JP4574738B1 - Biodegradable molded products - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
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Abstract
【課題】 還元剤や金属塩、ポリ乳酸などの生分解性プラスチックを含まず、強度や耐水性に優れ、しかも、尿素臭などの異臭発生の可能性が少ない生分解性の容器やシートを提供する。
【解決手段】 ０〜２５.０質量％のデンプンと２５.０〜５５.０質量％のタンパク質と１１.０〜３７.０質量％のセルロース繊維と１８.０〜３５.０質量％の水と、必要に応じて１０.０質量％以下のグリセリンなどの軟化剤を室温で十分に捏ねた後、４０〜１３０℃好ましくは５０〜１２０℃の温度、２０〜１２０ｋｇｆ好ましくは２５〜１００ｋｇｆの圧力でプレス処理を行い、農業に用いられる各種シート又は食品用包装容器、食器などの各種成形品を得る。
【選択図】なしPROBLEM TO BE SOLVED: To provide a biodegradable container or sheet that does not contain a biodegradable plastic such as a reducing agent, a metal salt, or polylactic acid, has excellent strength and water resistance, and is less likely to generate a strange odor such as urea odor. To do.
SOLUTION 0-25.0% starch, 25.0-55.0% protein, 11.0-37.0% cellulose fiber and 18.0-35.0% water. And, if necessary, a softening agent such as 10.0% by mass or less glycerin is sufficiently kneaded at room temperature, and then a temperature of 40 to 130 ° C., preferably 50 to 120 ° C., 20 to 120 kgf, preferably 25 to 100 kgf. Is pressed to obtain various molded products such as various sheets used in agriculture, food packaging containers, and tableware.
[Selection figure] None
Description
本発明は生分解性成形品に関する。 The present invention relates to a biodegradable molded article.
これまでに、ポリ乳酸や脂肪酸ポリエステルなどの生分解性樹脂やデンプンなどの天然素材を主成分とした数多くの生分解性容器やシートが提案されている。 So far, many biodegradable containers and sheets based on biodegradable resins such as polylactic acid and fatty acid polyester and natural materials such as starch have been proposed.
例えば、特開平７−１７５７１号公報（特許文献１）には、デンプンを主たる成分とし、植物性繊維及び／又はタンパク質を加えて発泡成形した生分解性の緩衝材が開示されている。また、特開２００５−１１９７０８号公報（特許文献２）には、デンプン、ポリオール、単糖若しくはオリゴ糖、タンパク質を配合した生分解性樹脂組成物が開示されている。特開平５−３２０４０１号（特許文献３）には小麦粉とデンプン、セルロース、油などを配合し、発泡焼成した生分解性成形品が開示されている。 For example, Japanese Patent Application Laid-Open No. 7-17571 (Patent Document 1) discloses a biodegradable cushioning material which is formed by foaming with starch as a main component and adding vegetable fiber and / or protein. Japanese Patent Laying-Open No. 2005-119708 (Patent Document 2) discloses a biodegradable resin composition containing starch, polyol, monosaccharide or oligosaccharide, and protein. Japanese Patent Laid-Open No. 5-320401 (Patent Document 3) discloses a biodegradable molded product obtained by blending wheat flour and starch, cellulose, oil, and the like and foaming and firing.
しかしながら、デンプンなどの天然素材を用いた場合には耐水性が十分でない場合が多く、強度的にも不足する傾向にあった。このため、例えば特開平５−２７８７３８号公報（特許文献４）や特開平５−５７８３３公報（特許文献５）、特開２００２−３５５９３２公報（特許文献６）にはそれぞれ生分解性組成物から成形した加工品の表面に、耐水用の樹脂をコーティングする方法が開示されているが、この方法ではコーティングが必須の工程であり、工程数が多くなってしまう。 However, when natural materials such as starch are used, the water resistance is often insufficient and the strength tends to be insufficient. For this reason, for example, JP-A-5-278738 (Patent Document 4), JP-A-5-57833 (Patent Document 5), and JP-A-2002-355932 (Patent Document 6) are molded from biodegradable compositions, respectively. A method of coating a water-resistant resin on the surface of a processed product is disclosed, but in this method, coating is an essential process, and the number of processes increases.
一方、耐衝撃性や耐熱性を向上させた生分解性組成物として、例えば、特開平６−２４８０４０号公報（特許文献７）には、フェノール類と砂糖、デンプンとからなる組成物が開示されている。この組成物はフェノール類と砂糖の反応による樹脂形成を応用したものである。また、特開２００４−１３７７２６号公報（特許文献８）には、デンプン、タンニン又はポリフェノール、さらにはタンパク質並びに鉱物粉砕末、タンニン又はポリフェノールとキレート媒染効果を有する二価金属末（又は金属塩）とからなる生分解性砂利製品用の組成物が開示されている。しかしながら、この組成物は金属塩とポリフェノールの縮合化合物をデンプンに担持させたものであって、二価の金属末（又は金属塩）が用いられているので食器などの用途には好ましくない。また、ここで用いられているタンニン、ポリフェノール類は、柿しぶやお茶のタンニン、樹皮タンニンなどの縮合型タンニンであって、砂利の代替品には適しているが、縮合型タンニンと二価の金属塩を用いているために強度が高くなりすぎて食器などの加工品には適さない。そして、金属塩が用いられているため、分解された後にこれらの金属が残り、環境に悪影響を与える可能性も考えられた。 On the other hand, as a biodegradable composition having improved impact resistance and heat resistance, for example, JP-A-6-248040 (Patent Document 7) discloses a composition comprising phenols, sugar and starch. ing. This composition is an application of resin formation by reaction of phenols with sugar. JP-A-2004-137726 (Patent Document 8) includes starch, tannin or polyphenol, further protein and mineral pulverized powder, tannin or polyphenol and a divalent metal powder (or metal salt) having a chelate mordanting effect. A composition for a biodegradable gravel product is disclosed. However, this composition is a compound in which a condensation compound of a metal salt and a polyphenol is supported on starch, and a divalent metal powder (or metal salt) is used. The tannins and polyphenols used here are condensed tannins such as tannins, tea tannins and bark tannins, which are suitable as substitutes for gravel, but condensed tannins and divalent metals. Because salt is used, the strength becomes too high and it is not suitable for processed products such as tableware. And since the metal salt is used, after decomposition | disassembly, these metals remain | survived and the possibility of having a bad influence on an environment was also considered.
特開２００５−２３２６２号公報（特許文献９）には、トウモロコシなどの穀類、雑草等の食物繊維、砂糖キビ等の１００％天然素材を微細化した主材と、柿渋やコンニャク粉などの天然バインダーを用いた生分解性組成物が開示されている。しかしながら、具体的な組成比が不明であり、現実に製品として製造できるのかどうか不明である。また、この組成物は穀物などの天然素材のみで構成されているため、出来上がった成形品の品質が担保されず、工業製品としては不適当なものであった。 JP 2005-23262 (Patent Document 9) discloses cereals such as corn, dietary fibers such as weeds, main materials obtained by refining 100% natural materials such as sugar millet, and natural binders such as strawberries and konjac flour. A biodegradable composition is disclosed. However, the specific composition ratio is unknown, and it is unknown whether it can actually be manufactured as a product. Further, since this composition is composed only of natural materials such as grains, the quality of the finished molded product is not guaranteed, and it is unsuitable as an industrial product.
