JPH08134266A - Water-resistant plant polymer composition and its production - Google Patents

Abstract

PURPOSE: To improve the biodegradability, water resistance, and strengths of a plant polymer component by mixing it with water, a compatibilizer, and a modifier, molding the mixture, and degassing, drying, and thermally modifying the resulting molded item. CONSTITUTION: 100 pts.wt. plant polymer component comprising 50-90wt.% starch and 50-10wt.% fibers is compounded with at least 10 pts.wt. water, 540 pts.wt. volatile compatibilizer having a b.p. of 75-160 deg.C, and 0.1-20 pts.wt. modifier, heated to 80-140 deg.C, and vigorously mixed. The resulting compsn. is molded at 100 deg.C or lower or at 120-180 deg.C and degassed and dried, giving a molded item having a water content of 10wt.% or lower. The item is thermally modified at 160-220 deg.C in the state of being fastened tightly or left open.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明は、澱粉と植物繊維物を主
体とする耐水性を付与した植物高分子の複合構造組成物
にあり、従来の汎用合成樹脂成形分野や紙分野に同様に
用いて有用で且つ使用後の廃棄物は生分解性であり形態
崩壊が容易で環境を阻害しない植物高分子耐水組成物及
びその製法に関する。FIELD OF THE INVENTION The present invention relates to a composite structure composition of starch and a plant polymer mainly composed of vegetable fibers and imparting water resistance, and is used in the conventional general-purpose synthetic resin molding field and paper field. The present invention relates to a plant polymer water-resistant composition which is useful as a waste, is biodegradable after use, is easy to disintegrate, and does not disturb the environment, and a method for producing the same.

【０００２】[0002]

【従来の技術】石油を原料とする合成樹脂や再生産より
急速な消費で森林資源を圧迫している紙パルプなどは有
限の資源に立脚していると云へる。回収再生・消費節減
が叫ばれているが資源・環境保全には人工栽培資源例え
ば農産物などの大量生産資源への転換が必要であり究極
のところであろう。一方、合成樹脂の廃棄物は環境汚染
となり特に包装物流分野での合成樹脂製品廃棄物の分別
・回収・再生資源化は環境保全からも当面する重要な課
題であるが、廃棄処理技術などの諸課題は多岐過大であ
ってその対応は模索段階と云える現状である。2. Description of the Related Art It can be said that synthetic resins made from petroleum and paper pulp, which presses forest resources by consuming them more rapidly than reproduction, is based on limited resources. Although there is a call for recovery, regeneration, and consumption reduction, it will be the ultimate because it is necessary to convert to artificially cultivated resources such as agricultural products for mass production in order to conserve resources and the environment. On the other hand, synthetic resin waste becomes environmental pollution, and sorting, recovery, and recycling of synthetic resin product waste, especially in the field of packaging and logistics, is an important issue from the viewpoint of environmental protection. The challenges are numerous and overwhelming, and the current situation can be said to be how to deal with them.

【０００３】そこで近々澱粉（スターチ）や繊維素（セ
ルロース）を用いた成形体で、合成樹脂成形物や紙分野
に使用し、使用後廃棄物の自然分解する生分解性材料の
製品技術が提案されている。澱粉には、アイスクリーム
のコーンカップ状の耐水性を補ったとされるコーン容器
（パッキング）、澱粉や化工澱粉とポリエチレン・ポリ
ビニルアルコール系など合成高分子とのブレンド・複合
技術、生分解高分子の製出技術及び天然・合成高分子と
のブレンド、セルロース繊維及び誘導体とキトサン・ポ
リビニルアルコール系などの天然・合成高分子との組合
せ複合技術などがある。また旧来から澱粉・セルロース
は、酸化・エステル化・エーテル化・グラフト化・架橋
など化学反応や熱・機械的な物理変性によって多くの化
工澱粉・セルロース誘導体が発達して市場を形成してお
り、今日では環境問題に対応する新規な誘導体及び添加
複合の技術提案も見当る。Therefore, a product technology of a biodegradable material, which is a molded product using starch (starch) or fibrin (cellulose), will be used in the field of synthetic resin molded products and paper, and the waste will naturally decompose after use is proposed. Has been done. For starch, a cone container (packing) that is said to have supplemented the water resistance of ice cream in a cone cup, blending / combining technology of starch and modified starch and synthetic polymer such as polyethylene / polyvinyl alcohol, and biodegradable polymer Production technology and blending with natural / synthetic polymers, combination technology of cellulosic fibers and derivatives with natural / synthetic polymers such as chitosan / polyvinyl alcohol. Traditionally, starch / cellulose has formed a market with many modified starch / cellulose derivatives developed by chemical reactions such as oxidation / esterification / etherification / grafting / crosslinking and thermal / mechanical physical modification. Today, we can find new derivative and additive composite technology proposals that address environmental problems.

【０００４】[0004]

【本発明が解決しようとする課題】澱粉・セルロースな
ど植物高分子の成形物は、程度の化学物理的な修飾を施
しても汎用合成樹脂成形物に比較し、水に溶解したり湿
潤状態での強度が低下するなどの耐水性に、また被膜力
が劣る機械強度に、一方では成形加工製品化の諸技術に
開発を要する点があるなどの諸課題がある。また、耐水
・強度・成形加工性を改善するには、煩雑な処理工程や
高価格な物質添加を要し、なお物理・強度や廃棄物処理
に問題が残るものも多く、概して植物高分子主体の製品
は価格／物性が汎用合成樹脂成形品に劣ることは否めな
い現状と云える。即ち、澱粉やセルロースなど植物高分
子主体の成形物を汎用合成樹脂成形物や紙製品と同様に
使用できる物性／価格とし、且つ使用後の廃棄物が簡単
容易に生分解し形態崩壊するなど環境阻害のないことが
望まれる。A molded product of a plant polymer such as starch or cellulose is more soluble in water or wet than a general-purpose synthetic resin molded product even if it is chemically and physically modified to some extent. There are various problems such as water resistance such as decrease in strength, mechanical strength such as inferior film strength, and development of various technologies for forming processed products. In addition, in order to improve water resistance, strength and molding processability, complicated treatment steps and addition of expensive materials are required, and many problems still remain in physical strength, strength and waste treatment. It can be said that the price / physical properties of these products are inferior to those of general-purpose synthetic resin molded products. In other words, molded products mainly composed of plant polymers such as starch and cellulose should be used in the same physical properties / price as general-purpose synthetic resin molded products and paper products, and wastes after use may be easily biodegraded and form collapsed. No inhibition is desired.

【０００５】[0005]

【問題を解決するための手段】上記の観点から研究検討
の結果、澱粉と合成樹脂とのブレンド・複合、生分解性
高分子の合成やその応用など従来の手法と異り、成形加
工性に優れ耐水性・強度など諸物性が得られ安価容易に
大量生産できる澱粉と繊維物との植物高分子による従来
にない耐水組成物に着目した。[Means for solving the problem] As a result of research and study from the above viewpoints, unlike conventional methods such as blending / compositing starch and synthetic resin, synthesizing biodegradable polymer and its application, molding processability is different. We focused on an unprecedented water-resistant composition that uses plant polymers of starch and fibers, which have various properties such as excellent water resistance and strength and can be mass-produced inexpensively and easily.

【０００６】澱粉・植物繊維物に配合水と相溶剤を混合
して８０〜１４０℃で強力に混練分散すれば、糊化澱粉
中に繊維物は均質に分散し、相溶剤も寄与して繊維物と
糊化澱粉は親和密着する。これを成形乾燥すれば糊化澱
粉は植物繊維物に密着凝集して接着固化する。次いで乾
燥状態で加熱すれば澱粉は解重合・再結合し、膨潤性を
失いカラメル化焼成も始り、一方植物繊維物は加熱分解
活性化するなどの状態の植物高分子密着複合構造物とな
る。このとき変性剤があり澱粉・植物繊維物に共架橋自
体の架橋・その他の反応結合が生じたと思われることに
より、飛躍的に強い耐水性と強度が増大された組成物と
なる。When the starch / vegetable fiber material is mixed with the compounding water and the compatibilizer and strongly kneaded and dispersed at 80 to 140 ° C., the fiber material is homogeneously dispersed in the gelatinized starch, and the compatibilizer also contributes to the fiber. The substance and gelatinized starch are closely adhered to each other. When this is molded and dried, the gelatinized starch is adhered and agglomerated to the plant fiber material to be adhered and solidified. Then, by heating in a dry state, the starch depolymerizes and recombines, loses its swelling property, and begins caramelization and calcination, while the plant fiber material becomes a plant-polymer-adhesive composite structure in a state of being activated by thermal decomposition. . At this time, there is a modifier and it is considered that co-crosslinking itself or other reactive bonds have occurred in the starch / vegetable fiber material, resulting in a composition having dramatically improved water resistance and strength.

【０００７】この組成物は常態の微生物が少い環境では
湿度が高くとも形状・強度など物性に変化のない耐水性
から実用的に水に呈んど影響されない耐水性が得られ、
また機械的強度などの諸物性も向上する。この植物高分
子耐水組成物は物性／価格が汎用合成樹脂や紙製品に匹
敵すること並びに廃棄物は簡単な処理で生分解・形態崩
壊が容易で環境を阻害しない処理が可能であることを見
出し本発明を完成するに至った。[0007] In the environment where there are few normal microorganisms, this composition provides water resistance that is not affected by water and is practically unaffected by water resistance that does not change physical properties such as shape and strength even when humidity is high.
Also, various physical properties such as mechanical strength are improved. We have found that this plant-polymer water-resistant composition has physical properties / price comparable to general-purpose synthetic resins and paper products, and waste can be easily decomposed into biodegradable and morphologically degrading substances that do not hinder the environment. The present invention has been completed.

【０００８】即ち本発明は澱粉と繊維物との植物高分子
に配合水・相溶剤・変性剤を必須配合として、混練分散
・脱気成形乾燥・加熱変成することを特徴とする植物高
分子耐水組成物及びその製法にあり、更には必要に応じ
組成物表面に耐水性を強化する提案である。。[0008] That is, the present invention is a plant polymer water-resistant, characterized by kneading dispersion, degassing, molding drying and heat denaturation, in which water, a compatibilizer, and a modifier are inevitably blended with a plant polymer of starch and fibers. It is in the composition and its manufacturing method, and further, it is a proposal to enhance water resistance on the surface of the composition if necessary. .

