JP6829598B2 - Starch / resin composite molding processing material - Google Patents
Starch / resin composite molding processing material Download PDFInfo
- Publication number
- JP6829598B2 JP6829598B2 JP2016255266A JP2016255266A JP6829598B2 JP 6829598 B2 JP6829598 B2 JP 6829598B2 JP 2016255266 A JP2016255266 A JP 2016255266A JP 2016255266 A JP2016255266 A JP 2016255266A JP 6829598 B2 JP6829598 B2 JP 6829598B2
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- Prior art keywords
- starch
- resin composite
- molding
- resin
- melting point
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- 229920002472 Starch Polymers 0.000 title claims description 367
- 239000008107 starch Substances 0.000 title claims description 366
- 235000019698 starch Nutrition 0.000 title claims description 366
- 239000000805 composite resin Substances 0.000 title claims description 240
- 239000000463 material Substances 0.000 title claims description 213
- 238000000465 moulding Methods 0.000 title claims description 173
- 238000012545 processing Methods 0.000 title claims description 69
- 239000008187 granular material Substances 0.000 claims description 138
- 239000000654 additive Substances 0.000 claims description 133
- 238000002844 melting Methods 0.000 claims description 123
- 230000008018 melting Effects 0.000 claims description 120
- 230000000996 additive effect Effects 0.000 claims description 113
- 229920005992 thermoplastic resin Polymers 0.000 claims description 61
- 239000002994 raw material Substances 0.000 claims description 56
- 239000002131 composite material Substances 0.000 claims description 53
- 239000012778 molding material Substances 0.000 claims description 52
- -1 glycerin fatty acid ester Chemical class 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 29
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 19
- 239000000194 fatty acid Substances 0.000 claims description 19
- 229930195729 fatty acid Natural products 0.000 claims description 19
- 238000001125 extrusion Methods 0.000 claims description 17
- 230000005484 gravity Effects 0.000 claims description 17
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- 239000011347 resin Substances 0.000 claims description 16
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 14
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- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 11
- 238000001746 injection moulding Methods 0.000 claims description 10
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- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
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- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
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- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 8
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- 239000004368 Modified starch Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
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- RPZANUYHRMRTTE-UHFFFAOYSA-N 2,3,4-trimethoxy-6-(methoxymethyl)-5-[3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxyoxane;1-[[3,4,5-tris(2-hydroxybutoxy)-6-[4,5,6-tris(2-hydroxybutoxy)-2-(2-hydroxybutoxymethyl)oxan-3-yl]oxyoxan-2-yl]methoxy]butan-2-ol Chemical compound COC1C(OC)C(OC)C(COC)OC1OC1C(OC)C(OC)C(OC)OC1COC.CCC(O)COC1C(OCC(O)CC)C(OCC(O)CC)C(COCC(O)CC)OC1OC1C(OCC(O)CC)C(OCC(O)CC)C(OCC(O)CC)OC1COCC(O)CC RPZANUYHRMRTTE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SJZRECIVHVDYJC-UHFFFAOYSA-M 4-hydroxybutyrate Chemical compound OCCCC([O-])=O SJZRECIVHVDYJC-UHFFFAOYSA-M 0.000 description 1
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Landscapes
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、澱粉・樹脂複合成形加工材料に関するものであり、より詳しくは、飲食用容器を初め、シート、フィルムなどの各種包装材料、緩衝材、生活用品、農業用品など広範囲の用途に用いることができ、廃棄処理されたときに短期間に生分解又は崩壊する澱粉を主成分とする澱粉・樹脂複合成形加工材料に関する。特に、真空成形、押出成形、インジェクション成形（射出成形）、インフレーション成形、ブロー成形（吹込成形）などプラスチックの各種成形法に適合した物性及び成形加工性を有するバラツキの少ない澱粉・樹脂複合成形加工材料に関する。 The present invention relates to a starch / resin composite molding processing material, and more specifically, it is used for a wide range of applications such as food and drink containers, various packaging materials such as sheets and films, cushioning materials, daily necessities, and agricultural products. The present invention relates to a starch / resin composite molding process material containing starch as a main component, which biodegrades or disintegrates in a short period of time when it is disposed of. In particular, a starch / resin composite molding processing material having physical properties and molding processability suitable for various plastic molding methods such as vacuum molding, extrusion molding, injection molding (injection molding), inflation molding, and blow molding (injection molding). Regarding.
石油資源等に基づくプラスチック成形品は、飲食用容器を初め、シート、フィルムなどの各種包装材料、緩衝材、生活用品、農業用品など産業資材として広範囲の用途に用いられている。一方で、大量消費により温室効果ガスによる地球温暖化や石油資源の枯渇が地球規模で長期的に取り組む重要な課題となっている。さらに、従来から石油系のプラスチック成形品が廃棄された際、自然環境では分解、崩壊し難く、長期にわたり自然の中に残存し、自然環境を汚染することが依然として課題として残っている。 Plastic molded products based on petroleum resources are used in a wide range of applications such as food and drink containers, various packaging materials such as sheets and films, cushioning materials, daily necessities, and agricultural products. On the other hand, global warming due to greenhouse gases and depletion of petroleum resources due to mass consumption have become important issues to be tackled on a global scale in the long term. Furthermore, when petroleum-based plastic molded products have been disposed of, they are difficult to decompose and collapse in the natural environment, remain in nature for a long period of time, and pollute the natural environment.
今日、プラスチック成形品の原材料として石油の代替材料となり、温暖化に影響しない、あるいは自然環境の中で比較的速やかに崩壊し、自然環境に優しい新たな材料として、天然素材が着目され、温暖化や資源の枯渇及び環境の汚染の課題を解消する一つの手段として、近年大きく進歩したバイオ技術に着目し、生物由来の有機資源であるバイオマス素材の活用が特に進められている。 Today, as a raw material for plastic molded products, it has become an alternative material to petroleum, and it does not affect global warming, or it collapses relatively quickly in the natural environment. As a means to solve the problems of resource depletion and environmental pollution, attention has been paid to biotechnology, which has made great progress in recent years, and the utilization of biomass materials, which are organic resources derived from living organisms, is being particularly promoted.
そのようなバイオマス素材としてポリ乳酸、澱粉、変性澱粉、セルロース等の天然素材の使用が提案されている。バイオマス素材は、廃棄されても自然環境下で最終的に分解されることから、環境に悪影響を与えないものである。 The use of natural materials such as polylactic acid, starch, modified starch, and cellulose has been proposed as such biomass materials. Biomass materials do not adversely affect the environment because they are finally decomposed in the natural environment even if they are discarded.
バイオマス素材の代表例が澱粉である。澱粉は、生分解性樹脂や他のバイオマス由来プラスチックに比べて安価であり、生分解性の促進、焼却時の低エネルギー化を実現できるバイオマス素材である。澱粉を充填剤として用いることで、自己分解性、崩壊性の組成物をより安価に提供することができる。また、澱粉は、温暖化や石油資源の枯渇に対応でき、低コスト化を実現することを目的に近年、着目され、使用する割合が増している。 A typical example of a biomass material is starch. Starch is a biomass material that is cheaper than biodegradable resins and other biomass-derived plastics, and can promote biodegradability and reduce energy consumption during incineration. By using starch as a filler, a self-degradable and disintegrating composition can be provided at a lower cost. In addition, starch has been attracting attention in recent years for the purpose of being able to cope with global warming and depletion of petroleum resources and realizing cost reduction, and the proportion of starch being used is increasing.