さらに特表平９−５００９２４号公報（特許文献１０）には、デンプンとタンパク質、セルロース、フェノール及びタンニン、トール油やワックスを含む生分解性組成物が開示されている。しかしながら、この組成物はトール油やワックスを含むものであるため、ワックス等の滲出が懸念される。従って、木工品などの製作には適しているとしても、食器などの加工品に適用した場合には安全性の観点から好ましくない問題を生じる可能性がある。 Further, JP-A-9-500944 (Patent Document 10) discloses a biodegradable composition containing starch and protein, cellulose, phenol and tannin, tall oil and wax. However, since this composition contains tall oil or wax, there is a concern about exudation of wax or the like. Therefore, even if it is suitable for the production of woodwork, etc., it may cause an undesirable problem from the viewpoint of safety when applied to processed products such as tableware.
生分解性のシートに関して言えば、例えば、特表平１０−５１１１４５号公報（特許文献１１）には、熱可塑性デンプンと生分解性のポリマー及びセルロース繊維並びにタンパク質などから作製された延伸フィルムが開示されている。特開２００２−３７１２０１号公報（特許文献１２）には、ポリ乳酸などの生分解性の樹脂と炭酸カルシウムなどの無機充填剤、さらにポリエチレングリコールなどの水溶性樹脂が用いられた生分解性のフィルムやシートが開示されている。また、特開平６−３１３０６３号公報（特許文献１３）には、デンプンと生分解性の脂肪酸ポリエステルに補強用添加剤としてタンパク質及び天然ゴムが添加された生分解性のフィルムが開示されている。しかしながら、これらのフィルムは脂肪酸ポリエステルを含むものであるのでコストが高くなる傾向にあり、生分解性に劣ることが考えられた。 With regard to the biodegradable sheet, for example, JP 10-511145 A (Patent Document 11) discloses a stretched film made from thermoplastic starch, a biodegradable polymer, cellulose fiber, protein, and the like. Has been. Japanese Patent Laid-Open No. 2002-371201 (Patent Document 12) discloses a biodegradable film using a biodegradable resin such as polylactic acid, an inorganic filler such as calcium carbonate, and a water-soluble resin such as polyethylene glycol. And sheets are disclosed. Japanese Patent Laid-Open No. 6-313063 (Patent Document 13) discloses a biodegradable film in which protein and natural rubber are added as reinforcing additives to starch and biodegradable fatty acid polyester. However, since these films contain fatty acid polyesters, the cost tends to be high, and it is considered that the biodegradability is poor.
特開２００３−２９２５５４号公報（特許文献１４）には、でんぷんなどの活性水素を有する生分解性化合物を主成分としてこれにアクリロイル基を有する化合物、さらに尿素やグリセリン、さらにはセルロースなどの天然繊維が用いられた生分解性のフィルムが開示されている。特開２００３−１０５１３０号公報（特許文献１５）には、デンプン、尿、カルボン酸基を有する化合物及び／又はグリセリンなどの水素結合性水溶性高沸点溶剤、架橋剤からなる生分解性のフィルムが開示されている。特開２００４−３３９４９６号公報（特許文献１６）には、デンプン類とそれに対して６０〜３００％の尿素並びに１０〜１５０質量％のグリセリンなどの多価アルコールさらには天然素材として紙や麻などの繊維が用いられた生分解性のフィルムが開示されている。しかしながら、これらのフィルムはグリセリンなどの多価アルコールを含むものであるので、使用中にこれらの多価アルコールが漏出する可能性が考えられた。 Japanese Patent Application Laid-Open No. 2003-292554 (Patent Document 14) discloses a biodegradable compound having active hydrogen such as starch as a main component and a compound having an acryloyl group, and urea, glycerin, and natural fibers such as cellulose. A biodegradable film in which is used is disclosed. JP-A-2003-105130 (Patent Document 15) discloses a biodegradable film comprising starch, urine, a compound having a carboxylic acid group and / or a hydrogen-bonding water-soluble high-boiling solvent such as glycerin and a crosslinking agent. It is disclosed. Japanese Patent Application Laid-Open No. 2004-339496 (Patent Document 16) discloses starches and polyhydric alcohols such as 60 to 300% urea and 10 to 150% by mass of glycerin, and natural materials such as paper and hemp. A biodegradable film using fibers is disclosed. However, since these films contain polyhydric alcohols such as glycerin, it was considered that these polyhydric alcohols might leak during use.
特開２００１−２８８２９５号（特許文献１７）には、コーングルテンミールと天然ゴムに可塑剤として尿素が用いられたフィルムが開示されているが、このフィルムは天然ゴムを含むので分解性に劣る可能性が考えられる。さらに特表２００２−５１２９２９号公報（特許文献１８）には、デンプンとタンパク質、天然セルロース繊維並びに金属塩水和物、可塑剤として尿素を含む組成物からなる生分解性のフィルムが開示されているが、このフィルムは金属塩を含むので分解後に周囲の環境を汚染する可能性が考えられる。 Japanese Patent Application Laid-Open No. 2001-288295 (Patent Document 17) discloses a film in which urea is used as a plasticizer for corn gluten meal and natural rubber. However, since this film contains natural rubber, it may be inferior in degradability. Sex is conceivable. Further, JP 2002-512929 A (Patent Document 18) discloses a biodegradable film comprising a composition containing starch and protein, natural cellulose fiber, metal salt hydrate, and urea as a plasticizer. Since this film contains a metal salt, there is a possibility of contaminating the surrounding environment after decomposition.
そして、特表２００１−５１７２５３号公報（特許文献１９）には穀物タンパク質とデンプンとグリセリンなどの可塑剤及び亜硫酸塩などの還元剤を含む組成物が、米国特許第５５２３２９３号公報（特許文献２０）には大豆タンパク質とデンプンフィラーとグリセリンなどの可塑剤、亜硫酸水素ナトリウムやメルカプトエタノールや還元剤などからなる組成物が開示されている。これらの組成物は還元剤によってデンプン中に存在するジスルフィド結合を還元処理することで、変性グルテンを生成させている。しかしながら、これらの組成物では還元剤が残留する可能性があり、衛生上好ましくないことが考えられた。 And in Japanese translations of PCT publication No. 2001-517253 (patent document 19), the composition containing a grain protein, a plasticizer, such as starch and glycerin, and a reducing agent such as sulfite is disclosed in US Pat. No. 5,523,293 (patent document 20). Discloses a composition comprising a soy protein, a starch filler, a plasticizer such as glycerin, sodium bisulfite, mercaptoethanol, a reducing agent, and the like. These compositions produce modified gluten by reducing disulfide bonds present in starch with a reducing agent. However, in these compositions, a reducing agent may remain, which is considered unfavorable for hygiene.
このような状況下において、本願発明者らによって、強度を高めた生分解性容器のための組成物として、特許第４０７７０２６号公報（特許文献２１）にデンプン、タンパク質、セルロース繊維、ポリフェノール類及び塩化ナトリウムからなる組成物が、また、耐水性を高めた生分解性シートのための組成物として、特許第４０７７０２７号公報（特許文献２２）にはタンパク質、セルロース繊維及び尿素からなり、必要に応じてデンプンが加えられた組成物が提案されている。 Under such circumstances, the inventors of the present application disclosed starch, protein, cellulose fiber, polyphenols, and chloride as a composition for a biodegradable container with increased strength in Japanese Patent No. 4077026 (Patent Document 21). Japanese Patent No. 4077027 (Patent Document 22) is composed of protein, cellulose fiber and urea as a composition for a biodegradable sheet with increased water resistance. Compositions with added starch have been proposed.