【０００９】以下に本発明を詳細に説明する。本明細書
記載の％は重量％（ｗｔ％）である、部は重量部（ＰＨ
Ｒ）の略記であり、植物高分子１００（重量）部に対す
る配合物の（重量）部である。The present invention will be described in detail below. In this specification,% means% by weight (wt%), part means part by weight (PH
R) is an abbreviation, and is (weight) part of the compound with respect to 100 (weight) part of the plant polymer.

【００１０】組成物澱粉と繊維物の植物高分子、配合
水、相溶剤、変性剤、及び無機微粉物、ラテックス等、
滑剤、着色剤、発泡剤、安定剤などであり、耐水合成樹
脂膜である。Composition Starch and fibrous plant polymer, compounding water, compatibilizer, modifier, inorganic fine powder, latex, etc.
It is a water resistant synthetic resin film such as a lubricant, a coloring agent, a foaming agent and a stabilizer.

【００１１】植物高分子 澱粉及び化工澱粉５０〜９０
％と農産廃棄物・葦・竹などの禾本科植物を主とする植
物繊維物５０〜１０％で構成する。澱粉５０％以下では
繊維物など添加組成物全体を均質に分散親和密着して空
隙などなく覆うことが不可能となり、また繊維物１０％
以下では本要旨の糊化澱粉・植物繊維の密着複合構造か
ら得られる強度・耐水性など諸物性が得難くなるので澱
粉５０〜９０％繊維物５０〜１０％とした。他の天然動
植物由来の高分子及び誘導体は使用量も少く相溶剤の可
撓剤水溶性高分子に包含する。Plant Polymer Starch and Modified Starch 50-90
% And 50 to 10% of plant fiber materials mainly composed of agricultural waste, reeds, bamboo and other plants belonging to the family. If the starch content is 50% or less, it is impossible to cover the entire additive composition such as the fibrous material in a homogeneously dispersed and closely adhered state without voids, and the fibrous material is 10%.
In the following, it is difficult to obtain various physical properties such as strength and water resistance obtained from the adhered composite structure of gelatinized starch / vegetable fiber of the present gist, so the starch is 50 to 90% and the fiber material is 50 to 10%. Polymers and derivatives derived from other natural animals and plants are included in the flexible solvent water-soluble polymer which is a compatibilizer in a small amount used.

【００１２】澱粉 トウモロコシ（コーン）・コメ・ム
ギなど穀類、バレイショ（ポテト）・カンショ・タピオ
カなどイモ類（根茎類）、豆類など澱粉含有植物または
これらから製出した通常の任意の澱粉即ち澱粉を主とす
る粉体であり、小麦粉（うどん粉）・米粉・コーンスタ
ーチ・ポテトスターチ・大豆粉・片栗粉などである。食
料品の如く精製・微粉にする必要はなく混練分散によっ
て均質な糊化澱粉となるならば制限はないが粉粒径２０
０μφ以下が好ましい。Starch Grains such as corn (corn), rice and wheat, potatoes (rhizomes) such as potato (potato), sweet potato, tapioca, beans and other starch-containing plants, or any ordinary starch produced from them, that is, starch The main powders are wheat flour (udon powder), rice flour, cornstarch, potato starch, soybean flour, potato starch and the like. It is not necessary to purify and pulverize it like food products, and there is no limitation as long as it becomes a homogeneous gelatinized starch by kneading and dispersing.
It is preferably 0 μφ or less.

【００１３】化工澱粉 混練分散を容易に均質な糊化澱
粉を形成し繊維物との接着強度を向上するデキストリン
・酸処理澱粉・α−澱粉など分解・物理変性型の汎用化
工澱粉を澱粉配合量の５０％以下を置換使用する場合も
ある。化工澱粉のうち特に重要なものは接着強度向上に
耐水性を加えた耐水澱粉誘導体であり、例えば澱粉の２
ケ所以上の水酸基に多官能基を結合（架橋）させた誘導
体ホルムアルデヒド・エピクロヒドリン・リン酸・アク
ロレイン・ジイソシアネートなどの架橋澱粉、水酸基に
疎水基の導入の高分子グラフト共重合澱粉・アリル澱粉
・ベンジル澱粉など耐水性の澱粉誘導体を表層に用いる
ことがあり、配合量は表層澱粉の０〜１００％を置換え
ることができる。Modified starch Starch compounded general-purpose modified starch of degradable / physically modified type such as dextrin / acid-treated starch / α-starch that easily forms a homogeneous gelatinized starch by kneading and dispersing to improve the adhesive strength with fiber materials. In some cases, 50% or less may be replaced and used. A particularly important one of the modified starches is a water-resistant starch derivative in which water resistance is added to improve the adhesive strength.
Derivatives in which polyfunctional groups are bonded (crosslinked) to hydroxyl groups above or above crosslinked starches such as formaldehyde, epichlorohydrin, phosphoric acid, acrolein, diisocyanate, polymer graft copolymerized starch with introduced hydrophobic groups in hydroxyl groups, allyl starch, benzyl starch A water-resistant starch derivative may be used for the surface layer, and the compounding amount can replace 0 to 100% of the surface starch.

【００１４】繊維物 ワラ・バガス・トウモロコシなど
の茎葉や籾殻・ヤシ繊維などの種子物の農産廃棄物並び
に竹・葦などの禾本科植物を主に木粉・枝葉・小材木な
ど木材系も用いられる。これら植物繊維物はセルロース
・ヘミセルロース・リグニンなどでなる天然植物をその
まま洗浄・乾燥・切断し粉砕機やリファイナーなどで短
繊維を目標に軽るく粗砕・磨砕して、比較的粗大な機械
パルプ状の短繊維を得ると共に微細繊維や粒粉物とが発
生するがこれら総てを本（植物）繊維物とする。一般に
漂白して用いるが漂白しない場合もある。セルロース誘
導体は繊維物に含まない。Fiber materials Agricultural wastes such as foliage of straw, bagasse, corn, etc. and seeds of rice husk, coconut fiber, etc. To be These plant fiber materials are relatively coarse machines that wash, dry and cut natural plants made of cellulose, hemicellulose, lignin, etc. as they are and then crush and grind short fibers lightly with a crusher or refiner etc. Fine fibers and granules are generated as well as pulp-like short fibers are obtained, and all of them are used as book (vegetable) fibers. Generally, it is used after bleaching, but it may not be bleached. The cellulose derivative is not included in the fiber material.

【００１５】短繊維と粒粉物の大きさ分布は径６０μｍ
以下長さ５ｍｍ以下の短繊維４０〜９０％と径６０μｍ
粒粉物６０〜１０％であり、粉砕・磨砕や混合の処理方
法によって予測し製造することが可能で種々の繊維物が
構成できる。大きさ分布の選定は短繊維・粒粉物の径が
製品厚みの１／５以下で１／１０以下が主であることが
大凡その目安であり、例えば後記する実施例に用いる繊
維物は、表層及び単層に径１０μｍ以下で径５μｍ長さ
２０μｍ以上のものが８５％以上の短繊維８０％と径１
０μｍ以下で３〜６μｍのものが９５％以上の粒粉物２
０％の構成の繊維物が、内層に径５０μｍ以下で径２０
μｍ長さ８０μｍ以上のものが８０％以上の短繊維７０
％と径５０μｍで径５〜２０μｍのものが９０％以上の
粒粉物２０％の構成の繊維物が用いられている。The size distribution of short fibers and granules is 60 μm in diameter.
40 to 90% of short fibers with a length of 5 mm or less and a diameter of 60 μm
Granular powder is 60 to 10%, which can be predicted and manufactured by a processing method such as crushing / grinding or mixing, and various fiber materials can be constituted. The general rule of thumb for selecting the size distribution is that the diameter of the short fiber / granular powder is ⅕ or less and 1/10 or less of the product thickness. For example, the fiber materials used in the examples described below are 80% or more of 85% or more short fibers with a diameter of 10 μm or less, a diameter of 5 μm, and a length of 20 μm or more, and a diameter of 1
95% or more of granular powder 2 having a size of 0 μm or less and 3 to 6 μm 2
A fiber material with a composition of 0% has a diameter of 50 μm or less and a diameter of 20
80% or more of short fibers 70 having a length of 80 μm or more
% And 50 μm in diameter and 5 to 20 μm in diameter are used as fiber materials having a composition of 90% or more and 20% of granular powder.

【００１６】上記の如く繊維物は農産廃棄物や竹・葦な
ど禾本科植物の未利用資源を主に使用し、粉砕・磨砕に
発生する微細繊維・粒粉物も使用して収率を高め、比較
的粗大で分布幅も大きく許容されて加工費も低減できる
などを特徴とする繊維物である。As described above, the fibrous material mainly uses the unutilized resources of agricultural plants such as agricultural wastes, bamboo and reeds, and the fine fiber / granular material generated during crushing / grinding is also used to increase the yield. It is a fiber product characterized by being relatively high, relatively coarse, and having a wide distribution width, which can reduce processing costs.

【００１７】水分（配合・含水量） 使用する水は飲料
水程度のものならば問題なく使用でき蒸留水・浄化処理
水などはより好適で不純物が少い程好ましい。配合水は
１０部以上としているが混練分散には組成の１５％程度
使用が一般でありまた稀釈増量（糊化澱粉溶液化）は混
練後配合水を添加することが多い。１６０〜２２０℃加
熱変性は含水量が組成の１０％以下で実施するので含水
は加熱気化発泡して組成物は実質的に風乾状態で加熱変
成すると想定している。Moisture (blending / water content) Water used can be used without problem as long as it is drinking water, and distilled water, purified water, etc. are more preferable, and the smaller the amount of impurities, the more preferable. The compounding water is 10 parts or more, but about 15% of the composition is generally used for kneading and dispersion, and the compounding water is often added after kneading to increase the dilution amount (solution of gelatinized starch). Since the heat denaturation at 160 to 220 ° C. is carried out at a water content of 10% or less of the composition, it is assumed that the water content is vaporized and foamed by heating so that the composition is heat-denatured in a substantially air-dried state.