しかしながら、広範な用途にバイオマス素材を適用するためには、機械的特性、熱的特性、溶融加工性などが要求され、環境対応素材の多くは、十分な物性を有さず、成形することが困難である。 However, in order to apply biomass materials to a wide range of applications, mechanical properties, thermal properties, melt processability, etc. are required, and many environmentally friendly materials do not have sufficient physical properties and can be molded. Have difficulty.
そこで、物性や加工性を改善し、プラスチック成形加工材料の代替を可能とするため、バイオマスを原料としたポリ乳酸やバイオポリエチレン、澱粉やセルロースを、ポリオレフィン等の合成樹脂材料と複合材料化し、対応したものがある（特許文献１、２）。 Therefore, in order to improve physical properties and processability and make it possible to substitute for plastic molding processing materials, polylactic acid, biopolyethylene, starch and cellulose made from biomass are made into composite materials with synthetic resin materials such as polyolefins. (Patent Documents 1 and 2).
澱粉は、高分子量の素材であり、澱粉のままでは通常の形状が微粒体であること、さらに密度が低いことなどにより、粉塵が舞いやすいとともに粉体の流動安定性が悪く、定量供給しにくく、澱粉のままでは成形加工時、材料の流動性に欠け、取り扱い性、成形加工性に難点がある。さらに、澱粉と合成樹脂との複合化により形成される澱粉・樹脂複合成形加工材料は均一性や均質性の面で安定しない。すなわち、材料の形態や性質の異なる澱粉とプラスチックスの複合材料であり、混合し複合成形加工材料を形成できても、できた
ものは、製品全体の物性、性質にバラツキを生じてしまう。複合化のためには自ずと使用量が制限されるばかりでなく、使用量が多い場合は、強制的に澱粉を供給させるような特殊な定量フィーダーや成形機が必要である。そのため、製造コストを押し上げる要因ともなっている。
Starch is a high molecular weight material, and as it is, the normal shape of starch is fine particles, and the density is low. Therefore, dust is likely to fly and the flow stability of the powder is poor, making it difficult to supply a fixed amount. If starch is left as it is, the material lacks fluidity during molding, and there are problems in handleability and molding processability. Further, the starch / resin composite molding processed material formed by combining starch and synthetic resin is not stable in terms of uniformity and homogeneity. That is, it is a composite material of starch and plastics having different material forms and properties, and even if the composite molded material can be formed by mixing, the resulting product will have variations in the physical properties and properties of the entire product. Not only is the amount used limited naturally for compounding, but when the amount used is large, a special quantitative feeder or molding machine that forcibly supplies starch is required. Therefore, it is also a factor that pushes up the manufacturing cost.
バラツキの少ない澱粉・樹脂複合成形加工材料は、各種成形法、例えば、押出成形、Ｔ−ダイ押出成形、インジェクション成形、真空成形などの成形法により、各種包装材料や使い捨ての製品である買物袋、生ゴミ収集袋、使い捨て弁当箱、コップ、食品トレー、ナイフ、フォーク、スプーン、歯ブラシ、クシや農業用製品である農業用袋、育苗ポット、栽培セット、コンポスト袋や緩衝材、飲食容器などが製造でき、製造された成形物は、近年、分解性又は崩壊性が付与され、早く減容でき、環境に優しい成形物として、石油系の合成樹脂成形物に代わり利用され始めている。 The starch / resin composite molding processing material with less variation can be obtained by various molding methods, for example, extrusion molding, T-die extrusion molding, injection molding, vacuum molding, etc., to obtain various packaging materials and disposable products such as shopping bags. Manufactures garbage collection bags, disposable lunch boxes, cups, food trays, knives, forks, spoons, toothbrushes, combs and agricultural products such as agricultural bags, seedling pots, cultivation sets, compost bags and cushioning materials, food and drink containers, etc. In recent years, the produced molded articles have been imparted with degradability or disintegration property, can be quickly reduced in volume, and have begun to be used in place of petroleum-based synthetic resin molded articles as environmentally friendly molded articles.
そのような環境に優しい素材として澱粉を含む成形材料を製造するためには、合成樹脂の添加量を少なくするように考慮する必要があり、澱粉の量を多くすると澱粉・合成樹脂複合材料として機械的特性や成形性の低下が起きるため、澱粉の添加量や成形自由度に制限が出るなどの課題があった。 In order to produce a molding material containing starch as such an environment-friendly material, it is necessary to consider reducing the amount of synthetic resin added, and when the amount of starch is increased, the machine becomes a starch / synthetic resin composite material. There is a problem that the amount of starch added and the degree of freedom of molding are limited because the characteristics and moldability are deteriorated.
本発明は、種々の用途分野へ澱粉・樹脂複合材料を使用するに際して、上記のような環境対応を重視しつつ、均一で均質な、物性が改善された、しかも各種成形加工法における成形加工性、作業性にも優れた、安価でさらに安定して得られる、澱粉を５０重量％以上含有していてもバラツキの少ない澱粉・樹脂複合成形加工材料を提供する。特に、５０重量％以上の澱粉を含有する場合であっても澱粉と粒状体（ペレット）の熱可塑性樹脂を容易に安定的に混練、混合でき、しかも原材料として作業性及び定量性に優れ、形態安定性を有し、飲食用容器を初め、各種包装材料、緩衝材、農業用製品、生活用品などの成形加工材料として用いることができ、均一で均質な材料が得られ、しかも各種成形加工法における成形加工性、作業性に優れた、２０〜４０重量％の熱可塑性樹脂、低融点添加剤と高融点添加剤を含む、熱可塑性樹脂をコア部とし、そのコア部の表面に、低融点添加剤を含有する澱粉を含む粉粒体の被覆層を有する澱粉・樹脂複合中間粒体を原材料とする澱粉・樹脂複合成形材料であって、ＪＩＳ Ｋ７１１２測定法による比重１．１４〜１．２０で変動幅が±０．０１以内、ＪＩＳ Ｋ７１６１測定法による、引張伸度（％）がＭＤ方向の伸度が３６〜１６０％であって、変動幅が±７％以内であるバラツキが少なく、安定した材質を有する澱粉・樹脂複合成形加工材料を提供する。 In the present invention, when a starch / resin composite material is used in various fields of application, while emphasizing the above-mentioned environmental measures, the present invention is uniform and uniform, has improved physical properties, and has molding processability in various molding methods. Provided is a starch / resin composite molding processing material having excellent workability, which is inexpensive and can be obtained more stably, and which has little variation even if it contains 50% by weight or more of starch. In particular, even when 50% by weight or more of starch is contained, the starch and the thermoplastic resin of granules (pellets) can be easily and stably kneaded and mixed, and the workability and quantification as a raw material are excellent. It has stability and can be used as a molding material for various packaging materials, cushioning materials, agricultural products, daily necessities, etc., including food and drink containers, and a uniform and uniform material can be obtained, and various molding processing methods. A thermoplastic resin containing 20 to 40% by weight of a thermoplastic resin having a low melting point additive and a high melting point additive, which is excellent in molding processability and workability, is used as a core part, and a low melting point is formed on the surface of the core part. A starch / resin composite molding material using a starch / resin composite intermediate granule having a coating layer of a powder / granule containing starch containing an additive as a raw material, and having a specific gravity of 1.14 to 1.20 according to the JIS K7112 measurement method. The fluctuation range is within ± 0.01, the tensile elongation (%) according to the JIS K7161 measurement method is 36 to 160% in the MD direction, and the fluctuation range is within ± 7% with little variation. Provided is a starch / resin composite molding processing material having a stable material.