しかしながら、特許文献２１に記載の生分解性組成物にあっては、ポリフェノール類が用いられているので、場合によっては十分に生分解されないことが想定される。特許文献２２に記載の生分解性組成物は尿素を含有するために、シートそのものに尿素臭が感じられ、シートが水に接触した際には尿素臭がはっきりと感じられるという問題があった。また、富栄養化の観点から窒素の含有量が少ないことが望まれる。 However, in the biodegradable composition described in Patent Document 21, since polyphenols are used, it is assumed that the biodegradable composition is not sufficiently biodegraded in some cases. Since the biodegradable composition described in Patent Document 22 contains urea, a urea odor is felt on the sheet itself, and the urea odor is clearly felt when the sheet comes into contact with water. Further, it is desired that the nitrogen content is low from the viewpoint of eutrophication.
本願発明は上記の背景技術に鑑みてなされたものであって、還元剤や金属塩、ポリ乳酸などの生分解性プラスチックを含まず、強度や耐水性に優れ、しかも、尿素臭の発生の可能性が少ない生分解性容器やシートなどの成形品を提供することを目的としている。 The present invention has been made in view of the above-described background art, does not include a biodegradable plastic such as a reducing agent, metal salt, or polylactic acid, has excellent strength and water resistance, and can generate urea odor. It aims at providing molded articles, such as a biodegradable container and a sheet | seat with little property.
本願発明者らは、上記目的を達成するため、特許文献２２に開示された生分解性組成物の改良に取り組んだところ、グリセリンなどの多価アルコール類や尿素を用いずとも耐水性や強度に優れた生分解性容器やシートが得られることを見いだし、本願発明を完成するに至った。 In order to achieve the above object, the inventors of the present application have worked on improving the biodegradable composition disclosed in Patent Document 22, and the water resistance and strength can be improved without using polyhydric alcohols such as glycerin and urea. It has been found that excellent biodegradable containers and sheets can be obtained, and the present invention has been completed.
本発明の生分解性加工品は、１０ＭＰａ以上の引っ張り強度を有する生分解性成形品であって、タンパク質を２５.０質量％以上５５.０質量％以下、セルロース繊維を１１.０質量％以上３７.０質量％以下、デンプン０以上２５.０質量％以下、水１８.０質量％以上３５.０質量％以下を含み、金属塩、還元剤その他の添加剤（着色料及び安定剤を除く）を含まない生分解性組成物を１０ＭＰａ以上の引っ張り強度を有する加工品が得られるまで混練した混練物を、４０℃以上１３０℃以下の温度、２０ｋｇｆ以上１２０ｋｇｆ以下の加圧条件下でプレス加工して得られたものである。 The biodegradable processed product of the present invention is a biodegradable molded product having a tensile strength of 10 MPa or more, wherein protein is 25.0% by mass or more and 55.0% by mass or less, and cellulose fiber is 11.0% by mass or more. 37.0% by weight or less, starch 0 to 25.0% by weight, water 18.0% to 35.0% by weight, including metal salts, reducing agents and other additives (excluding colorants and stabilizers) ), A kneaded product obtained by kneading a biodegradable composition not containing) until a processed product having a tensile strength of 10 MPa or more is obtained , is pressed under a temperature of 40 ° C. to 130 ° C. and a pressure of 20 kgf to 120 kgf. It was obtained.
本発明によると、非常に単純な系の組成物から耐水性や強度に優れた生分解性の成形品やシートが得られる。本発明の成形品は尿素を含んでいないので尿素臭の発生や窒素の排出量が抑えられる。また、この成形品はタンパク質やセルロース繊維、デンプンと言った安価な材料から構成され、ポリ乳酸などの生分解性プラスチックや還元剤を含まないので、コストを安価にできる。しかも、ポリフェノール類を含まないので生分解されずに残る残留物の発生が少なく、アルミニウム塩、カルシウム塩などの金属塩や還元剤を含まないので、これらによる環境負荷を極めて少なくできる。 According to the present invention, a biodegradable molded article or sheet having excellent water resistance and strength can be obtained from a very simple composition. Since the molded article of the present invention does not contain urea, generation of urea odor and nitrogen discharge are suppressed. In addition, this molded article is composed of inexpensive materials such as protein, cellulose fiber, and starch, and does not contain biodegradable plastic such as polylactic acid or a reducing agent, so that the cost can be reduced. In addition, since polyphenols are not included, there is little generation of residues that remain without being biodegraded, and since metal salts such as aluminum salts and calcium salts and reducing agents are not included, the environmental burden due to these can be extremely reduced.
本発明の生分解性加工品は、１０ＭＰａ以上の引っ張り強度を有する生分解性成形品であって、タンパク質を２５.０質量％以上５５.０質量％以下、セルロース繊維を１１.０質量％以上３７.０質量％以下、デンプン０以上２５.０質量％以下、水１８.０質量％以上３５.０質量％以下を含み、金属塩、還元剤その他の添加剤（着色料及び安定剤を除く）を含まない生分解性組成物を１０ＭＰａ以上の引っ張り強度を有する加工品が得られるまで混練した混練物を、４０℃以上１３０℃以下の温度、２０ｋｇｆ以上１２０ｋｇｆ以下の加圧条件下でプレス加工して得られたものである。
The biodegradable processed product of the present invention is a biodegradable molded product having a tensile strength of 10 MPa or more, wherein protein is 25.0% by mass or more and 55.0% by mass or less, and cellulose fiber is 11.0% by mass or more. 37.0% by weight or less, starch 0 to 25.0% by weight, water 18.0% to 35.0% by weight, including metal salts, reducing agents and other additives (excluding colorants and stabilizers) ), A kneaded product obtained by kneading a biodegradable composition not containing) until a processed product having a tensile strength of 10 MPa or more is obtained , is pressed under a temperature of 40 ° C. to 130 ° C. and a pressure of 20 kgf to 120 kgf. It was obtained.
本発明で用いられる生分解性組成物は、上記のようにタンパク質とセルロース繊維と水の３成分から構成され、必要に応じ増量剤としてデンプンが配合されたものである。そして、さらに必要に応じて、グリセリンなどの軟化剤が添加されたものであって、金属塩及び還元剤並びにその他の添加剤（着色料及び安定剤を除く）を実質的に含まない。 The biodegradable composition used in the present invention is composed of the three components of protein, cellulose fiber, and water as described above, and is blended with starch as a bulking agent as necessary. Further, if necessary, a softener such as glycerin is added, and the metal salt, the reducing agent, and other additives (excluding colorants and stabilizers) are substantially not included.