【００１８】上記水分の量は総ての水分を含むものであ
る。例えば澱粉の通常１２〜１７％程度の含水・植物繊
維物の湿潤量・ラテックスなど水分も測定（または計算
・乾燥）して配合水量に含まれる。従って記載の澱粉や
ラテックス量は澱粉や樹脂分のみの重量である。The above amount of water includes all water. For example, the water content of starch is usually about 12 to 17%, the wet amount of vegetable fiber, and the water content of latex are also measured (or calculated and dried) and included in the blended water content. Therefore, the amount of starch and latex described is the weight of starch and resin only.

【００１９】相溶剤 組成配合物に親和相溶性で糊化澱
粉生成を促進し植物繊維物へ浸透親和密着し組成物の接
着強度など諸物性向上に相溶寄与する物質である。配合
分散に必要充分に使用し水分の蒸発除去と共に蒸発する
蒸発（相溶）剤０〜２０部、組成物に浸透含浸して残存
し接着強度など諸物性に資し相溶可撓性あるいは反応変
性もある可撓剤は多価アルコール系及び／または水溶性
高分子であり配合量は５〜３０部である。蒸発相溶剤は
必要に応じ用いられ相溶剤の総配合量は５〜４０部であ
る。A compatibilizer is a substance that is compatible with the composition formulation, promotes the formation of gelatinized starch, adheres to the plant fiber material with permeation affinity, and compatibilizes to improve various physical properties such as the adhesive strength of the composition. 0 to 20 parts of an evaporation (compatibility) agent that is used sufficiently and sufficiently for compounding dispersion and evaporates with the removal of water by evaporation, remains impregnated and impregnated in the composition, and contributes to various physical properties such as adhesive strength. The flexible agent which is also modified is a polyhydric alcohol and / or a water-soluble polymer, and the compounding amount is 5 to 30 parts. The evaporation compatibilizer is used as necessary, and the total amount of the compatibilizing agents is 5 to 40 parts.

【００２０】蒸発剤 沸点７５〜１６０℃のアルコール
系物質であり、例えばエタノール・ｎ−プロパノール・
ｎ・ヘキサノール・シクロヘキサノールなどである。Evaporating agent An alcoholic substance having a boiling point of 75 to 160 ° C., such as ethanol / n-propanol /
Examples include n-hexanol and cyclohexanol.

【００２１】可撓剤・多価アルコール系 ＢＰ１９０℃
以上の多価アルコールとその誘導体は、エチレングリコ
ール〜重合度１０００までのポリエチレングリコールと
そのエーテル・アセテート、プロピレンにグリコール〜
重合度５００までのポリプロピレングリコールとそのエ
ーテル・アセテート、グリセリン・グリセリンジアセテ
ート・グリセリントリアセテートなどグリセリンとその
アセテートである。Flexible agent / polyhydric alcohol BP 190 ° C
The above polyhydric alcohols and their derivatives are ethylene glycol ~ polyethylene glycol up to a degree of polymerization of 1000 and its ether acetates, propylene glycol ~
Glycerin and its acetate such as polypropylene glycol having a degree of polymerization of up to 500 and its ether / acetate and glycerin / glycerin diacetate / glycerin triacetate.

【００２２】可撓剤・水溶性高分子 天然高分子にアル
ギン酸ナトリウム（金属塩）の海藻類、天然ゴム・アラ
ビヤゴムなど植物粘質物、グルテン・カゼイン・ゼラチ
ンなど蛋白質、キチン・キトサンなど動物質などであ
る。半合成物に酢酸・メタクリル酸・コハク酸などの有
機酸エステルセルロース、エチルセルロース・カルボキ
シメチルセルロースなどセルロースエーテルのセルロー
ス誘導体、合成物にポリビニルアルコールとエチレン・
酢ビケン化物などの誘導体、ポリエチレンオキシド、ポ
リアクリル酸ナトリウムなどである。Flexible agents / water-soluble polymers Natural polymers such as seaweed of sodium alginate (metal salt), plant mucilages such as natural rubber and arabic gum, proteins such as gluten, casein and gelatin, and animal substances such as chitin and chitosan is there. Organic compounds such as acetic acid, methacrylic acid and succinic acid cellulose as semi-synthetic products, cellulose derivatives of cellulose ethers such as ethyl cellulose and carboxymethyl cellulose, synthetic products as polyvinyl alcohol and ethylene
Derivatives such as a vinegarized vinegar, polyethylene oxide, sodium polyacrylate and the like.

【００２３】変性剤 植物高分子１００部に対し、表層
に１〜２０部、内層に０．１〜５部を配合使用する。１
６０〜２００°の加熱によって化学反応しまた配合組成
物の熱分解活性化に呼応して共架橋・自体の架橋・その
他の反応変性を生じ耐水・強度など諸物性を向上する物
質である。共架橋剤０．１〜２０部・有機過酸化物０〜
５部・酸その他０〜１０部で構成し、変性剤総配合量は
０．１〜２０部である。Modifier: 1 to 20 parts of the surface layer and 0.1 to 5 parts of the inner layer are used in combination with 100 parts of the plant polymer. 1
It is a substance that undergoes a chemical reaction by heating at 60 to 200 ° C., and in response to thermal decomposition activation of the compounding composition, causes co-crosslinking, crosslinking of itself, and other reaction modification to improve various properties such as water resistance and strength. Co-crosslinking agent 0.1 to 20 parts, organic peroxide 0 to
It is composed of 5 parts, an acid and 0 to 10 parts, and the total amount of the modifier is 0.1 to 20 parts.

【００２４】共架橋剤 トリアリルイソシアヌレート
ジアリルフタレートなどのアリル化合物、ポリエチレン
グリコールジメタクリレート・トリメチロールプロパン
トリメタクリレート・アルミニウムメタクリレートなど
のメタクリル酸化合物、同様のアクリル酸化合物、Ｎ・
Ｎ−メチレンビスアクリルアミド・ジビニルベンゼンな
どこれらの類系の多官能物質である。Co-crosslinking agent triallyl isocyanurate
Allyl compounds such as diallyl phthalate, methacrylic acid compounds such as polyethylene glycol dimethacrylate / trimethylolpropane trimethacrylate / aluminum methacrylate, similar acrylic acid compounds, N.
These are polyfunctional substances of these types such as N-methylenebisacrylamide and divinylbenzene.

【００２５】有機過酸化物 １４０℃で半減期を得る時
間が３０分以上である。例えばジクミルパーオキシド・
ｔ−ブチルパーオキシド・２・５−ジ−ｔ−ブチルパー
オキシヘキサン・ジ−ｔ−ブチルパーオキシドなど必要
に応じ０〜５部用いられる。Organic peroxide The half-life time at 140 ° C. is 30 minutes or more. For example, dicumyl peroxide
If necessary, 0 to 5 parts of t-butyl peroxide, 2,5-di-t-butylperoxyhexane, di-t-butyl peroxide, etc. may be used.

【００２６】酸その他 フタル酸・コハク酸・マレイン
酸などの高級脂肪酸とその無水物、ジイソシアネート、
酸化亜鉛・二酸化ケイ素など金属酸化物、不飽和シラン
化合物などである。Acids and Others Higher fatty acids such as phthalic acid, succinic acid and maleic acid, and their anhydrides, diisocyanates,
Examples include metal oxides such as zinc oxide and silicon dioxide, and unsaturated silane compounds.

【００２７】無機微粉物 混練分散に際して植物繊維物
の絡り凝集を防止して均一分散や解繊・微細化を助長し
また組成物の剛性向上などの補強や着色効果（いんぺい
力）に寄与し、組成配合物との混練・加熱変成に変質し
ない非相溶の固体であり、配合・分散が良好な物質であ
る。例えば炭酸カルシウム・タルク・クレー・アルミナ
・ガラス粉・スラグ・金属粉などの粒粉物、マイカなど
薄片状物の平均粒径が５０μ以下の無機微粉物である。
配合量は植物高分子１００部に対し３０部以下である。Inorganic fine powder When kneading and dispersing, it prevents entanglement and aggregation of plant fiber materials, promotes uniform dispersion, defibration and micronization, and contributes to reinforcement such as improvement in rigidity of the composition and coloring effect (impermeability). The composition is a non-compatible solid that does not deteriorate by kneading with the composition / mixture and heat denaturation, and is a substance with good composition / dispersion. For example, it is a granular powder such as calcium carbonate, talc, clay, alumina, glass powder, slag, and metal powder, or an inorganic fine powder having a mean particle size of 50 μm or less such as mica.
The compounding amount is 30 parts or less with respect to 100 parts of the plant polymer.

【００２８】ラテックス等 必要に応じ表層に配合し、
混練分散・成形・乾燥・加熱変性して組成物に安定混在
するか表面に樹脂膜を構成するラテックス例えば天然ゴ
ム・ポリ酢酸ビニル系・スチレン−ブタジェン系・アク
リル系のラテックス及び樹脂とその共重合体の乳化物で
ある。Latex, etc. may be added to the surface layer if necessary,
Kneading dispersion / molding / drying / heat denaturation to allow stable mixing in the composition or latex forming a resin film on the surface, for example, natural rubber / polyvinyl acetate / styrene-butadiene / acrylic latex and resin and its co-weight It is a combined emulsion.

【００２９】滑剤 配合して安定に混在し混練成形時に
離型など成形加工性を良好にしあるいは順次分離滲出し
て表面疎水性もあるなどの物質であり、ステアクリル酸
モノグリセライドなど脂肪酸エステル・脂肪酸アルカノ
ールアミドなどの非イオン界面活性剤、シリコーンラテ
ックスなどである。Lubricants are substances that are mixed stably to improve moldability such as mold release during kneading molding, or that are leached out in sequence and have surface hydrophobicity. Steric acid monoglyceride and other fatty acid esters / fatty acid alkanols. Examples include nonionic surfactants such as amides and silicone latex.

【００３０】その他 着色剤は酸化チタン（ホワイト）
など無機系であり主に表層に用いられる。発泡剤は分解
温度１４０℃以上の有機・無機分解型発泡剤を使用す
る。酸化防止剤・紫外線防止剤などその他樹脂用の配合
剤が用いられる。Other colorants are titanium oxide (white)
It is an inorganic type and is mainly used for the surface layer. As the foaming agent, an organic / inorganic decomposition type foaming agent having a decomposition temperature of 140 ° C. or higher is used. Other compounding agents for resins such as antioxidants and ultraviolet ray inhibitors are used.