本発明者等は、上記課題を解決するため鋭意検討を重ねた結果、本発明の澱粉・樹脂複合成形加工材料は、所定の成分組成から製造される澱粉・樹脂複合中間粒体を原材料とし、溶融混練し、澱粉・樹脂複合材料の樹脂溶融物として押し出すことによって、従来得ることができなかった、澱粉を高濃度で含有しても均一で均質な、さらに安定してバラツキの少ない澱粉・樹脂複合成形加工材料を、特に、澱粉・樹脂複合中間粒体を形成し、成形加工材料の原材料とすることにより製造するように、及び／又は、カレンダ成形により外表面に厚みが制御されたスキン層を形成する又はスキン層を形成しない、冷却された澱粉・樹脂複合シート状物に成形することによって、製造され、提供するものである。 As a result of diligent studies to solve the above problems, the present inventors have made the starch / resin composite molding processed material of the present invention a raw material of a starch / resin composite intermediate granules produced from a predetermined component composition. By melt-kneading and extruding as a resin melt of a starch / resin composite material, a starch / resin that is uniform and uniform even if it contains a high concentration of starch, and is more stable and has little variation, which could not be obtained in the past. A skin layer whose outer surface thickness is controlled by calender molding so that the composite molding material is produced, in particular, by forming a starch / resin composite intermediate granule and using it as a raw material of the molding material. It is manufactured and provided by molding into a cooled starch / resin composite sheet that does not form a skin layer or a skin layer.
本発明の澱粉・樹脂複合成形加工材料は、より詳細には、５０重量％以上の澱粉と、２０重量％以上５０重量％未満の熱可塑性樹脂と、融点が６０℃〜１００℃のグリセリン系エステル等の低融点添加剤及び融点が１００℃〜１５０℃の脂肪酸金属塩等の高融点添加剤を含む原材料を加熱撹拌して形成した流動性の澱粉・樹脂複合材料を、冷却撹拌し、再固化し、熱可塑性樹脂をコア部とし、その表面を澱粉を含む粉粒体で被覆した澱粉・樹脂複合中間粒体を形成すること、及び該澱粉・樹脂複合中間粒体の材料劣化を抑えつつ溶融混練し、澱粉・樹脂複合材料の樹脂溶融物として押し出すことによって、優れた物性と材質を有するバラツキのない澱粉・樹脂複合成形加工材料ができることを見出した。 More specifically, the starch / resin composite molding processing material of the present invention comprises 50% by weight or more of starch, 20% by weight or more and less than 50% by weight of a thermoplastic resin, and a glycerin-based ester having a melting point of 60 ° C. to 100 ° C. A fluid starch / resin composite material formed by heating and stirring raw materials containing a low melting point additive such as, and a high melting point additive such as a fatty acid metal salt having a melting point of 100 ° C. to 150 ° C. is cooled and stirred and resolidified. The starch / resin composite intermediate granules are formed by using a thermoplastic resin as a core portion and the surface thereof is coated with starch-containing powder granules, and the starch / resin composite intermediate granules are melted while suppressing material deterioration. It has been found that by kneading and extruding as a resin melt of a starch / resin composite material, a starch / resin composite molding processed material having excellent physical properties and materials and having no variation can be produced.
本発明は、澱粉・樹脂複合中間粒体を形成する工程によりバイオマス、例えば、澱粉（工業用トウモロコシ（デントコーン））を５０重量％以上含有されている、粉粒状バイオマスと粒状体の熱可塑性樹脂の澱粉・樹脂複合材料であっても、あるいは、さらに、分散剤、脂肪酸金属塩、相溶化剤などの配合剤を含む、形状・形態の異なる原材料からなる複合材料を原材料とする成形材料の製造においても、取り扱い性のよい、原材料の製造工程への安定供給を可能にし、シート状物などの均一化、均質化したバラツキの少ない澱粉・樹脂複合成形加工材料を製造することができる。 In the present invention, a thermoplastic resin of powdery granular biomass and granular material containing 50% by weight or more of starch, for example, starch (industrial corn (dent corn)) by the step of forming a starch / resin composite intermediate granule. In the production of molding materials using composite materials of different shapes and forms, including starch / resin composite materials or compounding agents such as dispersants, fatty acid metal salts, and compatibilizers. In addition, it is possible to stably supply raw materials to the manufacturing process with good handleability, and it is possible to produce a starch / resin composite molding processed material having homogenization such as a sheet-like material and having little variation.
本発明は、５０重量％以上の澱粉が配合されることにより発生する材料の成形加工性や機械特性の偏りを澱粉と熱可塑性樹の界面を近づける添加剤などの配合剤を添加する技術を駆使すること、及び材料配合だけではなく、成形加工条件などを工夫することで機械的特性を改善させることができる。しかも澱粉臭の発生を抑制でき、退色の発生を抑えることもできる。 The present invention makes full use of a technique for adding a compounding agent such as an additive that brings the interface between starch and a thermoplastic tree closer to the molding processability and mechanical property bias of a material generated by blending 50% by weight or more of starch. The mechanical properties can be improved by devising not only the material composition and the molding processing conditions. Moreover, the generation of starch odor can be suppressed, and the generation of fading can also be suppressed.
さらには、本発明の澱粉・樹脂複合成形加工材料は、押出成形、Ｔ−ダイ押出成形、真空成形、インジェクション成形、インフレーション成形、カレンダ成形などの各種成形法に適した成形加工性にも優れた、環境対応型で、かつ澱粉臭が少なく、退色の発生も抑えられたものが得られる。 Furthermore, the starch / resin composite molding processing material of the present invention is also excellent in molding processability suitable for various molding methods such as extrusion molding, T-die extrusion molding, vacuum molding, injection molding, inflation molding, and calender molding. It is possible to obtain an environment-friendly type, which has less starch odor and suppresses fading.