本発明において用いられるタンパク質は、植物由来のタンパク質や動物由来のタンパク質のいずれでもよく、合成タンパク質であってもよい。植物由来のタンパク質（植物性タンパク質）には、例えば、大豆タンパク、小麦タンパク、米タンパクなど種々の豆類や穀類から得られるタンパク質が例示される。また、動物由来のタンパク質（動物性タンパク質）には、例えば、乳タンパクなど各種動物、鳥類、魚類由来のタンパク質が例示される。また、これらのタンパク質は抽出しただけで精製していない粗タンパク質のみならず、濃縮した濃縮タンパク質であってもよい。例えば、植物由来のタンパクであれば、大豆濃縮タンパク、動物由来のタンパクであれば、濃縮乳タンパクが例示される。一方、粗タンパク質を精製したタンパク質であってもよく、植物由来のタンパク質としてグルテン、ゼイン、ホルデイン、アベニン、カフィリンなどが例示され、動物由来のタンパク質としてカゼイン、アルブミン、コラーゲン、ゼラチン、ケラチンなどが例示される。これらのタンパク質は１種若しくは２種以上を用いることができる。 The protein used in the present invention may be either a plant-derived protein or an animal-derived protein, or a synthetic protein. Examples of plant-derived protein (plant protein) include proteins obtained from various beans and cereals such as soybean protein, wheat protein, and rice protein. Examples of animal-derived proteins (animal proteins) include proteins derived from various animals such as milk protein, birds, and fish. These proteins may be not only crude proteins that have been extracted but not purified, but also concentrated proteins that have been concentrated. For example, if it is plant-derived protein, soybean concentrated protein is exemplified, and if it is animal-derived protein, concentrated milk protein is exemplified. On the other hand, it may be a protein obtained by purifying a crude protein. Examples of plant-derived proteins include gluten, zein, hordein, avenin, and kafilin. Examples of animal-derived proteins include casein, albumin, collagen, gelatin, and keratin. Is done. These proteins can be used alone or in combination of two or more.
本発明において用いられるセルロース繊維は、天然若しくは人工のセルロース繊維のいずれでもよい。天然由来のセルロール繊維には、各種の植物、例えば籾殻などの穀類の種皮、草、木材、わら、さとうきび、綿、葉、トウモロコシの皮やさとうきびの絞り滓から得られたガバス、新聞紙などの加工品が例示される。これらのセルロース繊維は、わらや穀類の種皮などを乾燥させた後繊維状にほぐし、それを適当な長さに切断して用いられる。用いることのできるセルロース繊維は、太さが１〜１００μｍ程度、長さが１０μｍ〜３０ｍｍ程度であるが、成形品の用途や要求される強度などに応じて適宜決定される。 The cellulose fiber used in the present invention may be either natural or artificial cellulose fiber. Naturally-derived cellulose fibers include various seeds such as seed coats of cereals such as rice husks, grass, wood, straw, sugar cane, cotton, leaves, corn peel and sugar cane obtained from sugar cane, newspapers, etc. Goods are illustrated. These cellulose fibers are used by drying straw or cereal seed coats and then loosening them into fibers and cutting them into suitable lengths. Cellulose fibers that can be used have a thickness of about 1 to 100 μm and a length of about 10 μm to 30 mm, and are appropriately determined depending on the use of the molded product, the required strength, and the like.
本発明において用いられるデンプンは、天然物由来によるデンプン（天然デンプン）のみならず、天然デンプンを化学的に処理し、化学修飾を行った化学修飾デンプンのいずれでもよく、また、これらを適宜混合して用いることもできる。 The starch used in the present invention may be not only a starch derived from a natural product (natural starch) but also any chemically modified starch obtained by chemically treating natural starch and subjecting it to chemical modification. Can also be used.
天然デンプンとは、トウモロコシデンプン、ジャガイモデンプン、サツマイモデンプン、小麦デンプン、米デンプン、タピオカデンプン、ソルガムデンプンなど種々の植物から得られるデンプンであって、起源となる植物は限定されない。また、デンプン中に含まれるアミロース、アミロペクチン含量も特に問われるものでもなく、高アミローストウモロコシデンプンのようにアミロース含量を高めたデンプンを用いてもよい。また、本発明においては単一のデンプンのみならず、２種以上の天然デンプンを用いてもよい。 The natural starch is starch obtained from various plants such as corn starch, potato starch, sweet potato starch, wheat starch, rice starch, tapioca starch, sorghum starch, and the origin plant is not limited. Further, the amylose and amylopectin contents contained in the starch are not particularly limited, and starch having a high amylose content such as high amylose corn starch may be used. In the present invention, not only a single starch but also two or more kinds of natural starches may be used.
化学修飾デンプンは、デンプンを構成するグルコースの水酸基に置換基を導入したものである。置換基は特に限定されるものではなく、被修飾デンプンである天然デンプンの種類も限定されるものではない。化学修飾デンプンとしては、例えば、ヒドロキシプロピルデンプン、カルボキシメチルデンプン、アセチル化高アミロースデンプン、酢酸デンプン、マレイン酸デンプン、オクテニルコハク酸デンプン、コハク酸デンプン、フタル酸デンプン、ヒドロキシプロピル高アミロースデンプン、架橋デンプン、リン酸デンプン、リン酸ヒドロキシプロピルジデンプンが例示される。これらの化学修飾デンプンも、単一種に限られず、２種以上を混合して用いても差し支えない。ここにいう架橋デンプンとは、リン酸塩化物、エピクロルヒドリン、リン酸誘導体等の種々の架橋剤によりデンプン分子を架橋したものをいう。 Chemically modified starch is obtained by introducing a substituent into the hydroxyl group of glucose constituting starch. The substituent is not particularly limited, and the type of natural starch that is the modified starch is not limited. As the chemically modified starch, for example, hydroxypropyl starch, carboxymethyl starch, acetylated high amylose starch, acetate starch, starch maleate, octenyl succinate starch, succinate starch, phthalate starch, hydroxypropyl high amylose starch, cross-linked starch, Examples include phosphate starch and hydroxypropyl distarch phosphate. These chemically modified starches are not limited to a single type, and two or more types may be mixed and used. The term “crosslinked starch” as used herein refers to those obtained by crosslinking starch molecules with various crosslinking agents such as phosphates, epichlorohydrin, phosphoric acid derivatives and the like.
本発明の組成物におけるセルロース繊維の配合量は１１.０質量％以上３７.０質量％以下、タンパク質の配合量は２５.０質量％以上５５.０質量％以下である。セルロース繊維の配合量やタンパク質の配合量がこれよりも少ない場合やこれよりも多い場合のいずれにおいても、捏ねが十分に出来なかったり、捏ねが出来たとした場合でもプレス成形ができなかったりする。 The blending amount of the cellulose fiber in the composition of the present invention is 11.0% by mass or more and 37.0% by mass or less, and the blending amount of the protein is 25.0% by mass or more and 55.0% by mass or less. In both cases where the blending amount of cellulose fiber and the blending amount of protein is smaller or larger than this, kneading cannot be performed sufficiently, or even if kneading is performed, press molding cannot be performed.
本発明の組成物において、デンプンは任意成分であって、必要に応じて前記セルロース繊維やタンパク質に加えて使用され、あるいはそれらの一部に置き換えて使用されるものである。また、本発明においては、特許文献１９や２０に開示されているような還元剤による処理を不要とする。 In the composition of the present invention, starch is an optional component and is used in addition to the cellulose fiber or protein as necessary, or a part thereof. In the present invention, treatment with a reducing agent as disclosed in Patent Documents 19 and 20 is not required.