【００３１】耐水合成樹脂膜 請求項３の積層構成する
耐水樹脂膜は、組成物表面の部分に即ち組成物表面の全
体を覆うこと無く、水に接する面とか湿潤状態に長時間
接する面とかに積層する。（シート状の場合には片面に
積層する場合が多い）ポリエチレン・ポリプロピレン及
コーポリマを含むオレフイン樹脂・ビニル樹脂などの透
湿度〔ＪＩＳ防湿包装材の透湿試験法Ｚ０２０８〕１０
０ｇ／ｍ^２・２４ｈｒ・４０℃・９０ｐＨ（０．０２５
ｍｍ厚）以下である熱可塑性合成樹脂薄膜でり、厚み
０．２ｍｍ以下好ましくは０．０５ｍｍ以下である。フ
イルム状の接着積層・溶融押出コート・溶液やラテック
スの塗布などによって組成物表面の部分に積層する。積
層は加熱（加圧）接着するが、加熱（加圧）しない場合
やより積層接着を強くするには酢酸ビニル系・ウレタン
系・ブタジエン系などの接着剤を用いたり組成物表面を
火炎・コロナ放電など処理する。Water-Resistant Synthetic Resin Film The laminated water-resistant resin film according to claim 3 is formed on the surface of the composition, that is, on the surface which is in contact with water or the surface which is in a wet state for a long time without covering the entire surface of the composition. Stack. (In the case of sheet form, it is often laminated on one side) Moisture vapor transmission rate of olefin resin, vinyl resin, etc. containing polyethylene / polypropylene and copolymer [JIS Moisture Permeability Testing Method Z0208] 10
0 g / m ² · 24 hr · 40 ° C · 90 pH (0.025
The thickness is 0.2 mm or less, preferably 0.05 mm or less. The composition is laminated on the surface of the composition by film-like adhesive lamination, melt extrusion coating, application of solution or latex, and the like. Laminates are heated (pressurized) bonded, but when not heated (pressurized) or to strengthen the adhesion of the laminate, vinyl acetate / urethane / butadiene adhesives are used or the surface of the composition is exposed to flame / corona. Discharge and treat.

【００３２】製法 植物高分子に配合水・相溶剤・変性
剤・無機微粉物・その他配合物を表層（スキン層）と内
層（コアー層）など配合組成毎に混練押出機・密閉槽混
練機で強力に混練分散し、次いで諸成形法によって脱気
成形乾燥し、加熱変性して本発明耐水組成物とする。更
には表面耐水増強処理することもある。Manufacturing method Mixing water, a compatibilizer, a modifier, an inorganic fine powder, and other compounds into a plant polymer with a kneading extruder or a closed tank kneader for each composition such as the surface layer (skin layer) and the inner layer (core layer). The mixture is strongly kneaded and dispersed, then degassed by various molding methods, dried, and heat-denatured to obtain the water resistant composition of the present invention. Further, surface water resistance enhancement treatment may be performed.

【００３３】混練分散 所要配合物を同時か順次常温で
混合し、水分など蒸発を抑制して８０〜１４０℃の温度
範囲で強力に混練し、澱粉を配合水１０部以上の存在に
よって糊化し所要粘度の糊化澱粉溶液（溶体）とする。
混練温度が８０℃以下では良好な糊化澱粉の生成が難し
く配合組成物の親和密着も不充分となり、また１４０℃
以上では澱粉や配合組成物が分解・反応・変性が発生す
ることもあり混練分散に支障が起り始めるので混練温度
範囲を８０〜１４０℃とした。好適な混練温度は１１０
〜１３０℃である。Kneading and Dispersion The required compounds are mixed simultaneously or sequentially at room temperature, and the mixture is strongly kneaded in the temperature range of 80 to 140 ° C. while suppressing evaporation of water and the starch is gelatinized by the presence of 10 parts or more of compounding water. Use a gelatinized starch solution (solution) of viscosity.
When the kneading temperature is 80 ° C. or lower, it is difficult to form a good gelatinized starch, and the affinity adhesion of the compounding composition becomes insufficient, and 140 ° C.
In the above, since the starch, the compounded composition, or the like may be decomposed, reacted, or modified to cause a trouble in kneading and dispersion, the kneading temperature range was set to 80 to 140 ° C. Suitable kneading temperature is 110
~ 130 ° C.

【００３４】混練分散を良好にする配合水は植物高分子
１００部に対し１０部以上であり、組成の含水量は成形
に必要な最低水量で少い程望ましいが混練分散・親和密
着を良好にするには含水量１５％程度以上が一般であ
る。糊化澱粉溶液粘度を低くする場合・澱粉量が少い場
合（植物繊維物や無機微粉物が多い場合）・分散性の劣
る配合物のある場合、などには必要適宜に配合水（含水
量）や蒸発（相溶）剤を増量して配合物相互に空隙など
なく親和密着・均質分散が充分に達成できるようにす
る。また混練前に配合物を常温で混合することは容易に
良好な混練分散が可能となる。Mixing water for good kneading / dispersion is 10 parts or more per 100 parts of the plant polymer, and the water content of the composition is preferably the minimum amount of water required for molding. To achieve this, the water content is generally about 15% or more. When the viscosity of gelatinized starch solution is reduced, when the amount of starch is small (when there are many plant fiber substances or inorganic fine powder substances), when there is a compound with poor dispersibility, etc. ) Or an evaporative (compatibility) agent is added so that affinity adhesion and homogeneous dispersion can be sufficiently achieved without forming voids between the compounds. Further, mixing the compound at room temperature before kneading enables easy kneading and dispersion.

【００３５】混練分散装置は熱可塑性合成樹脂と同様の
装置が適用できる。ローターなどを有する高剪断混練ス
クリューの２軸・１軸混練押出機が好適であり、混練押
出機は加熱ゾーン毎に温水など循環またはヒーター加熱
して最高温度１４０℃で強力に充分に混練する。混練押
出機以外にはニーダー・インテンシブミキサーあるいは
高速混合機など密閉混合槽とした密閉槽混合機で水分量
を調整して加熱混練し冷却して使用する。以上当該混練
分散は合成樹脂に比較して低い混練温度・粘度であり、
混練分散効率は良好である。As the kneading and dispersing device, the same device as for the thermoplastic synthetic resin can be applied. A twin-screw / single-screw kneading extruder having a high shear kneading screw having a rotor or the like is suitable, and the kneading extruder circulates hot water in each heating zone or heats with a heater to knead strongly and sufficiently at a maximum temperature of 140 ° C. In addition to the kneading extruder, a kneader / intensive mixer, a high-speed mixer, or a closed-vessel mixer such as a high-speed mixer, which is a closed-vessel mixer, is used to adjust the water content, heat-knead, and cool. As described above, the kneading dispersion has a lower kneading temperature and viscosity as compared with the synthetic resin,
The kneading and dispersing efficiency is good.

【００３６】混練押出機の混練物は混練機に直結（タン
デム配列）する成形押出機や混練機に増設する装置即ち
押出機能によって１００℃以下の低温成形か１２０℃以
上で高温成形する。また混練終了後に冷却水を圧入混合
稀釈して冷却し含水量１５％以上１００゜以下の糊化澱
粉溶液として溶液成形に供する。（混練前・混練中に稀
釈することもある。）ニーダー・インテンシブミキサー
など密閉槽混合機は混練後冷水を注入して混合稀釈冷却
して溶液成形に供する糊化澱粉溶液製造に用いられるこ
とが多い。The kneaded product of the kneading extruder is subjected to low temperature molding at 100 ° C. or lower or high temperature molding at 120 ° C. or higher depending on a molding extruder directly connected to the kneading machine (tandem arrangement) or a device added to the kneading machine, that is, an extrusion function. Further, after the kneading, cooling water is press-mixed and diluted to cool, and the mixture is subjected to solution molding as a gelatinized starch solution having a water content of 15% or more and 100 ° or less. (May be diluted before and during kneading.) A closed tank mixer such as a kneader / intensive mixer is used for the preparation of gelatinized starch solution in which cold water is injected after mixing and the mixture is diluted and cooled for solution formation. Many.

【００３７】低温成形 ８０〜１４０℃混練物は、混練
押出機と吐出口（ダイ）との間に外筒に冷却水を循環す
る所要長さの単管（スタテックミキサー内装もる）で混
練物を冷却調質する冷却装置や冷却する成形押出機を混
練押出機に直結しタンデム配列して１００℃以下で単層
に成形製出する。またこれらの押出装置を２系列以上設
置して１００℃以下で積層に成形製出（積層押出）す
る。この低温成形物は１００℃以下で乾燥し所要含水量
にして１６０〜２２０℃で加熱変性する。Low-temperature molding 80-140 ° C. The kneaded product is kneaded with a single pipe of a required length (including a static mixer internal) for circulating cooling water in an outer cylinder between a kneading extruder and a discharge port (die). A cooling device for cooling and refining the material and a molding extruder for cooling are directly connected to the kneading extruder and arranged in tandem to form a single layer at 100 ° C. or less. Further, two or more series of these extruders are installed and molded and produced into a laminate (lamination extrusion) at 100 ° C. or less. The low-temperature molded product is dried at 100 ° C. or lower to a required water content, and heat-denatured at 160 to 220 ° C.

【００３８】フイルム・シート・プレートなど平面状成
形物（以下シート状物と称す）はＴダイで単層にフイー
ドブロック〜Ｔダイ・マルチマニホールドダイを用いて
積層に製出し乾燥する。また冷却混練物を１００℃以下
のロール間に供給しロール圧延しつつ水分を蒸発し所要
水分量の単層シート状物とすることもできる。積層シー
ト状物は上記積層押出以外に単層からの方法があり、乾
燥した表層配合シートを捲取っておき乾燥内層配合シー
トの両面か片面に繰出し積層する方法、乾燥内層配合シ
ートの両面か片面に表層配合の糊化澱粉溶液を塗布また
は吹付けて積層乾燥する方法がある。A flat molded article such as a film sheet plate (hereinafter referred to as a sheet material) is produced by T die in a single layer from a feed block to a T die multi-manifold die to be laminated and dried. It is also possible to supply the cooled kneaded product between rolls at 100 ° C. or less and evaporate the water while rolling to obtain a single-layer sheet having a required water content. There is a method from a single layer for the laminated sheet material other than the above-mentioned laminated extrusion, a method of winding a dried surface layer compounding sheet and feeding it to both sides or one side of the dry inner layer compounding sheet, and laminating, a surface layer on both sides or one side of the dry inner layer compounding sheet. There is a method in which a gelatinized starch solution having a composition is applied or sprayed and laminated and dried.