本発明の澱粉・樹脂複合成形加工材料は、機械的特性の低下を抑え、薄もの成形や深ものの深絞り容器の成形を可能とし、石油資源の節約、焼却時発生二酸化炭素の削減、主原料が澱粉なので紙質感があるが、熱可塑性を持つためデザイン性に優れ、耐水性もある。また、包装資材として利用された際、使用時は十分な製品強度を持つが、使用後は軽い力でつぶせるため、ゴミの減容化にも貢献できる。 The starch / resin composite molding process material of the present invention suppresses deterioration of mechanical properties, enables molding of thin and deep drawn containers, saves petroleum resources, reduces carbon dioxide generated during incineration, and is the main raw material. Since it is starch, it has a paper texture, but because it has thermoplasticity, it has excellent design and water resistance. In addition, when used as a packaging material, it has sufficient product strength when used, but it can be crushed with a light force after use, which can contribute to reducing the volume of dust.
本発明は、配合からシート押出まで一貫した生産ラインを作り上げ製品化を実現することができる。さらに、製造されたシートは、澱粉を含むすべての原材料をポジティブリストから選定されまた、環境影響評価においてＬＣＡを実施し、ポリプロピレンシートのライフサイクルと比較して３２％の二酸化炭素削減効果が明らかになった。 The present invention can realize a commercialization by creating a consistent production line from compounding to sheet extrusion. In addition, all raw materials, including starch, were selected from the positive list for the manufactured sheets, and LCA was performed in the environmental impact assessment, revealing a 32% carbon dioxide reduction effect compared to the life cycle of polypropylene sheets. became.
本発明は、このため、本発明の澱粉・樹脂複合材料として石油系プラスチックの代替として一層、好適な環境対応型の材料であり、各種食品容器類や包装材料、緩衝材、生活用品、農業用製品などへの応用が十分可能となる材料を提供することができる。 Therefore, the present invention is a more suitable environment-friendly material as a substitute for petroleum-based plastic as the starch / resin composite material of the present invention, and is used for various food containers, packaging materials, cushioning materials, daily necessities, and agriculture. It is possible to provide a material that can be sufficiently applied to products and the like.
（澱粉・樹脂複合成形加工材料）
上記の本発明の澱粉・樹脂複合成形加工材料について、以下にさらに詳しく説明する。
本発明に係る澱粉・樹脂複合成形加工材料は、特殊な手段、設備を使用することなく、形態安定性を有する安定した品質の澱粉・樹脂複合中間粒体を原材料とすることで、従来、得られ難かった澱粉が５０重量％以上含有されていても、均一性、均質性に優れ、バラツキの少ない澱粉・樹脂複合成形加工材料である。
すなわち、澱粉・樹脂複合成形加工材料は、澱粉と、低融点添加剤とを加熱撹拌して混合し、澱粉に溶融した低融点添加剤を絡ませ、付着させ、溶融した低融点添加剤を含有する澱粉を形成する。
(Starch / resin composite molding material)
The starch / resin composite molding processing material of the present invention described above will be described in more detail below.
The starch / resin composite molding processing material according to the present invention has been conventionally obtained by using a starch / resin composite intermediate granule having stable morphology and stable quality as a raw material without using special means or equipment. Even if it contains 50% by weight or more of starch, which is difficult to obtain, it is a starch / resin composite molding processing material having excellent uniformity and homogeneity and little variation.
That is, the starch / resin composite molding processing material contains the low melting point additive which is melted by mixing the starch and the low melting point additive by heating and stirring, and entwining and adhering the melted low melting point additive to the starch. Form starch.
そして、さらに熱可塑性樹脂の粒状体と高融点添加剤を加熱撹拌しながら混合し、溶融した低融点添加剤及び高融点添加剤と、澱粉と、熱可塑性樹脂の粒状体を均一分散させ、流動性の澱粉・樹脂複合材料とする。 Then, the granular material of the thermoplastic resin and the high melting point additive are mixed while heating and stirring, and the molten low melting point additive and high melting point additive, starch, and the granular material of the thermoplastic resin are uniformly dispersed and flowed. Uses a sex starch / resin composite material.
その後、流動性の澱粉・樹脂複合材料を撹拌しながら冷却し、少なくとも溶融状態にある高融点添加剤を再固化することにより、熱可塑性樹脂の粒状体をコア部とし、そのコア部の表面に低融点添加剤を含有する澱粉を含む粉粒体の被覆層を有する澱粉・樹脂複合中間粒体を形成した後、澱粉・樹脂複合中間粒体を原材料とし、材料劣化を抑えつつ溶融混練し、澱粉・樹脂複合材料の樹脂溶融物として押し出すことにより、澱粉が５０重量％以上含有されていても、均一性、均質性に優れ、バラツキの少ない澱粉・樹脂複合成形加工材料が製造されるものである。 Then, the fluid starch-resin composite material is cooled with stirring, and at least the melted high melting point additive is resolidified to form a granular material of the thermoplastic resin as a core portion, and the surface of the core portion is formed. After forming a starch-resin composite intermediate granule having a coating layer of a powder granule containing starch containing a low melting point additive, the starch-resin composite intermediate granule is used as a raw material and melt-kneaded while suppressing material deterioration. By extruding as a resin melt of starch / resin composite material, even if starch is contained in an amount of 50% by weight or more, a starch / resin composite molding processed material having excellent uniformity and homogeneity and little variation can be produced. is there.
（澱粉）
本発明の澱粉・樹脂複合成形加工材料は、成分原料を一度、澱粉・樹脂複合中間粒体の形態とし、複合中間粒体を経て混練し、溶融押し出しし、成分組成の澱粉・樹脂複合成形加工材料が製造されたものである。本発明の澱粉・樹脂複合成形加工材料においてバイオマス材料として用いる原材料の澱粉としては、安価に入手できる生澱粉を用いることができ、例えば、トウモロコシ澱粉、豆澱粉、タピオカ澱粉、いも澱粉、麦澱粉、米澱粉、キツサバ澱粉、ヒシ澱粉、ハス澱粉、サゴ澱粉、わらび澱粉、クズ澱粉等が挙げることができる。
(starch)
In the starch / resin composite molding processing material of the present invention, the component raw material is once formed into a starch / resin composite intermediate granule, kneaded through the composite intermediate granule, melt-extruded, and the starch / resin composite molding processing of the component composition is performed. The material is manufactured. As the raw material starch used as the biomass material in the starch / resin composite molding processing material of the present invention, inexpensively available raw starch can be used, for example, corn starch, bean starch, tapioca starch, potato starch, wheat starch, etc. Examples thereof include rice starch, fox starch, mustard starch, lotus starch, sago starch, warabi starch, and waste starch.
他に、物理的な変性澱粉も用いることができ、アルファー化澱粉、湿熱澱粉などが挙げることができる。さらに、生分解性に影響ない程度に化学修飾した澱粉も用いることができ、例えば、アセト酢酸エステル化澱粉、酢酸エステル化澱粉、ヒドロキシメチルエーテル化澱粉、ヒドロキシプロピルエーテル澱粉、カルボキシメチルエーテル化澱粉、アリルエーテル化澱粉、メチルエーテル化澱粉、コハク酸エステル化澱粉、キサントゲン酢酸エステル化澱粉、硝酸エステル化澱粉、尿素リン酸エステル化澱粉、リン酸エステル化澱粉、リン酸架橋澱粉、ホルムアルデヒド架橋澱粉、アクロレイン架橋澱粉、エピクロルヒドリン架橋澱粉などを挙げることができる。 In addition, physically modified starch can also be used, and examples thereof include pregelatinized starch and moist heat starch. Further, starch chemically modified to the extent that it does not affect biodegradability can also be used. For example, acetoacetate esterified starch, acetate esterified starch, hydroxymethyl etherified starch, hydroxypropyl ether starch, carboxymethyl etherified starch, etc. Allyl etherified starch, methyl etherified starch, succinic acid esterified starch, xantogen acetate esterified starch, nitrate esterified starch, urea phosphate esterified starch, phosphoric acid esterified starch, phosphoric acid crosslinked starch, formaldehyde crosslinked starch, achlorine Examples thereof include crosslinked starch and epichlorohydrin crosslinked starch.