デンプンを配合する際には、組成物中に０より多く、０.０１質量％以上、好ましくは０.１％質量％以上、２５.０質量％以下である。低廉価の観点からは、デンプンの配合量を多くするのが好ましいが、デンプンの配合量が多くなると得られた成形品やシートの透明性が低下する傾向にあり、２５.０質量％を越えると良好な成形（プレス加工）ができない。 When starch is blended, it is more than 0 and 0.01% by mass or more, preferably 0.1% by mass or more and 25.0% by mass or less in the composition. From the viewpoint of low cost, it is preferable to increase the blending amount of starch, but when the blending amount of starch increases, the transparency of the obtained molded product or sheet tends to decrease, exceeding 25.0% by mass. Good molding (press processing) is not possible.
さらに、本発明の組成物には必要に応じて軟化剤が添加される。本発明において軟化剤とは、捏ねた組成物に柔軟性を付与するだけでなく、組成物の流動性を向上させ、成形加工をしやすくするために用いられる。この意味において、本発明の軟化剤は合成樹脂組成物における可塑剤（Plasticizers）の機能と滑剤（Lubricants）の機能の双方を合わせ持つものと言える。この軟化剤として、グリセリンやジグリセリン、脂肪酸の炭素数が１２〜２２であるグリセリン脂肪酸エステル、炭素数が４〜１８の脂肪酸のいずれか１種又は２種以上が用いられる。グリセリン脂肪酸エステルは、グリセリンモノ脂肪酸エステル、グリセリンジ脂肪酸エステル、グリセリントリ脂肪酸エステルの何れでもよい。グリセリン脂肪酸エステルを構成する脂肪酸は飽和、不飽和を問わず炭素数１２〜２２の直鎖又は分岐鎖の脂肪酸が用いられ、その脂肪酸として、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、パルミトレイン酸、オレイン酸、リノール酸、リノレン酸が例示される。また、軟化剤として用いられる脂肪酸として、酪酸や吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ステアリン酸、パルミトレイン酸、オレイン酸、リノール酸、リノレン酸などの脂式モノカルボン酸が例示される。また、コハク酸やアジピン酸のように２以上のカルボキシル基を有する脂式ジ脂肪酸も用いることができる。なお、本発明では生分解性であることが望まれるので、芳香族脂肪酸は好ましくない。もっとも生分解性に影響を及ぼさない限りにおいてはこの限りではない。また、生分解性の観点や成形品からの滲出を考慮すれば、これらの軟化剤のうちグリセリンが最も好ましいと言える。 Furthermore, a softening agent is added to the composition of the present invention as necessary. In the present invention, the softener is used not only to impart flexibility to the kneaded composition, but also to improve the fluidity of the composition and facilitate molding. In this sense, it can be said that the softener of the present invention has both the functions of plasticizers and lubricants in the synthetic resin composition. As this softening agent, glycerin, diglycerin, glycerin fatty acid ester whose fatty acid has 12 to 22 carbon atoms, or fatty acid having 4 to 18 carbon atoms are used. The glycerin fatty acid ester may be any of glycerin mono-fatty acid ester, glycerin di-fatty acid ester, and glycerin tri-fatty acid ester. The fatty acid constituting the glycerin fatty acid ester is a linear or branched fatty acid having 12 to 22 carbon atoms regardless of whether it is saturated or unsaturated. As the fatty acid, lauric acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid And oleic acid, linoleic acid, and linolenic acid. Fatty acids used as softeners include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid And fatty monocarboxylic acids such as linoleic acid and linolenic acid. In addition, an aliphatic difatty acid having two or more carboxyl groups such as succinic acid and adipic acid can also be used. In the present invention, aromatic fatty acids are not preferred because they are desired to be biodegradable. However, this does not apply as long as it does not affect biodegradability. In view of biodegradability and exudation from a molded product, glycerin is most preferable among these softening agents.
軟化剤の添加量は組成物中１０.０質量％以下である。軟化剤は、軟化剤を除いた成分、すなわちタンパク質、セルロース繊維及び必要に応じて加えられたデンプンからなる２又は３成分系の組成物から良好なプレス成形性が得られる場合において、０より多く、０.０１質量％以上、好ましくは０.１％質量％以上、１０.０％質量％以下で任意に加えることができる。軟化剤の添加量が多くなり、１０.０質量％を越えると、捏ねが不十分になりやすく、プレス加工の際に破断される虞やプレス成形そのものができなくなる虞がある。従って、その添加量は少量であることがよく、好ましくは組成物中に８.０％質量以下、望ましくは５.０質量％以下、特にデンプンを用いない場合では組成物中に５.０％質量以下とするのが好ましい。 The addition amount of the softening agent is 10.0% by mass or less in the composition. A softener is more than 0 when good press formability is obtained from a two or three component composition consisting of ingredients excluding the softener, ie protein, cellulose fibers and optionally added starch. , 0.01% by mass or more, preferably 0.1% by mass or more and 10.0% by mass or less. If the amount of the softening agent increases and exceeds 10.0% by mass, the kneading tends to be insufficient, and there is a possibility that it may be broken during press working or the press molding itself cannot be performed. Therefore, the amount added should be small, preferably 8.0% by weight or less in the composition, desirably 5.0% by weight or less, and 5.0% in the composition when no starch is used. It is preferable to set it to mass or less.
水の配合量は上記２成分若しくは３成分からなる組成物に対して、十分な捏ねができるように適宜決められるが、好ましくは１８.０質量％以上３５.０質量％以下である。水の配合量が１８.０質量％よりも少ないと、いわゆる団子状となって捏ねが困難となる。また、３５.０質量％を越えると組成物に占める水の量が多くなり、この場合も十分に捏ねることができなくなる。 The amount of water is appropriately determined so that sufficient kneading can be performed with respect to the composition composed of the above two or three components, but is preferably 18.0% by mass or more and 35.0% by mass or less. When the blending amount of water is less than 18.0% by mass, so-called dumpling is formed and kneading becomes difficult. On the other hand, if it exceeds 35.0% by mass, the amount of water in the composition increases, and in this case, it cannot be sufficiently kneaded.
本発明で用いられる組成物は上記の成分から構成され、それ以外の添加剤、例えば、還元剤、合成樹脂組成物に配合され滑剤として使用されるワックスやパラフィン、可塑剤として使用されるフタル酸エステルやアジピン酸エステル、脂肪酸の金属塩、タンニンやポリフェノール、ポリ乳酸などの高分子物質を実質的に含まない。ここで実質的に含まないとは意図して加えないという意味で用いられ、不純物や混入物としてこれらの物質を全く含まないという意味で用いられるのではない。ただし、成形性、得られた成形品の物性（例えば強度など）に影響を及ぼさない限りにおいて、加熱による着色を防止するための着色防止剤や生分解速度を低下させ、成形品の寿命を引き延ばすための生分解速度調整剤（例えば、カルボジイミド化合物や天然物由来のキトサン、ハーブ、ポリリジン、ヨモギ等の抗菌剤）のような安定剤や着色料を含ませることができる。このような着色防止剤や生分解速度調整剤などの安定剤や着色料の配合量はそれらの合計量として多くても組成物中に１０.０質量％、好ましくは５.０質量％以下、より望ましくは３質量％以下、さらに望ましくは１質量％以下である。 The composition used in the present invention is composed of the above-mentioned components, and other additives such as a reducing agent, wax and paraffin used as a lubricant blended in a synthetic resin composition, and phthalic acid used as a plasticizer. It does not substantially contain high-molecular substances such as esters, adipic acid esters, fatty acid metal salts, tannins, polyphenols, and polylactic acid. Here, it is used in the sense that it is not intended to be substantially added, and is not used in the sense that it does not contain any of these substances as impurities or contaminants. However, as long as it does not affect the moldability and physical properties of the resulting molded product (for example, strength), it reduces the anti-coloring agent and biodegradation rate to prevent coloration by heating, and extends the life of the molded product. Stabilizers and colorants such as biodegradation rate modifiers (for example, carbodiimide compounds and antibacterial agents such as chitosan, herbs, polylysine, mugwort and the like derived from natural products) can be included. The blending amount of such stabilizers and coloring agents such as anti-coloring agents and biodegradation rate adjusting agents is at most 10.0% by mass, preferably 5.0% by mass or less in the composition, More preferably, it is 3 mass% or less, More preferably, it is 1 mass% or less.