【００３９】シート状物の１６０〜２２０℃の加熱変性
には、２本の支持ロールで緊張回転するエンドレスコン
ペアベルトを相対に設置し２帯ベルト間隙に乾燥シート
状物を狹締保持して加熱加圧し加熱変性する相対エンド
レスベルト装置により、実質的に密閉状態で加熱（加
圧）できるので、ベルト間隙を一定で無発泡にベルト間
隙を開いて発泡状態に制禦可能であり、組成の含水量と
相溶剤量による硬軟や加熱変性方法など自由に設定でき
る。ドラム（大口径ロ一ル）加熱や炉内般送加熱など開
放加熱は含水量を組成のＩ０％以下のできる限り低い含
水量とし１４０℃以下から逐次１６０〜２００℃に加熱
し変性して発泡シート状物とするが含水量を低く押へて
も発泡を免れることはできない。For heat denaturation of the sheet material at 160 to 220 ° C., two endless compare belts which rotate by tension with two supporting rolls are installed relative to each other, and the dried sheet material is clamped and held in the gap between the two belts and heated. Since the relative endless belt device that pressurizes and heat-denatures can heat (pressurize) in a substantially closed state, it is possible to open the belt gap to a non-foaming state with a constant belt gap and to control the foaming state. Hardness and softness depending on the amount of water and the amount of compatibilizer, and heat denaturation method can be freely set. Opening heating such as drum (large-diameter roll) heating and furnace internal heating is performed by setting the water content to the lowest possible water content of 10% or less of the composition and heating from 140 ° C or less to 160 to 200 ° C to modify and foam. Although it is a sheet-like material, foaming cannot be escaped even if the water content is low.

【００４０】低温成形乾燥（変性加熱前）の単層・積層
シート状物を裁断し絞り加工して内外型に狹締密閉して
加熱変性して単層・積層の容器など成形品の植物高分子
耐水組成物にする方法があり、裁断により発生する打抜
きカスは可逆性であり混練機で容易に再使用できる。内
外型挾締加熱によって発泡や変性するので接着剤は必要
なくコーナー部の補強もでき型通りの製品が得られる・
離型は高温で可能であり金型は冷却しないなど高生産性
であるなどの特徴を有するシート加工容器成形法があ
る。A single-layer / laminated sheet material that has been low-temperature molded and dried (before denaturation heating) is cut, drawn, squeezed and sealed in inner and outer molds, and heat-denatured to form a single-layer / laminated container. There is a method of making a molecular water resistant composition, and punching dust generated by cutting is reversible and can be easily reused in a kneader. Foaming and denaturing due to clamping heat inside and outside molds, no adhesive is needed and corners can be reinforced, resulting in a product as it is.
There is a sheet processing container forming method which has a feature that the mold release can be performed at a high temperature, the mold is not cooled, and the productivity is high.

【００４１】押出分岐−多層クロスヘットなどを用いて
ペレット状やパイプや異形断面諸形状に低温成形して乾
燥・加熱変性する緩衝材などの製法、低温成形ペレット
を保管後型内などで加熱変性発泡する諸形状成形物とす
る方法、その場合型を石膏・木・強化硝子などを用いて
高周波加熱によって発泡加熱変性することも有効な方法
である。Extrusion branching-Manufacturing method such as a cushioning material which is formed into a pellet shape, a pipe or various cross-sectional shapes at low temperature by using a multi-layer cross-head and dried and heat-denatured, and low-temperature molded pellets are heat-denatured in a mold after storage. It is also an effective method to form various shaped molded articles that foam, in which case the mold is subjected to foaming heat modification by high frequency heating using gypsum, wood, reinforced glass or the like.

【００４２】高温成形 混練押出機に加熱成形押出機を
直結しタンデム配列するか混練押出機に加熱成形部を増
設して混練物を１２０〜１８０℃でベント脱気して常態
へ押出製出する。水分含有の製出組成物は直ちに水分が
蒸発噴気して製出物の形状を整えることが難しく、一方
高温押出しは無含水とか僅少含水では高粘性・脆性とな
り押出製出は至難である。故に押出時気化発泡を押へ製
出物形状を調整するには、含水量を組成の１０％以下と
して含水量と相溶剤（可撓剤）との合計が１０％以上、
空気・水を吹付けるエアーナイフ・冷却サイジングダイ
・水槽これらの組合せを押出吐出口（リップ）に近接設
置、（ダイリップ・吐出組成物の冷却）、押出組成物に
架橋など変性が無いか僅少の望ましくは１６０℃以下で
製出などの制禦によって１２０〜１８０℃高温押出し製
出を可能とすることができ、調質された発泡組成物が得
られる。高温成形は含水気化によって乾燥工程を呈んど
必要なく生産上有利である。High-temperature molding The kneading extruder is directly connected to the heat-molding extruder and arranged in tandem, or a heat-molding section is added to the kneading extruder to vent the degassed kneaded product at 120 to 180 ° C. to extrude the kneaded product to a normal state. . In a water-containing production composition, it is difficult to immediately evaporate and eject water to adjust the shape of the product. On the other hand, high-temperature extrusion is highly viscous and brittle with little or no water, and extrusion production is extremely difficult. Therefore, in order to adjust the shape of the output product by pushing the vaporization foaming at the time of extrusion, the water content is set to 10% or less of the composition, and the total of the water content and the compatibilizer (flexible agent) is 10% or more,
An air knife that blows air and water, a cooling sizing die, and a water tank are installed close to the extrusion discharge port (lip), (die lip and discharge composition cooling), and there is little or no modification such as crosslinking in the extrusion composition. Desirably, high-temperature extrusion production at 120 to 180 ° C. can be made possible by controlling production at 160 ° C. or lower, and a tempered foam composition can be obtained. High-temperature molding is advantageous in production because it does not require a drying step due to water vaporization.

【００４３】上記制禦によっても１２０〜１８０℃高温
押出しは単層成形することが一般であり、シート状物・
発泡プレート・後記する押込（射出）成形物は内層配合
高温押出し調質後、表層配合糊化溶液を塗布・吹付けて
乾燥し加熱変性することが多い。押出混練加熱成形押出
装置を２系列以上での積層押出しは、丸棒・ペレット・
異形諸形状を１２０〜１６０℃でクロスヘットダイ−冷
却装置によって比較的良好に製造することが可能であ
る。有効な高温成形として単層の薄いシート状（フイル
ム）の製造があり、表層配合に準じて耐水配合し、押出
Ｔダイ製出口でエアーナイフと冷却ロール及び冷却サイ
ジングダイで急冷し、直ちに１８０〜２２０℃ロール間
で加熱加圧し更に緊張して加熱・ロール間加熱加圧して
加熱変性することによって品質良好に効率的に薄いシー
ト状（フイルム）が得られる。Due to the above control, it is general that the high temperature extrusion at 120 to 180 ° C. is a single layer molding.
In many cases, the foamed plate and the indentation (injection) molded product to be described later are heat-denatured by coating and spraying a gelatinizing solution containing the surface layer, followed by drying after heat-treating the mixture with the inner layer. Extruding, kneading, heating, molding, and extruding machines with two or more series
The deformed shapes can be produced relatively well at 120-160 ° C. with a crosshead die-cooling device. As an effective high temperature molding, there is a production of a single thin sheet (film), water resistant blending according to the blending of the surface layer, quenching with an air knife, a cooling roll and a cooling sizing die at the exit of the extruded T die, and immediately 180 ~ By heating and pressing between 220 ° C. rolls and further tensioning, heating and pressing between rolls to heat denaturate, a thin sheet (film) can be efficiently obtained with good quality.

【００４４】押込（射出）成形 混練押出機でベント脱
気し直結する加熱成形押出機の押込（射出）ノッズル
（インラインスクリュー射出成形様式が一般）から、１
６０〜１８０℃の押出成形可能の許容最高温度で含水量
１５％以下で１８０〜２２０℃の高温金型へ押込（射
出）成形する。金型交換時間や金型容量に見合う滞留部
（スクリューの後退・シリンダー等）を設け押込（射
出）量を調節し金型に密接するノッズルより金型へ押込
（射出）することなどは射出成形と同様であるが、金型
が１８０〜２２０℃の高温で離型など問題がなく、熱可
塑性樹脂の冷却型への高圧高速射出成形と全く異り、低
圧低速で金型内に押込むことが許容され、従って金型の
強い機械的強度や冷却装置を必要とせず、またロータリ
ー金型を用いて加熱変性時間を長くすることもできる。
高温低圧低速の押込成形は微細若干でも発泡は免れない
が押込量圧力調整などによって発泡率を自由に調節成形
できる。この混練−インライン射出装置を２系列以上設
置して積層ノッズルで積層成形できるが、多くは単層成
形物であり離型後乾燥して内層（コアー）成形物表面に
表層（スキン）配合溶液を吹付塗布して乾燥加熱変性す
る。Push-in (injection) molding From push-in (injection) nozzle (generally in-line screw injection molding method) of a heat-molding extruder that is vented and directly connected to a kneading extruder,
At a maximum allowable temperature for extrusion molding of 60 to 180 ° C., a water content of 15% or less is indented (injected) into a high temperature mold of 180 to 220 ° C. The retention part (screw retreat, cylinder, etc.) corresponding to the mold replacement time and the mold capacity is provided to adjust the amount of pushing (injection) and to push (inject) into the mold from the nozzle that is in close contact with the mold. Same as the above, but there is no problem such as mold release at a high temperature of 180 to 220 ° C, and it is completely different from high-pressure high-speed injection molding of a thermoplastic resin into a cooling mold, and it is pushed into the mold at a low pressure and low speed. Therefore, a strong mechanical strength of the mold and a cooling device are not required, and the heat denaturation time can be extended by using a rotary mold.
In the high-temperature low-pressure low-speed push-molding, even a slight amount of foaming is inevitable, but the foaming rate can be freely adjusted by adjusting the push-in amount pressure. Two or more series of this kneading-in-line injection device can be installed to laminate-mold with a stacking nozzle, but most of them are single-layer molded products, and after releasing, they are dried to give a surface layer (skin) mixture solution on the surface of the inner layer (core) molded product. Spray coating and dry heat to modify.