本発明において、澱粉として、生澱粉、物理的な変性澱粉又は化学修飾した澱粉の中から少なくとも１種以上、１種単独でも又は２種以上を組み合わせて配合して使用することもできる。好ましくは、生澱粉が用いられる。 In the present invention, as starch, at least one or more of raw starch, physically modified starch or chemically modified starch can be used alone or in combination of two or more. Preferably, raw starch is used.
（高分子材料）
本発明において、澱粉・樹脂複合成形加工材料の成分には、成形加工性、物性を改質するため少なくとも熱可塑性樹脂を含むものである。本発明では、さらに、生分解性を低下させず、生分解性材料の比率を高めるためコア部となる粒状体の高分子材料として生分解
性材料を用いることもできる。
(Polymer material)
In the present invention, the components of the starch / resin composite molding material include at least a thermoplastic resin in order to modify the molding processability and physical properties. In the present invention, a biodegradable material can also be used as a granular polymer material serving as a core portion in order to increase the ratio of the biodegradable material without lowering the biodegradability.
本発明において、使用される熱可塑性樹脂としては、ポリエチレン、ポリプロピレン等のポリオレフィン系の樹脂、ポリスチレン、ポリアミド、ポリエステル、エチレン／酢酸ビニル共重合体、アルキレン／アクリレート又はメタクリレート共重合体などの熱可塑性プラスチックを用いることができる。好ましくは、ポリエチレン、ポリプロピレンなどのポリオレフィン系樹脂が用いられる。特に、好ましくは、ポリプロピレンが用いられる。 The thermoplastic resin used in the present invention includes polyolefin-based resins such as polyethylene and polypropylene, and thermoplastics such as polystyrene, polyamide, polyester, ethylene / vinyl acetate copolymer, alkylene / acrylate or methacrylate copolymer. Can be used. Preferably, a polyolefin resin such as polyethylene or polypropylene is used. In particular, polypropylene is preferably used.
熱可塑性樹脂としては、ペレット状の粒状物が用いられ、本発明の均一、均質な澱粉・樹脂複合成形加工材料を形成するためには、２０重量％以上５０重量％未満の範囲にあることが好ましい。熱可塑性樹脂が、２０重量％未満であると、得られる澱粉・樹脂複合成形材料として比重が小さい澱粉の量が多くなり、バイオマス成形材料として均一化し難くなり、複合成形加工材料として均一、均質なものが得難くなる。しかも添加剤の量も多くする必要がある。結果、機械的特性の低下が著しく、成形時、偏肉、破れなどが生じ、薄物の成形、深物の深絞り成形が困難となり、質感が得られず、成形加工が困難になる。 As the thermoplastic resin, pellet-shaped granules are used, and in order to form the uniform, homogeneous starch / resin composite molding processed material of the present invention, it may be in the range of 20% by weight or more and less than 50% by weight. preferable. When the thermoplastic resin content is less than 20% by weight, the amount of starch having a small specific gravity as the obtained starch / resin composite molding material increases, making it difficult to homogenize as the biomass molding material, and uniform and homogeneous as the composite molding processing material. It becomes difficult to obtain things. Moreover, it is necessary to increase the amount of additives. As a result, the mechanical properties are significantly deteriorated, uneven thickness, tearing, etc. occur during molding, which makes it difficult to mold thin materials and deep drawn products, and it is difficult to obtain a texture and molding processing.
一方、熱可塑性樹脂が５０重量％だと、澱粉が熱可塑性樹脂の改質剤として、例えば、充填剤として位置付けられ、得られる澱粉・樹脂複合成形加工材料は、プラスチック成形材料としての物性、性質が強く出て、成形は可能であるが、得られる澱粉・樹脂複合成形材料は、澱粉が充填剤として添加されるものとなり、プラスチック材料の性質が強く、減容化がし難く、温室効果ガスの排出削減への貢献が低下し、バイオマス原料としての澱粉・樹脂複合成形加工材料が得られ難くなる。しかも、成形加工材料は、充填剤の澱粉が多く、成形加工材料の物性及び複合材料としての均一性、均質性の変動が大きく、安定した材料が得られ難くなる。 On the other hand, when the thermoplastic resin is 50% by weight, the starch is positioned as a modifier for the thermoplastic resin, for example, as a filler, and the obtained starch / resin composite molding processing material has physical properties and properties as a plastic molding material. However, in the obtained starch / resin composite molding material, starch is added as a filler, and the properties of the plastic material are strong, it is difficult to reduce the volume, and the greenhouse gas. Contribution to reduction of emissions will decrease, and it will be difficult to obtain starch / resin composite molding processed materials as biomass raw materials. Moreover, the molding-processed material contains a large amount of starch as a filler, and the physical properties of the molding-processed material and the uniformity and homogeneity of the composite material fluctuate greatly, making it difficult to obtain a stable material.
また、本発明の複合成形加工材料の製造方法において澱粉・樹脂複合中間粒体を形成することなく、原材料の各成分組成が同じ材料から成形加工材料を製造した場合、製造される成形材料の物性、複合材料としての均一性、均質性の変動が大きく、バラツキが大きく、安定した材料が得られ難くなる。 Further, in the method for producing a composite molding material of the present invention, when a molding material is produced from a material having the same composition of each component of the raw material without forming a starch / resin composite intermediate granule, the physical properties of the produced molding material. , The uniformity as a composite material, the variation of homogeneity is large, the variation is large, and it becomes difficult to obtain a stable material.
コア部を形成する生分解性材料としては、メチルセルロース、ヒドロキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシエチルメチルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシブチルメチルセルロースなどのセルロース誘導体、ポリビニルアルコール、カルボキシメチルセルロース、ポリアクリル酸系ポリマー、ポリアクリルアミドなどの親水性高分子材料、各種アクリレート、エチレン／酢酸ビニル共重合体、ポリウレタンなどのエマルジョン、脂肪族ポリエステル系樹脂であるカプロラクトン、ポリ乳酸、ポリブチレンアジペート、ポリブチレンサクシネート、ポリヒドロキシブチレート・バリレート共重合体などの生分解性材料を挙げることができる。 Biodegradable materials forming the core include cellulose derivatives such as methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and hydroxybutyl methyl cellulose, polyvinyl alcohol, carboxymethyl cellulose, and polyacrylic acid. Polymers, hydrophilic polymer materials such as polyacrylamide, various acrylates, ethylene / vinyl acetate copolymers, emulsions such as polyurethane, caprolactone, which is an aliphatic polyester resin, polylactic acid, polybutylene adipate, polybutylene succinate, poly Biodegradable materials such as hydroxybutyrate / variate copolymers can be mentioned.
