, a plasticizer, an oxidizing agent and a biodegradable resin, or a plasticizer, an oxidizing agent and a biodegradable resin, and forming the resulting mixture into a desired shape. Manufacturing method of molded article.
製造方法。9. The method according to claim 8, wherein the oxidizing agent is a peroxide.
ンモニウム、過硫酸ナトリウムからなる群から選ばれる
過硫酸塩又は過酸化水素である請求項９記載の製造方
法。10. The method according to claim 9, wherein the peroxide is a persulfate or hydrogen peroxide selected from the group consisting of potassium persulfate, ammonium persulfate, and sodium persulfate.
０．０１〜０．５０重量部の酸化剤を用いる請求項８〜
１０のいずれか１項に記載の製造方法。11. The method according to claim 8, wherein the oxidizing agent is used in an amount of 0.01 to 0.50 parts by weight per 100 parts by weight of the starch (based on dry matter).
The production method according to any one of items 10 to 10.
０〜５０重量部の水、又は澱粉(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、または澱粉(乾物基準)１００重量部当たり１〜
１００重量部の可塑剤を用いる請求項８〜１１のいずれ
か１項に記載の製造方法。12. 1 to 100 parts by weight of starch (based on dry matter)
0 to 50 parts by weight of water or 0.1 to 40 parts by weight of water per 100 parts by weight of starch (based on dry matter) and 1 to 100 parts by weight of a plasticizer or 1 to 100 parts by weight of starch (based on dry matter)
The method according to any one of claims 8 to 11, wherein 100 parts by weight of a plasticizer is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07203489A JP3078478B2 (en) | 1995-08-09 | 1995-08-09 | Composition for biodegradable molded article and method for producing biodegradable molded article |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07203489A JP3078478B2 (en) | 1995-08-09 | 1995-08-09 | Composition for biodegradable molded article and method for producing biodegradable molded article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0952901A JPH0952901A (en) | 1997-02-25 |
| JP3078478B2 true JP3078478B2 (en) | 2000-08-21 |
Family
ID=16475012
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07203489A Expired - Fee Related JP3078478B2 (en) | 1995-08-09 | 1995-08-09 | Composition for biodegradable molded article and method for producing biodegradable molded article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3078478B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013073402A1 (en) | 2011-11-15 | 2013-05-23 | 昭和電工株式会社 | Biodegradable resin composition, and biodegradable film |
| WO2013073403A1 (en) | 2011-11-15 | 2013-05-23 | 昭和電工株式会社 | Biodegradable resin composition, and biodegradable film |
| WO2016158331A1 (en) | 2015-04-02 | 2016-10-06 | Showa Denko K.K. | Resin composition and its film |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5053716B2 (en) * | 2007-05-31 | 2012-10-17 | 昭和電工株式会社 | Multilayer film |
| US9376648B2 (en) | 2008-04-07 | 2016-06-28 | The Procter & Gamble Company | Foam manipulation compositions containing fine particles |
-
1995
- 1995-08-09 JP JP07203489A patent/JP3078478B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013073402A1 (en) | 2011-11-15 | 2013-05-23 | 昭和電工株式会社 | Biodegradable resin composition, and biodegradable film |
| WO2013073403A1 (en) | 2011-11-15 | 2013-05-23 | 昭和電工株式会社 | Biodegradable resin composition, and biodegradable film |
| US9441105B2 (en) | 2011-11-15 | 2016-09-13 | Showa Denko K.K. | Biodegradable resin composition, and biodegradable film |
| WO2016158331A1 (en) | 2015-04-02 | 2016-10-06 | Showa Denko K.K. | Resin composition and its film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0952901A (en) | 1997-02-25 |
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