【００４５】溶液成形 混練押出機・密閉槽混練機の８
０〜１４０℃混練物に配合水５部以上を混入し稀釈冷却
して含水量１５％以上１００℃以下の糊化澱粉溶液とす
る。（混練前・混練中に稀釈することもある）シート状
物は１００℃以下で回転ドラムや一帯の無端ベルト（エ
ンドレスベルト）などの金属鈑上に溶液を流延コートす
るか高粘性の場合はナイフ・エッジなどを用いてシート
状に成形し乾燥する。乾燥したシート状物は前記〔００
３８〕の積層したり〔００３９〕記載の加熱など低温押
出成形シート状物と同様に取扱い加工する。成形物は糊
化溶液を型に流延・吹付付着するデッピングモールド・
スラッシュモールド法によって成形し乾燥しまたは更に
積層乾燥して開放下で加熱変性して単層・積層のモール
ド品（成形物）を製造する。Solution molding 8 of kneading extruder / closed tank kneader
Mixing 5 parts or more of compounding water into a kneaded product of 0 to 140 ° C. and diluting and cooling to obtain a gelatinized starch solution having a water content of 15% or more and 100 ° C. or less. Sheets (diluted before and during kneading) may be cast at 100 ° C or below on a metal drum such as a rotating drum or an endless belt (endless belt) by casting the solution or if it is highly viscous. Form into a sheet using a knife or edge and dry. The dried sheet-like material is [00
38] is laminated, and the same processing as the low temperature extrusion molded sheet material such as heating described in [0039] is performed. The molded product is a depping mold that casts and sprays the gelatinizing solution onto the mold.
Molded by the slush mold method and dried or further laminated and dried by heating under open condition to produce a single layer / laminated molded article (molded article).

【００４６】耐水強化処理 耐水性を増強した表層配合
糊化溶液を、コーン容器・紙器や当該内層配合成形物の
表面に塗布・吹付けて乾燥し加熱変性して耐水性を付与
する方法。当該植物高分子耐水組成物の表面に耐水合成
樹脂膜を積層して耐水性を強化する方法〔請求項３〕。
当該耐水組成物の表面に変性剤などを塗布したり塗布し
ないで、火炎（フレームプラズム処理）・コロナ放電・
紫外線などの照射によって表面処理して耐水性を強化す
る方法。これらの組合せが実施される。Water Resistance Strengthening Treatment A method of applying a surface layer-containing gelatinizing solution having enhanced water resistance to the surface of a corn container, a paper container, or the inner layer-containing molded article, followed by drying and heat denaturation to impart water resistance. A method for enhancing water resistance by laminating a water resistant synthetic resin film on the surface of the plant polymer water resistant composition [claim 3].
Flames (frame plasm treatment), corona discharge, etc. without or with a modifier applied to the surface of the water resistant composition.
A method to enhance water resistance by surface treatment by irradiation with ultraviolet rays. Combinations of these are implemented.

【００４７】[0047]

【作用】８０〜１４０℃の混練分散は澱粉と配合水によ
る糊化澱粉溶液（溶体）が植物繊維物や無機微分物を界
面に空隙などなく親和密着し均質に分散することが目標
であり、親和密着・均質分散は乾燥接着固化複合構造・
加熱変性による強度・耐水性など諸物性向上に大きく寄
与しその成果を左右する必須前処理である。The function of kneading and dispersion at 80 to 140 ° C. is that the gelatinized starch solution (solution) of starch and the compounding water is homogeneously dispersed by closely adhering the vegetable fiber and the inorganic derivative to the interface without voids. Affinity adhesion / homogeneous dispersion is a dry adhesion solidification composite structure
It is an essential pretreatment that greatly contributes to the improvement of various physical properties such as strength and water resistance by heat denaturation and influences the results.

【００４８】親和密着・混練分散の良好な糊化澱粉溶液
を得るには、比較的大きな径の短繊維・微粉物の植物繊
維物を用いて混練すれば絡ることなく均質に分散し、且
つ糊化澱粉中で強力混練剪断によって解繊・微細化し相
溶剤の浸透を助長し親和密着を促進する。（従って絡り
縫れて毛玉状とするビーダーなどによる叩解「たたきほ
ぐす打解・解繊」の製紙パルプのようなフイブリル微細
繊維にしない。）固体で比重が比較的重い無機微粉物の
存在は植物繊維物の絡りを防止して均質分散・解繊微細
化に寄与する。蒸発相溶剤は配合水で充分に溶融しない
澱粉誘導体などの均質糊化に有効であり、また含水量を
制限された場合などの糊化澱粉粘度の低下分散に効果が
大きい。混練温度１１０℃以上で強力な剪断混練を充分
に施工することが良質な本発明の組成物の糊化澱粉溶液
を形成する。In order to obtain a gelatinized starch solution having good affinity and kneading and dispersion, kneading with a short fiber / fine powdered plant fiber material having a relatively large diameter results in uniform dispersion without entanglement, and In gelatinized starch, strong kneading and shearing disintegrates and refines to promote the penetration of compatibilizer and promote affinity adhesion. (Therefore, it is not made into fine fibrils such as the paper pulp of "Tataki Hogusu Disintegration / Defibration", which is beaten by a beader that is entangled and sewn into pills.) The presence of inorganic fine powder that is solid and has a relatively high specific gravity is a plant Prevents entanglement of fibrous materials and contributes to uniform dispersion and fine defibration. The evaporative compatibilizer is effective for homogeneous gelatinization of starch derivatives and the like that do not melt sufficiently in the compounding water, and is also effective for lowering and dispersing the viscosity of gelatinized starch when the water content is limited. Sufficient shear kneading at a kneading temperature of 110 ° C. or higher forms a gelatinized starch solution of the composition of the present invention which is of good quality.

【００４９】組成配合物を混練分散して糊化澱粉溶液と
し、脱水成形し、次いで水分・蒸発溶剤を乾燥除去すれ
ば糊化澱粉は植物繊維物・無機微粉物に凝集密着固化し
いかり効果・ワンデルワールスカ・水素結合など接着力
が強力に得られる。含水量を極少に組成の１０％以下の
乾燥した組成物を１６０〜２２０℃に加熱すれば残留水
分は気化蒸発あるいは発泡して成形物を構成する組成物
は実質的に風乾状態となり、密着固化の澱粉は１６０〜
１８０℃で解重合・再結合し１８０〜２００℃で膨潤性
を失い〜２２０℃で順次カラメル化焼成が始りまた植物
繊維物は加熱分解活性化する。この密着固化加熱変性の
複合構造組成物は強度が大きく増大し程度の耐水性が得
られるなど諸物性が大きく向上する。If the composition mixture is kneaded and dispersed to form a gelatinized starch solution, dehydrated and molded, and then water and evaporation solvent are dried and removed, the gelatinized starch coagulates and adheres to plant fiber materials and inorganic fine powder materials. Provides strong adhesive force such as Wanderwarska and hydrogen bonding. When a dried composition having a water content of 10% or less of the composition is heated to 160 to 220 ° C., residual water vaporizes and evaporates or foams to form a molded article, and the composition constituting the molded article becomes substantially air-dried and adheres and solidifies. Starch is 160 ~
It depolymerizes and recombines at 180 ° C, loses swelling at 180 to 200 ° C, and starts caramelized firing at 220 ° C, and the plant fiber material is activated by thermal decomposition. The composite structure composition which is modified by adhesion, solidification and heating is greatly improved in various physical properties such as a large increase in strength and a degree of water resistance.

【００５０】加えて１６０〜２２０℃加熱は変性剤が分
解反応して澱粉・植物繊維や組成物相互に共架橋・自体
の架橋・その外の反応結合など化学反応が大きく加わっ
て活性反応したと思われることにより強い耐水性・高強
度の諸高物性の植物高分子耐水組成物となる。表層には
更に架橋澱粉など耐水澱粉誘導体を使用したり、合成樹
脂ラテックス・シリコーンラテックスなどを配合して表
面に薄膜や滲出膜を構成したり、火炎・放電・放電・照
射など物理的表面処理も加えることにより耐水性を増強
することができる。In addition, when heated at 160 to 220 ° C., the denaturing agent decomposes and a chemical reaction such as co-crosslinking with starch / vegetable fiber or composition, cross-linking of itself, or reaction bond outside the active agent is added to cause an active reaction. It is believed that the plant polymer water resistant composition has various properties such as strong water resistance and high strength. For the surface layer, water-resistant starch derivatives such as cross-linked starch are used, synthetic resin latex, silicone latex, etc. are mixed to form a thin film or exudation film on the surface, and physical surface treatment such as flame, discharge, discharge, irradiation is also performed. Water resistance can be enhanced by adding it.

【００５１】本組成物（製品）は内外または表裏の組成
配合の異る積層物とすることが好ましい。内層（コアー
層）は植物高分子を主に配合水・相溶剤・無機微粉物で
組成し、変性剤は０．１〜５部とし耐水澱粉誘導体やラ
テックス等は使用せず、多価アルコール可撓剤・水溶性
高分子を接着強度向上・可撓性に配合して極端な含水量
低減なく程度の発泡を許容し植物高分子など組成物の相
互親和接着固化して強度物性を向上した複合構造とし生
分解性を良好にする配合・処理工程にする。表層（スキ
ン層）は内層の両面か片面に積層し、変性剤の添加を必
須とし耐水澱粉誘導体や表面疎水処理も用いて耐水性を
強化し、含水量・可撓性を押えて無発泡か微細発泡の耐
水性を強く求め諸物性向上の配合・処理工程にする。内
層（コアー層）は積層厚みの６０％以上好ましくは８０
％以上であり表層（スキン層）は物性の許るす限り必要
最小限の厚みにする。この積層によって必要な耐水性は
表層で生分解性は内層で強く得られる構造となり植物高
分子の複合構造と共に諸物性の優れた植物高分子耐水組
成物となる。極めて薄いシート状物（フイルム）・成形
品は単層であり表層配合・処理工程に準じて製造され
る。It is preferable that the composition (product) of the present invention is a laminate having different composition blends on the inside and outside or on the front and back sides. The inner layer (core layer) is composed mainly of plant macromolecules and is composed of water, a compatibilizer, and an inorganic fine powder. The modifier is 0.1 to 5 parts, and water-resistant starch derivatives and latex are not used. A compounding compound that improves the adhesive strength and flexibility by blending a flexibilizer and a water-soluble polymer to allow foaming to some extent without extreme reduction of water content, and solidify the mutual affinity of compositions such as plant polymers to solidify Use a compounding / treatment process that creates a structure with good biodegradability. The surface layer (skin layer) is laminated on both sides or one side of the inner layer, and it is necessary to add a modifier to strengthen the water resistance by using a water-resistant starch derivative and surface hydrophobic treatment, and it is possible to suppress the water content and flexibility to prevent foaming. We strongly request the water resistance of fine foaming, and use a compounding / treatment process to improve various physical properties. The inner layer (core layer) is 60% or more of the laminated thickness, preferably 80
% Or more, and the surface layer (skin layer) has the minimum necessary thickness as long as the physical properties allow. By this lamination, the required water resistance is the surface layer and the biodegradability is strongly obtained in the inner layer, and the plant polymer water resistant composition is excellent in various physical properties together with the composite structure of the plant polymer. An extremely thin sheet (film) / molded product is a single layer and is manufactured according to the surface layer composition / treatment process.