本発明では、製造過程で形成された複合中間粒体、シート又は成形後の抜きかすを破砕し、粒状体にしたフラフも澱粉・樹脂複合材料あるいは澱粉材料からなる生分解性材料であることから、再利用し、熱可塑性樹脂とともに、コア部となる粒状体として用いることができる。 In the present invention, the fluff formed by crushing the composite intermediate granules, sheets or post-molded debris formed in the manufacturing process into granules is also a starch / resin composite material or a biodegradable material made of a starch material. , Can be reused and used as a granule to be a core part together with a thermoplastic resin.
本発明において、使用する熱可塑性樹脂の粒状体の平均粒径は、長軸１〜１０ｍｍ、短軸１〜１０ｍｍの範囲のものが採用される。この長軸の大きさを超えた場合又は大きさが小さい場合は、粒体の付着量のバランスが悪くなるため、いずれも澱粉と熱可塑性樹脂との澱粉・樹脂複合中間粒体として均一、均質性が劣る。さらには、成形物中での両者の分散性が劣る。粒径の大きい粒体が存在することもあって、物性や製品の外観も劣る結果と
なる。少ない量で効果的に粉粒体ができ、成形加工性がよく、製品の外観に影響しないことを総合的に考慮して、本発明の澱粉・樹脂複合成形加工材料に使用する熱可塑性樹脂は、平均粒径を上記の範囲のものを使用する。
In the present invention, the average particle size of the granular material of the thermoplastic resin used is in the range of 1 to 10 mm on the major axis and 1 to 10 mm on the minor axis. If the size of the major axis is exceeded or the size is small, the balance of the amount of adhered granules becomes unbalanced. Therefore, all of them are uniform and homogeneous as starch / resin composite intermediate granules of starch and thermoplastic resin. Inferior in sex. Furthermore, the dispersibility of both in the molded product is inferior. Due to the presence of granules having a large particle size, the physical properties and the appearance of the product are also inferior. The thermoplastic resin used in the starch / resin composite molding material of the present invention is comprehensively considered that it can effectively form powders and granules with a small amount, has good molding processability, and does not affect the appearance of the product. , Use one with an average particle size in the above range.
（添加剤）
本発明では、その流動性の澱粉・樹脂複合材料を形成し、澱粉・樹脂複合中間粒体を形成するため、加熱撹拌する工程では、添加剤が澱粉、熱可塑性樹脂に絡まり、付着し、澱粉と熱可塑性樹脂を親和し、付着させるように機能し、また澱粉と熱可塑性樹脂の粒状体を流動性の澱粉・樹脂複合材料の性状を保持できるようにするため、さらに、冷却撹拌し、少なくとも高融点添加剤が再固化されたとき、澱粉・樹脂複合中間粒体の形態を安定的に形成できるようにする接着剤的な役割を果たすことができる添加剤を加える必要がある。
(Additive)
In the present invention, the fluid starch / resin composite material is formed to form the starch / resin composite intermediate granules. Therefore, in the step of heating and stirring, the additive is entangled with the starch and the thermoplastic resin and adheres to the starch. Further cool and agitate, at least to allow the starch and the thermoplastic resin granules to retain the properties of the fluid starch-resin composite material, as well as to have an affinity for and adhere to the thermoplastic resin. When the refractory additive is resolidified, it is necessary to add an additive that can act as an adhesive to stably form the morphology of the starch-resin composite intermediate granules.
さらに、澱粉・樹脂複合成形材料の押出時には、澱粉と熱可塑性樹脂を均一に分散させる分散剤として機能し、さらに溶融混練し、溶融する樹脂と溶融しない澱粉とを材料劣化することなく押し出すことができるようにするため滑性を付与することができる添加剤を加える。
本発明は、添加剤を加えることにより成形加工性、機械的強度などが改善されたバラツキの少ない澱粉・樹脂複合成形加工材料が得られるように機能する添加剤が選択され、用いられる。
Further, when the starch / resin composite molding material is extruded, it functions as a dispersant that uniformly disperses the starch and the thermoplastic resin, and further melt-kneads and extrudes the melted resin and the unmelted starch without material deterioration. Add an additive that can impart slipperiness to allow.
In the present invention, an additive that functions so as to obtain a starch / resin composite molding processed material having less variation in molding processability, mechanical strength, etc. by adding the additive is selected and used.
（低融点添加剤）
本発明では、上記のように機能する添加剤として、投入直後は粉体だが、材料の昇温と共に溶融状態になり、澱粉に付着することで澱粉を熱可塑性樹脂と付着させやすくし、澱粉と均一、均質に混合され、澱粉の流動性を高めるように働くよう、内部滑性を高める添加剤を用いる。そして添加剤は、熱可塑性樹脂の溶融温度より低い溶融温度を有し、比較的低温度、例えば、１００℃以下で溶融するもの、好ましくは、６０〜１００℃で溶融するもの、しかも粘性があり、粉体と絡み粘着させるように機能し得る添加剤が用いられる。少なくとも前記のような性質、機能を果たすことができ、澱粉・樹脂複合中間粒体中に同時存在する、相対的に低温で溶融され、澱粉と絡ませ、付着され添加される添加剤を本発明では「低融点添加剤」と定義する。
(Low melting point additive)
In the present invention, as an additive that functions as described above, it is a powder immediately after being added, but it becomes a molten state as the temperature of the material rises, and by adhering to starch, it becomes easier for the starch to adhere to the thermoplastic resin, and the starch and starch. Additives that increase internal slipperiness are used so that they are mixed uniformly and uniformly and work to increase the fluidity of the starch. The additive has a melting temperature lower than the melting temperature of the thermoplastic resin, and melts at a relatively low temperature, for example, 100 ° C. or lower, preferably 60 to 100 ° C., and is viscous. , Additives that can function to entangle and adhere to the powder are used. In the present invention, an additive that can fulfill at least the above-mentioned properties and functions and coexists in the starch / resin composite intermediate granules and is melted at a relatively low temperature, entangled with starch, adhered and added is provided. Defined as "low melting point additive".
低融点添加剤として、モノグリセリド、ジグリセリド、トリグリセリド、アセチル化モノグリセリド、有機酸モノグリセリド、中鎖脂肪酸モノグリセリド、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、プロピレングリコール脂肪酸エステル、特殊脂肪酸エステル、高級アルコール脂肪酸エステルなどが挙げられる。好ましくは、グリセリン系脂肪酸エステル等の低融点添加剤、例えば、モノグリセリド（グリセリンモノステアレート）が好ましく用いられる。 Examples of low melting point additives include monoglyceride, diglyceride, triglyceride, acetylated monoglyceride, organic acid monoglyceride, medium chain fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, special fatty acid ester, and higher alcohol fatty acid ester. Be done. Preferably, a low melting point additive such as a glycerin fatty acid ester, for example, monoglyceride (glycerin monostearate) is preferably used.