本発明の成形品は次のようにして得られる。まず、タンパク質やセルロース繊維や水などを含む本発明の組成物を室温において十分に捏ねる。ここで室温とは、概ね１０〜３０℃程度の温度を示し、加温や冷却をしてこの温度範囲に維持する必要はないという意味で用いられる。もっとも、室温が極端に低い、例えば０℃以下であったり、極端に高い、例えば５０℃以上であったりして、捏ねが十分にできない場合には、適宜、加温したり冷却することは差し使えない。 The molded product of the present invention is obtained as follows. First, the composition of the present invention containing protein, cellulose fiber, water and the like is sufficiently kneaded at room temperature. Here, room temperature indicates a temperature of about 10 to 30 ° C., and is used in the sense that it is not necessary to maintain the temperature range by heating or cooling. However, if the room temperature is extremely low, for example, 0 ° C. or lower, or extremely high, for example, 50 ° C. or higher, and kneading cannot be sufficiently performed, heating or cooling may be appropriately performed. Not available.
捏ねはどのような方法によってもよく、例えば二軸ミキサーなどの混練機などを用いて行う。このとき、各成分が混ざるだけでは不十分であって、おおよそ耳たぶ程度の硬さ、好ましくはいわゆる麺の腰が出る程度まで十分に捏ねる。捏ねが不足すれば、グルテンの成長が足りず、プレス成形ができない可能性や得られた成形品の透明性が悪くなる可能性が高い。また、成形品がもろくなり、取り出し時に成形品が壊れる虞もある。 The kneading may be performed by any method, for example, using a kneader such as a twin screw mixer. At this time, it is not sufficient to mix the respective components, and it is sufficiently kneaded to a hardness of about the level of an earlobe, preferably a so-called noodle waist. If kneading is insufficient, there is a high possibility that the growth of gluten will be insufficient, the press molding may not be possible, and the transparency of the resulting molded product will deteriorate. Further, the molded product becomes fragile, and the molded product may be broken when taken out.
得られた混練物はプレス加工によって種々の成形品に加工される。本発明において成形品とは、プレス加工によって加工されうるあらゆる物品を意味し、それらの形状や大きさ、用途は限られず、シートやフィルムである膜状物を含む広い意味で用いられる。本発明における成形品としては、食品などの各種物品を収納する収納容器、例えばトレーやケースなど、使い捨て弁当箱のような食品用の包装容器、皿や匙、コップ、お椀、使い捨て用のフォークやナイフ、スプーンなどの食器類はもちろんのこと、食品包装用のラップ用材、いわゆるブルーシート、保温や防寒のために用いられる農業用シート材などの膜状物が例示される。成形品の厚みは、好ましくは膜状物であれば概ね１０μｍ〜１０００μｍ、好ましくは１０μｍ〜３００乃至５００μｍ、収納容器や包装容器であれば概ね０.５ｍｍ〜５ｍｍ、好ましくは０.５ｍｍ〜２乃至３ｍｍ程度である。さらに、得られた膜状物を加工して、ビニール袋やゴミ袋などのような袋状物を得ることもできる。もっとも、膜状物を経ることなく、前記組成物と金型を用いて直接袋状物を得ることも可能である。特に、弁当箱のような食品用の包装容器やゴミ袋とした場合、食品とそれ以外のプラスチック類を人手により分別することなくそのまま堆肥化できるというメリットがある。また、堆肥化した土壌も、金属塩を含まないので金属によって汚染されず、窒素過多に陥ることもなく、農業用土壌や園芸用土壌として好適に使用できる。 The obtained kneaded material is processed into various molded products by press working. In the present invention, the molded product means any article that can be processed by press working, and its shape, size, and use are not limited, and it is used in a broad sense including a film-like material such as a sheet or a film. As the molded product in the present invention, a storage container for storing various articles such as food, for example, a tray or a case, a food packaging container such as a disposable lunch box, a dish, a bowl, a cup, a bowl, a disposable fork, As well as tableware such as knives and spoons, film-like materials such as wrapping materials for food packaging, so-called blue sheets, and agricultural sheet materials used for heat insulation and cold protection are exemplified. The thickness of the molded article is preferably about 10 μm to 1000 μm, preferably 10 μm to 300 to 500 μm for a film-like product, and about 0.5 mm to 5 mm, preferably 0.5 mm to 2 to about a storage container or packaging container. It is about 3 mm. Furthermore, the obtained film-like product can be processed to obtain a bag-like product such as a plastic bag or a garbage bag. However, it is also possible to obtain a bag-like product directly using the composition and the mold without going through a film-like product. In particular, when a food packaging container such as a lunch box or a garbage bag is used, there is an advantage that food and other plastics can be composted as they are without being manually separated. In addition, since the composted soil does not contain a metal salt, it is not contaminated with metal and does not fall into excessive nitrogen, and can be suitably used as agricultural soil or horticultural soil.
プレス加工は一対の金型に素材を挟み込み、圧力をかけて所望する形状に加工するという一般的な意味で用いられ、膜状物への加工を含む意味で用いられる。膜状物への加工にはいわゆる圧延加工であるカレンダー法やロール加工が好ましく用いられ、上記捏ねられた組成物がそのまま圧延機に供給される。また、膜状物以外の成形品への加工には凹部を有する雌金型と凸部を有する雄金型が用いられ、上記捏ねられた組成物が雌金型と雄金型の間に直接供給され加圧される。あるいは、上記組成物から圧延などにより得られた中間品である膜状物が雌金型と雄金型の間に供給される。なお、中間品である膜状物を得る場合には高温に注意すべきである。高温にて圧延加工等を行うと塑性変形を生じ、皿やコップなどの成形品（最終製品）への加工ができなくなるからである。また、プレス加工前に捏ねた組成物や中間品を保存する場合には、例えば密閉容器に保存するなど過度の水分蒸発を防ぐ対策が必要である。 The press working is used in a general sense that a material is sandwiched between a pair of molds and processed into a desired shape by applying pressure, and is used in a sense including processing into a film-like product. For processing into a film-like material, a calendar method or roll processing which is so-called rolling processing is preferably used, and the kneaded composition is supplied as it is to a rolling mill. Moreover, a female mold having a concave portion and a male die having a convex portion are used for processing into a molded product other than a film-like product, and the kneaded composition is directly between the female die and the male die. Supply and pressurize. Alternatively, a film-like product, which is an intermediate product obtained from the above composition by rolling or the like, is supplied between the female die and the male die. It should be noted that high temperatures should be taken into account when obtaining an intermediate film. This is because if rolling or the like is performed at a high temperature, plastic deformation occurs, and it becomes impossible to process a molded product (final product) such as a dish or a cup. Further, when the composition or intermediate product kneaded before pressing is stored, it is necessary to take measures to prevent excessive moisture evaporation, for example, storing it in a sealed container.