【００５２】本組成物は熱可塑性樹脂でないので相対エ
ンドレス間隙の金属鈑間の加熱や低温（溶液）成形シー
トの裁断絞り加工して内外に狹締して加熱変性する金型
及び押込（射出）成形する金型は１８０〜２２０℃の高
温のままで離型できる大きな特徴を有するので冷却取出
し（冷却装置）は必要なく高生産性である。Since this composition is not a thermoplastic resin, it is heated between metal plates in the relative endless gap, cut and drawn at low temperature (solution) forming sheet, and is heat-modified by squeezing in and out and pressing (injection). Since the mold to be molded has a great feature that it can be released from the mold at a high temperature of 180 to 220 ° C., it does not require a cooling take-out (cooling device) and has high productivity.

【００５３】耐水性を得る表層配合は可撓剤も制限され
高温押出成形は難しいので配合水・蒸発（相溶）剤を充
分に用いることのできる低温成形糊化澱粉溶液が望まし
い。またこの表層配合は流延・吹付塗布して多くは０．
２耗以下で溶液流延膜の水分等蒸発除去に際して加熱乾
燥による発泡の心配が少く好都合であり、内層配合組成
物表面・他物質表面・単層シートとすることが甚だ有利
である。Since the surface layer formulation for obtaining water resistance is also limited by the flexibilizer and high temperature extrusion molding is difficult, a low temperature molding gelatinized starch solution which can sufficiently use the compounding water / evaporation (compatibility) agent is desirable. In addition, most of the surface layer compositions obtained by casting or spray coating had a surface area of 0.
There is little concern about foaming due to heat drying when evaporating and removing water and the like from the solution cast film under 2 abrasion, and it is very advantageous to use the composition of the inner layer composition, the surface of another substance, or the single layer sheet.

【００５４】本組成物は変性しても本来生分解性であり
環境を阻害しないものである。即ち使用後廃棄したシー
ト状物や成形容器など本組成物は、焼却しても燃焼カロ
リーは低く有害物質を発生しない・埋立てには生分解性
のため容積を低減し地盤の安定に寄与する・勿論リサイ
クルは可能である。廃棄物の有効な積極的活用として堆
肥・肥料として用いることであり、生ゴミ・落葉・枯草
・藁などと同様かそれ以上の速度で生分解する堆肥化
（コンポスト化）を有し、またこれらの混用にも優れた
効果を有する。直接土壌に散布埋散して通常の肥料と同
様に使用して肥料効果を発揮する。粉砕混合して飼料と
することも可能である。The composition of the present invention is inherently biodegradable when modified and does not disturb the environment. In other words, this composition, such as sheets and molded containers discarded after use, has low calories burned even when incinerated and does not generate harmful substances.It contributes to stability of the ground by reducing the volume because it is biodegradable for landfill.・ Of course, recycling is possible. It is to use it as compost / fertilizer for the effective and positive use of waste. It has composting (composting) that biodegrades at the same speed as or more than garbage, litter, hay, straw, etc. It also has an excellent effect when mixed with. It is sprayed and buried directly on the soil and used in the same manner as normal fertilizer to exert the fertilizer effect. It is also possible to grind and mix them to obtain feed.

【００５５】[0055]

【発明の効果】安価大量に生産される澱粉と農産廃棄物
などの粗砕植物繊維物とからなる植物高分子の複合構造
とし、耐水性・強度など諸物性を向上し、汎用合成樹脂
成形物や紙製品と同様の物性／価格とし、且つ使用後の
廃棄物は生分解性が容易で環境を阻害しないものであ
る。未利用資源を活用し大量生産できる再生産資源の製
品を供給し有限資源の合成樹脂（石油）や消費に再生産
が追付かぬ紙製品（木材資源）に換る植物高分子組成物
である。[Effects of the Invention] A general-purpose synthetic resin molded article having a composite structure of a plant polymer composed of inexpensively produced in large quantities and starch and coarsely crushed plant fiber materials such as agricultural wastes to improve various physical properties such as water resistance and strength. It has the same physical properties / price as paper and paper products, and the wastes after use are easily biodegradable and do not disturb the environment. It is a plant polymer composition that supplies recycled resource products that can be mass-produced by utilizing unused resources and replaces synthetic resin (petroleum) with limited resources and paper products (wood resources) whose reproduction does not catch up with consumption. .

【００５６】[0056]

【実施例１】表層配合澱粉のコーンスターチ８５部と
〔００１５〕記載構成の麦ワラ繊維物１５％との植物高
分子１００部に対し、配合水の水道水１６部、変性剤の
共架橋剤トリアリルイソシアヌレート２部過酸化物ジブ
チルパーオキシド０．３部、微粉物のタルク平均粒径３
μｍ１０部、滑剤のシリコーンラテックス０．２部、着
色剤の酸化チタン８部。内層配合澱粉のコーンスターチ
４０％小麦粉４０％と〔００１５〕記載構の竹・葦混合
繊維物２０％との植物高分子１００部に対し、配合水の
水道水２０部、可撓剤・水溶性高分子のポリエチレンオ
キシド１０部、変性剤の共架橋剤ジアリルフタレート
０．５部、微粉物の炭酸カルシウム平均粒子径３μｍ１
５部、滑剤の脂肪酸エステル２部。[Example 1] To 100 parts of a plant polymer consisting of 85 parts of corn starch as a surface-blended starch and 15% of a straw fiber product having a composition as described in [0015], 16 parts of tap water of compounding water and triallyl co-crosslinking agent of modifier Isocyanurate 2 parts Peroxide dibutyl peroxide 0.3 parts Fine talc average particle size 3
μm 10 parts, lubricant silicone latex 0.2 parts, colorant titanium oxide 8 parts. For 100 parts of plant macromolecules of inner starch starch 40% cornstarch 40% wheat flour and [0015] 20% bamboo / reed mixed fiber material, 20 parts tap water of compounded water, flexible agent / high water solubility Molecular weight polyethylene oxide 10 parts, modifier co-crosslinking agent diallyl phthalate 0.5 part, fine powder calcium carbonate average particle diameter 3 μm 1
5 parts, 2 parts of fatty acid ester of lubricant.

【００５７】表層配合物を混合し、高剪断スクリュー２
軸混練押出機で順次８０〜１４０℃に加熱混練し直結タ
ンデム配列押出成形機で冷却調質して９０〜９５℃で厚
み０．１ｍｍに押出し、伸長しつつ９５〜１００℃熱風
を吹付け乾燥し含水量組成の５％以下の厚み０．０７５
ｍｍシート状物を捲取った。内層配合物を１軸混練押出
機で８０℃〜１４０℃で強力に加熱混練し混練機に増設
した単管の冷却装置〔００３７〕で９２〜９５℃の厚み
０．０３５ｍｍに押出し、伸張しつつ９５〜１００℃熱
風を吹付け乾燥し含水量組成の８％±０．５％の０．３
ｍｍシートとする。表層配合の捲取った０．０７５ｍｍ
シート状物を内層シートの両面に積層して〔００３９〕
記載の相対エンドレスベルト間隙に送り順次昇温して２
１０℃で加熱変性する。Mix the surface layer formulation, high shear screw 2
Axial kneading extruder sequentially heats and kneads at 80 to 140 ° C, cools and tempers it with a direct connection tandem array extruder and extrudes it to a thickness of 0.1 mm at 90 to 95 ° C, and blows it to 95 to 100 ° C to dry it. Moisture content 5% or less of composition 0.075
mm sheet was wound up. The inner layer composition was strongly heat-kneaded at 80 ° C to 140 ° C with a single-screw kneading extruder and extruded to a thickness of 0.035 mm at 92 to 95 ° C with a single-tube cooling device [0037] added to the kneading machine, while expanding. 95 to 100 ° C. Hot air is blown and dried to obtain a moisture content of 8% ± 0.5% of 0.3.
mm sheet. 0.075mm rolled up surface layer
Laminating the sheet-like material on both sides of the inner layer sheet [0039]
It is sent to the relative endless belt gap described and the temperature is raised sequentially to 2
Denature by heating at 10 ° C.

【００５８】ベルト間隙を一定に保持して無発泡の０．
４５ｍｍ厚シートを、またベルト間隙を加熱途中から３
倍に開放して厚み１．３５ｍｍ（内層０．３×４倍＝
１．２ｍｍ）発泡シートとした。この植物高分子耐水組
成物のシートはケント紙・画用紙あるいはケーキなどの
折箱容器など高級白色厚板紙として有用である。使用後
廃棄物は農産廃棄物と共に堆肥とした。With the belt gap kept constant, a non-foaming value of 0.
45mm thick sheet and belt gap from the middle of heating 3
Double opening to a thickness of 1.35 mm (inner layer 0.3 x 4 times =
1.2 mm) Foamed sheet. The sheet of the plant polymer water resistant composition is useful as a high-grade white board such as a Kent paper, a drawing paper or a folding box container such as a cake. After-use waste was compost together with agricultural waste.