該低融点添加剤の添加量は、好ましくは、０．１〜１０．０重量％である。０．１重量％以下であると、付着剤としての機能が不十分であり、１０重量％以上であると、原材料にベタ付きを生じさせ、流動撹拌性が低下し、また、澱粉玉が形成されやすくなり、高温撹拌機中での流動性のある澱粉混合物の形成が遅れ、製造効率が低下する。しかも、加熱時間が長くなることで澱粉の黄変が観察される。 The amount of the low melting point additive added is preferably 0.1 to 10.0% by weight. If it is 0.1% by weight or less, the function as an adhesive is insufficient, and if it is 10% by weight or more, the raw material becomes sticky, the flow agitation property is lowered, and starch balls are formed. The formation of a fluid starch mixture in a high temperature stirrer is delayed, and the production efficiency is lowered. Moreover, yellowing of starch is observed as the heating time becomes longer.
（高融点添加剤）
本発明では、澱粉・樹脂複合中間粒体中に同時存在する、相対的に低温で溶融され、澱粉と絡ませ、付着される低融点添加剤よりも高い融点を有する添加剤をさらに添加する。この添加剤は、上述した低融点添加剤より高い融点を有しており、好ましくは、１００〜１５０℃の範囲のもので、低融点添加剤より先に固化する添加剤であって、熱可塑性樹脂
の溶融温度より低い融点を有するものであり、冷却撹拌したときに、低融点添加剤より先に再固化し、熱可塑性樹脂をコア部とし、そのコア部表面に低融点添加剤を付着し含有する澱粉を含む粉粒体の被覆層を付着させ、澱粉・樹脂複合中間粒体を形成する役割を果たすものである。
(High melting point additive)
In the present invention, an additive having a melting point higher than that of the low melting point additive which is melted at a relatively low temperature, entangled with starch and adhered to the starch / resin composite intermediate granules at the same time is further added. This additive has a higher melting point than the low melting point additive described above, preferably in the range of 100 to 150 ° C., and is an additive that solidifies before the low melting point additive and is thermoplastic. It has a melting point lower than the melting temperature of the resin, and when cooled and stirred, it resolidifies before the low melting point additive, and the thermoplastic resin is used as the core part, and the low melting point additive is attached to the surface of the core part. It plays a role of adhering a coating layer of powder or granular material containing starch to form a starch / resin composite intermediate particle.
高融点添加剤は、さらに、成形加工材料を製造するため使用されるまで澱粉・樹脂複合中間粒体から澱粉が剥離し、粉落ちすることなく、あるいは中間粒体が崩壊することなく複合中間粒体の形態を保持するように機能するような添加剤である。
高融点添加剤は、熱可塑性樹脂の種類、添加剤との相性をも考慮する必要があるが、澱粉・樹脂複合中間粒体を原材料として加工機中で均一、均質な澱粉・樹脂複合成形加工材料とするため複合原材料を分散させ、澱粉・樹脂複合材料として溶融混練するとき均一分散し、しかも加工機との摩擦を軽減させ、かつ加工機中の流動性を高め、外部滑性を高める滑性を付与することができる添加剤が好適に使用される。
少なくとも前記のような性質、機能を果たすことができる、澱粉・樹脂複合中間粒体中に同時存在する、相対的に高温で溶融される添加剤を、本発明では「高融点添加剤」と定義する。
The refractory additive further removes starch from the starch-resin composite intermediate granules until it is used to produce a molding process material, and the composite intermediate granules do not fall off or disintegrate. It is an additive that functions to maintain the shape of the body.
For the high melting point additive, it is necessary to consider the type of thermoplastic resin and compatibility with the additive, but starch / resin composite intermediate granules are used as the raw material for uniform and uniform starch / resin composite molding in the processing machine. The composite raw material is dispersed to make it a material, and when melt-kneaded as a starch / resin composite material, it is uniformly dispersed, yet it reduces friction with the processing machine, enhances fluidity in the processing machine, and enhances external slipperiness. Additives capable of imparting sex are preferably used.
In the present invention, an additive that is capable of fulfilling at least the above-mentioned properties and functions and that is simultaneously present in the starch / resin composite intermediate granules and is melted at a relatively high temperature is defined as a "high melting point additive". To do.
本発明では、澱粉・樹脂複合中間粒体を形成し、その溶融混練時の分散性を向上させる滑性を付与することができる高融点添加剤には、脂肪酸金属塩、炭化水素系、高級アルコール系、脂肪族アミド系、脂肪酸エステルなどが使用できる。本発明の高融点添加剤には、脂肪酸金属塩としては、炭素数が少なくとも１０個以上の飽和又は不飽和脂肪酸の金属塩であり、ステアリン酸などの脂肪酸系のものが好適に使用できる。 In the present invention, the high melting point additive capable of forming a starch-resin composite intermediate granule and imparting smoothness to improve the dispersibility during melt-kneading includes a fatty acid metal salt, a hydrocarbon type, and a higher alcohol. Systems, aliphatic amides, fatty acid esters, etc. can be used. In the high melting point additive of the present invention, the fatty acid metal salt is a metal salt of a saturated or unsaturated fatty acid having at least 10 carbon atoms, and a fatty acid-based substance such as stearic acid can be preferably used.
具体的には、ステアリン酸マグネシウム、ステアリン酸亜鉛、ステアリン酸カルシウム、ステアリン鎖アルミニウム、ラウリル硫酸ナトリウム、ラウリル硫酸マグネシウム、安息香酸カリウム、安息香酸ナトリウム、フマル酸ステアリルナトリウム等が挙げられる。これらのうち少なくとも１種類以上を併用することできる。
高融点添加剤の含有量は、好ましくは、１．０〜１５重量％である。
Specific examples thereof include magnesium stearate, zinc stearate, calcium stearate, aluminum stearate chain, sodium lauryl sulfate, magnesium lauryl sulfate, potassium benzoate, sodium benzoate, and sodium stearyl fumarate. At least one of these can be used in combination.
The content of the refractory additive is preferably 1.0 to 15% by weight.
本発明は、上記したような低融点及び高融点の添加剤を２種以上使用するものであって、加熱撹拌時に、澱粉や樹脂への付着と流動性を高め、冷却撹拌したとき、再固化することにより自動的に本発明の澱粉・樹脂複合中間粒体の形態が形成されるように添加剤を選択したものである。そして、形成された澱粉・樹脂複合中間粒体を原材料にして、加工機中で熱可塑性樹脂を溶融もしくは溶融混練することにより均一、均質な複合材料とすることができ、溶融押出を可能とするとともに、本発明の生産品である澱粉・樹脂複合成形加工材料に必要な配合剤を添加することにより必要な物性、成形加工性を備えた生産品を得ることができるものである。 The present invention uses two or more of the additives having a low melting point and a high melting point as described above, and enhances adhesion and fluidity to starch and resin during heating and stirring, and resolidifies when cooling and stirring. The additive is selected so that the form of the starch-resin composite intermediate granule of the present invention is automatically formed by the above. Then, by using the formed starch / resin composite intermediate granules as a raw material and melting or melt-kneading the thermoplastic resin in a processing machine, a uniform and homogeneous composite material can be obtained, which enables melt extrusion. At the same time, by adding a necessary compounding agent to the starch / resin composite molding processing material which is the product of the present invention, a product having the necessary physical properties and molding processability can be obtained.