プレス加工時の条件は適宜定めればよいが、本発明の組成物を用いた場合には、少なくとも１０ｋｇｆ程度の加圧及び４０℃の加熱が望まれる。本発明では、捏ねによるグルテンの成長が望まれるだけでなく、適度な圧力及び熱を加えることが高い強度及び耐水性のある成形品を得るために必要だからである。加熱や加圧が不足すれば、強度が不足したり、成形品の透明性や耐水性が低下したりする。また、加熱や加圧が過剰になれば、いわゆる熱やけを起こして褐変を生じたり、成形品がもろくなったりする。本発明の組成物では、４０℃以上１３０℃以下の加熱、好ましくは５０℃以上１２０℃以下の加熱及び１０ｋｇｆ以上１２０ｋｇｆ以下の加圧、好ましくは２５ｋｇｆ以上１００ｋｇｆ以下の加圧で良好な成形品が得られる。 The conditions at the time of pressing may be determined as appropriate, but when the composition of the present invention is used, pressurization of at least about 10 kgf and heating at 40 ° C. are desired. In the present invention, not only is growth of gluten by kneading desired, but it is necessary to apply an appropriate pressure and heat to obtain a molded product having high strength and water resistance. If heating or pressurization is insufficient, the strength will be insufficient, or the transparency and water resistance of the molded product will be reduced. Moreover, when heating and pressurization become excessive, so-called heat burn is caused to cause browning or the molded product becomes brittle. In the composition of the present invention, a good molded article can be obtained by heating at 40 ° C. or higher and 130 ° C. or lower, preferably 50 ° C. or higher and 120 ° C. or lower and pressure of 10 kgf or higher and 120 kgf or lower, preferably 25 kgf or higher and 100 kgf or lower. can get.
得られる成形品の強度は、引っ張り強度として少なくとも１０ＭＰａ以上、好ましい場合には１５ＭＰａ以上、より望ましい場合には２０ＭＰａ以上である。また、得られる成形品は、常温にて水に浸漬した場合、２週間の浸漬に耐えられる耐水性を有する。つまり、水に浸して室温に放置したとしても、２週間は初期の形状がほぼ維持される。このように本発明の生分解性成形品は、耐水処理をすることなく良好な耐水性が得られるが、さらに耐水性を増すために、例えばポリ乳酸（ＰＬＡ）やポリカプロラクタン（ＰＬＣ）などの生分解性物質による耐水コートを成形品表面に施しても良い。 The strength of the obtained molded product is at least 10 MPa or more as a tensile strength, 15 MPa or more when preferable, and 20 MPa or more when more desirable. Moreover, when the molded article obtained is immersed in water at room temperature, it has water resistance that can withstand immersion for 2 weeks. That is, even if it is immersed in water and left at room temperature, the initial shape is almost maintained for two weeks. As described above, the biodegradable molded article of the present invention can have good water resistance without being subjected to water resistance treatment. However, in order to further increase the water resistance, for example, polylactic acid (PLA) or polycaprolactan (PLC). A water-resistant coating with a biodegradable substance such as may be applied to the surface of the molded product.
次に本発明について下記の実施例に基づきさらに詳細に説明するが、本発明は下記の実施例に限定されることのないのは言うまでもない。 Next, the present invention will be described in more detail based on the following examples. However, it is needless to say that the present invention is not limited to the following examples.
まず、タンパク質、デンプン、セルロース繊維からなる組成物のプレス加工性について評価を行った。トウモロコシデンプン（ワコー純薬（株）社製「コーンスターチ」）、コムギタンパク（長田産業（株）社製 「フメリットＡ」）、セルロースファイバー（日本製紙ケミカル（株）製ＫＣフロック＃１００メッシュ又は＃２００）を表１の配合量に従って配合し、自転公転ミキサーを用いて室温（約２５℃）でいわゆる腰がでるまで混合混練した。この混練物を２軸プレス機により約３ｍｍ厚のシート状に延伸して、温度１２０℃圧力１００ｋｇｆにて金型プレスを用いて厚み１ｍｍのカップ状に成形した。その結果を表２に示した。表１には各成分量を質量比で示し、表２には組成比を示した。 First, the press workability of a composition comprising protein, starch, and cellulose fiber was evaluated. Corn starch (“Corn Starch” manufactured by Wako Pure Chemical Industries, Ltd.), wheat protein (“Fmerit A” manufactured by Nagata Sangyo Co., Ltd.), cellulose fiber (KC Flock # 100 mesh or # 200 manufactured by Nippon Paper Chemicals Co., Ltd.) ) Was blended and kneaded at room temperature (about 25 ° C.) using a rotating and rotating mixer until the so-called sag occurred. This kneaded product was stretched into a sheet shape of about 3 mm thickness by a biaxial press and formed into a cup shape of 1 mm thickness using a die press at a temperature of 120 ° C. and a pressure of 100 kgf. The results are shown in Table 2. Table 1 shows the amount of each component by mass ratio, and Table 2 shows the composition ratio.
これによると、デンプンを加えない場合では、タンパク質１０質量部に対しセルロース繊維が４質量部以上１１質量部以下、水が５質量部以上１０質量部以下でプレス成形性が確保された。また、タンパク質１０質量部、セルロース繊維が３質量部の組成物に対してデンプンを６質量部、水を１３質量部まで加えてもプレス成形性が確保された。これらの結果から、表２に示すようにタンパク質２５.０〜５５.０質量％、セルロース繊維１１.０〜３７.０質量％、デンプン０〜２５.０質量％、水１８.０〜３５.０質量％からなる組成物が良好な生分解性組成物として利用できることが示された。 According to this, when no starch was added, press moldability was ensured with 4 to 11 parts by mass of cellulose fiber and 5 to 10 parts by mass of water with respect to 10 parts by mass of protein. Moreover, press moldability was ensured even when 6 parts by mass of starch and 13 parts by mass of water were added to a composition having 10 parts by mass of protein and 3 parts by mass of cellulose fiber. From these results, as shown in Table 2, 25.0-55.0 mass% protein, 11.0-37.0 mass% cellulose fiber, 0-25.0 mass% starch, 18.0-35. It was shown that a composition consisting of 0% by mass can be used as a good biodegradable composition.
次にグリセリンの添加可能性について評価を行った。上記トウモロコシデンプン、コムギタンパク、セルロースファイバー、グリセリン（健栄製薬（株）社製 「局方グリセリン」：グリセリンとして８６％含有）を表３に従って配合し、実施例１と同様に成形性を評価した。その結果を表４に示す。表３には各成分量を質量比で示し、表４には組成比を示した。なお、グリセリンについては、表３では用いた局方「グリセリン」の配合量を示し、表４にはグリセリンの絶対量に換算した値を示している。 Next, the possibility of adding glycerin was evaluated. The above corn starch, wheat protein, cellulose fiber, and glycerin (“Keiei Pharmaceutical Co., Ltd.“ Phosphorus glycerin ”: 86% contained as glycerin) were blended according to Table 3, and the moldability was evaluated in the same manner as in Example 1. . The results are shown in Table 4. Table 3 shows the amount of each component by mass ratio, and Table 4 shows the composition ratio. As for glycerin, Table 3 shows the blending amount of the pharmacopoeia “glycerin” used, and Table 4 shows values converted to the absolute amount of glycerin.