【００５９】[0059]

【実施例２】表層内層共に配合を実施例１と同一とす
る。各々の配合物を２軸混練押出機と直結タンデム配列
ベント押出成形機の装置で〜１３５℃強力混練し冷却ベ
ント脱気調質して含水量を組成の内層８％以下表層１０
％以下とし、フイードブロック−Ｔダイに送り、表層
（両面）０．０５ｍｍ×２ 内層０．２５ｍｍ 厚み
０．３５ｍｍの積層シートを９０〜９５℃で２種３層に
積層押出する。熱風９５〜１００℃を吹付け表層を乾燥
して含水量を５％以下として、所要形状に裁断し絞り加
工して１８０〜２２０℃加熱内外型に押込み狹締密閉加
熱発泡変性する。裁断した打抜カスは内層配合に粉砕混
入し混練分散して再使用した。Example 2 The composition of both the inner and outer layers is the same as in Example 1. Each compound was intensively kneaded by a device of a twin-screw kneading extruder and a tandem-arranged vent extruder with a direct connection at ~ 135 ° C, and cooling vent was degassed to have a water content of 8% or less of the inner layer of the composition and the surface layer 10
%, And sent to a feed block-T die, and a layered sheet having a surface layer (both sides) of 0.05 mm × 2 inner layer of 0.25 mm and a thickness of 0.35 mm is laminated and extruded into two layers of three layers at 90 to 95 ° C. Hot air is blown at 95 to 100 ° C. to dry the surface layer so that the water content is 5% or less, and the product is cut into a desired shape and drawn, and then pressed into an inner and outer mold heated at 180 to 220 ° C., and closed by heat-sealing to effect foaming modification. The cut punched dust was pulverized and mixed into the inner layer mixture, kneaded and dispersed, and reused.

【００６０】内外型で狹締密閉して〜２２０℃に加熱発
泡変性して得られた発泡倍率２倍厚み０．７ｍｍ（内層
０．２５×２．４倍＝０．６）のトレーなど容器成形物
はコーナー部が補強されるなど包装容器として優れたも
のであった。使用後の廃棄物は粗砕して堆肥にした。A container such as a tray having an expansion ratio of 2 times and a thickness of 0.7 mm (inner layer: 0.25 × 2.4 times = 0.6) obtained by foaming and denaturing by heat-sealing up to 220 ° C. The molded product was excellent as a packaging container because the corners were reinforced. The used waste was crushed into compost.

【００６１】[0061]

【実施例３】コーンスターチ７０％リン酸架橋澱粉２０
％の澱粉９０％と〔００１５〕記載構成の稲ワラ繊維物
１０％との植物高分子１００部に対し、配合水の浄化処
理水道水２０部、相溶剤の可撓性・多価アルコール系グ
リセリンジアセテート１０部、変性剤の共架橋剤メチロ
ールプロパンジメタクリレート１．８部過酸化物ブチル
クミルパーオキシド０．５部、アクリ系ラテックス５
部、滑剤のシリコーンラテックス０．１部、着色剤の酸
化チタン１０部。Example 3 Corn Starch 70% Phosphoric Acid Cross-Linked Starch 20
% Starch 90% and rice straw fiber material 10% described in [0015] 100 parts of plant polymer, 20 parts of tap water for purification of compounding water, flexible polyhydric alcohol glycerin as compatibilizer Diacetate 10 parts, modifier co-crosslinking agent methylol propane dimethacrylate 1.8 parts peroxide butyl cumyl peroxide 0.5 parts, acrylic resin latex 5
Parts, 0.1 part of a silicone latex as a lubricant, and 10 parts of titanium oxide as a colorant.

【００６２】上記単層配合物を２軸混練押出機と直結タ
ンデム配列ベント押出成形機の装置で〜１４０℃強力混
練し〜１７０℃で加温ベント脱気調質し、含水量組成の
８％以下、１６０℃・リップ間隙０．０５ｍｍで押出
し、ダイ吐出口に接してエアーナイフ（ダイリップも冷
却）と冷却サイジングダイ（流水冷却）によって急冷し
直ちに２１０℃ロールで狹締加熱加工する。伸張しつつ
２１０〜２１５℃の加熱炉及ロール加熱加圧を重ねて微
細な１％以下発泡の０．０４ｍｍの薄いシート状物（フ
イルム）を得た。The above single layer composition was intensively kneaded by a twin-screw kneading extruder and a tandem-arrangement vent extruder with a direct connection at 140 ° C. and heated at 170 ° C. and vented by degassing to obtain 8% of the water content composition. Then, it is extruded at 160 ° C. and a lip gap of 0.05 mm, brought into contact with a die discharge port, rapidly cooled by an air knife (cooling the die lip) and a cooling sizing die (cooling with running water), and immediately subjected to squeezing and heating with a 210 ° C. roll. While being stretched, a heating furnace at 210 to 215 ° C. and roll heating and pressurization were repeated to obtain a fine sheet-like material (film) of 0.04 mm with fine 1% or less foaming.

【００６３】このフイルムは包装用とし有用であり、廃
棄物は堆肥とした。This film was useful for packaging and the waste was compost.

【００６４】[0064]

【実施例４】表層（溶液）配合澱粉のコーンスターチ９
０％と〔００１５〕記載構成の稲ワラ１０％との植物高
分子１００部に対し、配合水の浄化処理水道水２０部稀
釈冷却水１０部、変成剤の共架橋剤トリアリルフタレー
ト２部・酸化亜鉛１部、スチレンブタジェンラテックス
５部、着色剤の酸化チタン７部。内層配合コーンスター
チ５０％ポテトスターチ３０％の澱粉８０％と〔００１
５〕記載構成のバガス繊維物２０％との植物高分子１０
０部に対し、相溶剤の可撓剤・多価アルコール タクリレート１部、微粉物の重炭酸カルシウム平均粒径
１μｍ１５部、滑剤の脂肪酸グリセライド２部、着色剤
の酸化チタン４部。[Example 4] Corn starch 9 of starch mixed with surface layer (solution)
0% and 100% of plant macromolecules of 10% of rice straw having the composition described in [0015], 20 parts of purification treatment tap water with 10 parts of diluted cooling water, 2 parts of co-crosslinking agent triallyl phthalate as a modifier 1 part zinc oxide, 5 parts styrene butadiene latex, 7 parts titanium oxide colorant. Inner layer blended corn starch 50% potato starch 30% starch 80% and [001
5] Plant polymer 10 with 20% bagasse fiber material of the described composition
Compliant with 0 parts, flexible solvent and polyhydric alcohol 1 part of tacrylate, 15 parts of finely divided calcium bicarbonate having an average particle diameter of 1 μm, 2 parts of fatty acid glyceride as a lubricant, and 4 parts of titanium oxide as a colorant.

【００６５】２軸混練押出機に加熱混合ベント調整装置
を増設し、内層配合物を〜１４０℃で強力に混練し１４
０〜１６０℃に加熱混合しつつベント脱気して含水量を
７％以下に調質して直結するインラインスクリュー型射
出成形機に供給する。射出成形機で１６０〜１８０℃に
加熱混合してノッズルより１８０℃で２００〜２２０℃
金型に押込（射出）成形し、金型で加熱変性し、高温の
まま金型より取出す。A heat-mixing vent adjusting device was added to the twin-screw kneading extruder to strongly knead the inner layer mixture at ˜140 ° C.
The mixture is heated and mixed at 0 to 160 ° C., vented and degassed to adjust the water content to 7% or less and supplied to an in-line screw type injection molding machine directly connected. 200-220 ℃ at 180 ℃ from Nozzle by heating and mixing at 160-180 ℃ with an injection molding machine.
It is pressed (injected) into the mold, heat-denatured with the mold, and taken out from the mold at high temperature.

【００６６】２軸混練押出機に水供給口冷却混合装置を
増設し、表層配合物を〜１３０℃で強力に混練し稀釈冷
却水を供給して冷却混合して９５℃以下の表層配合糊化
澱粉溶液とする。A water supply port cooling / mixing device was added to the twin-screw kneading extruder, the surface layer composition was strongly kneaded at ~ 130 ° C, diluted cooling water was supplied, and the mixture was cooled and mixed to form a surface layer composition gelatinization of 95 ° C or less. Use the starch solution.

【００６７】内層配合高温成形物の表面に表層配合溶液
を熱風噴射して吹付塗布し、乾燥し、２１０゜〜２２０
℃加熱炉で加熱変性した。以上によって植物高分子耐水
組成の成形物を得た。Inner layer blending The surface layer blending solution was sprayed with hot air onto the surface of the high-temperature molded article by spraying, drying and drying at 210 ° to 220 °.
It was denatured by heating in a ℃ heating furnace. As described above, a molded product having a plant polymer water resistant composition was obtained.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 澱粉と繊維物との植物高分子に配合水・
相溶剤・変性剤を必須配合として、８０〜１４０℃で混
練分散し、脱気成形乾燥し、１６０〜２２０℃で加熱変
性することを特徴とする植物高分子耐水組成物。1. Water mixed with plant macromolecules of starch and fiber materials
A plant polymer water-resistant composition characterized by kneading and dispersing at 80 to 140 ° C, deaeration molding and drying, and heat-denaturing at 160 to 220 ° C, with a compatibilizer / modifying agent as an essential component. 【請求項２】 澱粉５０〜９０％と繊維物５０〜１０％
との植物高分子１００部に対し、配合水１０部以上・相
溶剤５〜４０部・変性剤０．１〜２０部を必須配合とし
て、８０〜１４０℃で強力に混練分散し、１００℃以下
か１２０〜１８０℃で製出成形し、その前後で脱気乾燥
して含水量を組成の１０％以下とし、狭締してか開放で
１６０〜２２０℃で加熱変成することを特徴とする植物
高分子耐水組成物の製法。2. Starch 50 to 90% and fibrous material 50 to 10%
With 100 parts of the plant polymer, and 10 parts or more of the compounding water, 5 to 40 parts of the compatibilizer, and 0.1 to 20 parts of the modifier, as essential components, strongly knead and disperse at 80 to 140 ° C. and 100 ° C. or less. Or a plant characterized by being produced by molding at 120 to 180 ° C., deaerated and dried before and after that to make the water content 10% or less of the composition, and heat-denatured at 160 to 220 ° C. by tightening or opening. Method for producing a polymer water resistant composition. 【請求項３】 請求項１組成物表面の部分に耐水性合成
樹脂膜を積層構成した植物高分子耐水組成物。3. A plant polymer water resistant composition comprising a water resistant synthetic resin film laminated on the surface of the composition.