これによると、上記表１に示されかつ良好な成形性が得られた範囲にあるタンパク質とセルロース繊維からなる組成物に対してグリセリンを２質量部以下で加えた場合では良好なプレス成形性が得られたが、３質量部以上加えた場合には良好なプレス成形性が得られなかった。また、タンパク質とセルロース繊維及びデンプンからなる組成物に対してはグリセリンを３質量部まで加えられることができた。これらの結果から、表４に示すように、デンプン０〜２５.０質量％、タンパク質２５.０〜５５.０質量％、セルロース繊維１１.０〜３７.０質量％、水１８.０〜３５.０質量％からなる組成物に対してグリセリンを１０質量部以下で加えた組成物が良好な生分解性組成物として利用できることが確認された。 According to this, in the case where glycerin is added in an amount of 2 parts by mass or less with respect to the composition consisting of protein and cellulose fiber in the range shown in Table 1 and in which good moldability is obtained, good press moldability is obtained. Although it was obtained, when 3 parts by mass or more was added, good press formability was not obtained. In addition, up to 3 parts by mass of glycerin could be added to a composition comprising protein, cellulose fiber and starch. From these results, as shown in Table 4, starch 0-25.0 mass%, protein 25.0-55.0 mass%, cellulose fiber 11.0-37.0 mass%, water 18.0-35. It was confirmed that a composition in which glycerin was added in an amount of 10 parts by mass or less based on a composition consisting of 0.0% by mass can be used as a good biodegradable composition.
プレス条件について検討を加えた。実施例１及び実施例２において良好な成形性が得られた組成物（Ｎｏ.６とＮｏ.２１、表５参照）について、プレス加工時の温度及び圧力条件について検討を加えた。 The press conditions were examined. With respect to the compositions (No. 6 and No. 21, see Table 5) in which good moldability was obtained in Example 1 and Example 2, examination was made on the temperature and pressure conditions during press working.
グリセリンを加えた場合加えない場合のいずれの場合も同様な結果が示され、それらを代表してグリセリンを加えない場合の結果を表６に示した。表６に示すようにいずれも、４０〜１３０℃の温度範囲で、２０〜１２０ｋｇｆの圧力範囲で良好なプレス加工性が得られた。特に表中に◎で示された範囲、つまり５０〜１２０℃の温度範囲で、２５〜１００ｋｇｆの圧力の条件において、より良好な成形性が得られた。 Similar results were shown in both cases where glycerin was added and not added. Table 6 shows the results when glycerin was not added. As shown in Table 6, in all cases, good press workability was obtained in the temperature range of 40 to 130 ° C. and in the pressure range of 20 to 120 kgf. In particular, better moldability was obtained in the range indicated by ◎ in the table, that is, in the temperature range of 50 to 120 ° C. and under the pressure of 25 to 100 kgf.
実施例１及び実施例２において良好な成形性が得られた組成物（Ｎｏ.６、２２、２８）について強度試験を行った。強度試験は引張強度試験器（島津製作所社製：オートグラフAGS-10KNG、JIS K 6251 2004準拠、試験片形状：ダンベル状３号形、試験速度：５００mm/分）によって実施された。上記各組成物を１２５℃、１００ｋｇｆの条件で５分間プレスして作製した試験片を用いた。その結果を表７に示す。表７に示すように、グリセリンの有無によらず、またデンプンが配合された場合であっても、最低でも１５ＭＰａ、平均すると２０ＭＰａ以上の強度が得られた。 A strength test was performed on the compositions (Nos. 6, 22, and 28) in which good moldability was obtained in Example 1 and Example 2. The strength test was carried out using a tensile strength tester (manufactured by Shimadzu Corporation: Autograph AGS-10KNG, JIS K 6251 2004, test piece shape: dumbbell shape No. 3, test speed: 500 mm / min). A test piece prepared by pressing each of the above compositions under the conditions of 125 ° C. and 100 kgf for 5 minutes was used. The results are shown in Table 7. As shown in Table 7, regardless of the presence or absence of glycerin, and even when starch was blended, a strength of at least 15 MPa and an average of 20 MPa or more were obtained.
実施例１及び実施例２において良好な成形性が得られた組成物（Ｎｏ.６、２２、１６、２８）について耐水性試験を行った。耐水性試験は水に浸漬して室温に放置した。その結果を表８に示す。表８に示すように、水に浸漬した場合、１４日間でも初期の形状が維持され、本発明の成形品は十分な耐水性があることが示された。これによると、グリセリンが１０質量％以下で配合された場合でもグリセリンを含まない場合と同様の耐水性を示した。また、デンプンの配合の有無にも関係なく良好な耐水性を示した。 A water resistance test was performed on the compositions (Nos. 6, 22, 16, and 28) from which good moldability was obtained in Example 1 and Example 2. The water resistance test was immersed in water and left at room temperature. The results are shown in Table 8. As shown in Table 8, when immersed in water, the initial shape was maintained even for 14 days, indicating that the molded article of the present invention has sufficient water resistance. According to this, even when glycerin was blended at 10% by mass or less, the same water resistance as when no glycerin was contained was shown. Moreover, good water resistance was exhibited regardless of the presence or absence of the starch.
本発明の生分解性成形品は、シートや食器、包装容器などとして利用される。 The biodegradable molded product of the present invention is used as a sheet, tableware, a packaging container or the like.
Claims (6)
セルロース繊維を１１.０質量％以上３７.０質量％以下、
デンプン０以上２５.０質量％以下、
水１８.０質量％以上３５.０質量％以下を含み、
金属塩、還元剤その他の添加剤（着色料及び安定剤を除く）を含まない生分解性組成物を１０ＭＰａ以上の引っ張り強度を有する加工品が得られるまで混練した混練物を、４０℃以上１３０℃以下の温度、２０ｋｇｆ以上１２０ｋｇｆ以下の加圧条件下でプレス加工して得られた１０ＭＰａ以上の引っ張り強度を有する生分解性成形品。 25.0% to 55.0% by weight of protein,
11.0% by weight or more and 37.0% by weight or less of cellulose fiber,
0 to 25.0% by weight of starch,
Including 18.0% by weight or more and 35.0% by weight or less of water,
A kneaded product obtained by kneading a biodegradable composition not containing a metal salt, a reducing agent and other additives (excluding colorants and stabilizers) until a processed product having a tensile strength of 10 MPa or more is obtained. A biodegradable molded article having a tensile strength of 10 MPa or more obtained by pressing under a temperature of 20 ° C. or less and a pressure of 20 kgf or more and 120 kgf or less.
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| KR20150013055A (en) | 2013-07-26 | 2015-02-04 | 박찬오 | A bio-degradable composition comprising cellulose, a manufacturing method for the same, and a water-proof agnet and goods using the same |
| JP2015135914A (en) * | 2014-01-17 | 2015-07-27 | 三菱化学株式会社 | Solar cell module built-in film material |
| RU2725039C1 (en) * | 2019-12-30 | 2020-06-29 | федеральное государственное автономное образовательное учреждение высшего образования "Южно-Уральский государственный университет (национальный исследовательский университет)" | Biodegradable dishware production method |
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| JP2011084709A (en) | 2011-04-28 |
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