（その他の添加剤）
本発明は、澱粉・樹脂複合中間粒体を用いることにより、均一、均質なバラツキの少ない澱粉・樹脂複合成形加工材料が得られるように、また各種成形加工法における成形加工性を有し、作業性に優れた材料が得られるように、さらに食品容器を初めとして、シート、フィルムなどの包装材料、緩衝材、生活用品、農業用製品など各種用途に好適に加工して使用が可能となるように、添加剤を選択し用いることが好ましい。その際、上記の澱粉、熱可塑性樹脂及び上記添加剤以外に各種の添加剤が各用途及び求められる物性、機能に応じて選択され、本発明の目的を損なわない範囲で１種又は２種以上を組み合わせて添加することもできる。
(Other additives)
According to the present invention, by using a starch / resin composite intermediate granule, a uniform and uniform starch / resin composite molding processing material with little variation can be obtained, and the molding processability in various molding processing methods can be obtained. In order to obtain materials with excellent properties, it can be processed and used for various purposes such as food containers, packaging materials such as sheets and films, cushioning materials, daily necessities, and agricultural products. It is preferable to select and use an additive. At that time, various additives other than the above-mentioned starch, thermoplastic resin and the above-mentioned additives are selected according to each application and required physical properties and functions, and one or more kinds are selected as long as the object of the present invention is not impaired. Can also be added in combination.
本発明では、澱粉と熱可塑性樹脂との親和性を向上させるため相溶化剤を添加することもできる。相溶化剤としては、酸変性ポリオレフィン、酸変性ナイロン、酸変性ポリスチ
レン、酸変性EVA、酸変性エチレン共重合ポリマー、酸変性アクリレート、アクリル酸変性EVA、変性エチレンアクリレートなどが使用できる。
In the present invention, a compatibilizer can be added in order to improve the affinity between the starch and the thermoplastic resin. As the compatibilizer, acid-modified polyolefin, acid-modified nylon, acid-modified polystyrene, acid-modified EVA, acid-modified ethylene copolymer polymer, acid-modified acrylate, acrylic acid-modified EVA, modified ethylene acrylate and the like can be used.
本発明の澱粉・樹脂複合成形加工材料を製造するために使用する添加剤としては、必要に応じて、酸化チタン、カーボンブラック、染料、顔料などの着色剤が使用できる。その他にも必要に応じて、エラストマ、酸化防止剤、架橋剤、紫外線吸収剤、発泡剤などの添加剤を適宜添加することができる。 As the additive used for producing the starch / resin composite molding processed material of the present invention, a colorant such as titanium oxide, carbon black, dye, or pigment can be used, if necessary. In addition, if necessary, additives such as elastomer, antioxidant, cross-linking agent, ultraviolet absorber, and foaming agent can be appropriately added.
本発明において澱粉・樹脂複合中間粒体の形状や大きさは、この澱粉と混合される粒状の熱可塑性樹脂の粒状体の形状や粒体径等を考慮して適宜決定できる。粒体の大きさは、直径が、例えば、１〜１０ｍｍの範囲であり、長さが１〜１０ｍｍの範囲である。 In the present invention, the shape and size of the starch / resin composite intermediate particles can be appropriately determined in consideration of the shape and diameter of the granular materials of the granular thermoplastic resin mixed with the starch. The size of the granules has a diameter in the range of, for example, 1 to 10 mm and a length in the range of 1 to 10 mm.
本発明の澱粉・樹脂複合成形加工材料の製造に用いる複合中間粒体は、上記材料のとおり粒状体の熱可塑性樹脂をコア部とし、澱粉を主成分とする粉粒体により形成された被覆層を表面に有する形態としたものである。この複合中間粒体は、本発明の澱粉・樹脂複合成形材料を製造するため溶融混練されるまで澱粉・樹脂複合中間粒体の形態が崩れを起こさない程度の、あるいは澱粉が剥離しない程度の粘着力で付着されている形態安定性を有し、複合中間粒体材料として安定した状態を維持できるように形成されることが好ましい。そのことにより、澱粉を主成分として含有するバイオマス・樹脂複合材料からなる成形材料の製造において複合成形加工材料としてバラツキが少なく、均一、均質性、成形加工性、作業性及び定量性が改善できる。 The composite intermediate granules used in the production of the starch / resin composite molding processing material of the present invention have a coating layer formed of powder granules containing starch as a main component and having a granular thermoplastic resin as a core portion as described above. Is in the form of having a surface. In order to produce the starch / resin composite molding material of the present invention, the composite intermediate particles are adhered to such an extent that the morphology of the starch / resin composite intermediate particles does not collapse or the starch does not peel off until they are melt-kneaded. It is preferably formed so that it has morphological stability attached by force and can maintain a stable state as a composite intermediate granule material. As a result, in the production of a molding material made of a biomass / resin composite material containing starch as a main component, there is little variation as a composite molding processing material, and uniformity, homogeneity, molding processability, workability and quantitativeness can be improved.
（澱粉・樹脂複合成形加工材料の製造）
本発明の澱粉・樹脂複合中間粒体を用いた澱粉・樹脂複合成形加工材料の製造は、例えば、澱粉複合中間粒体を構成する成分組成の材料を原材料とし、又は澱粉・樹脂複合中間粒体を原材料とし、生産品である澱粉・樹脂複合成形加工材料までを連続的に一貫して製造する方法として組み立てられている。澱粉・樹脂複合成形加工材料は、図１に示す澱粉・樹脂複合成形加工材料連続一貫製造装置により製造される。
(Manufacturing of starch / resin composite molding processing material)
In the production of the starch / resin composite molding processed material using the starch / resin composite intermediate granules of the present invention, for example, a material having a component composition constituting the starch composite intermediate granules is used as a raw material, or a starch / resin composite intermediate granules. Is used as a raw material, and it is assembled as a method of continuously and consistently manufacturing up to the starch / resin composite molding processed material which is a product. The starch / resin composite molding processing material is manufactured by the starch / resin composite molding processing material continuous integrated manufacturing apparatus shown in FIG.
本発明の連続一貫製造装置は、本発明の成形加工材料の製造を可能にする澱粉・樹脂複合中間粒体を製造し、貯蔵し得る澱粉・樹脂複合中間粒体製造装置部Ａと、前記複合中間粒体を原材料とし、生産品である澱粉・樹脂複合成形加工材料を製造し、及び又はカレンダ成形等の二次加工し、最終製品の原材料を製造する粉・樹脂複合成形加工材料製造装置部Ｂを含む装置からなっている。 The continuous integrated manufacturing apparatus of the present invention comprises the starch / resin composite intermediate granule manufacturing apparatus A capable of producing and storing the starch / resin composite intermediate granules capable of producing the molding processing material of the present invention, and the composite. The powder / resin composite molding processing material manufacturing equipment section that manufactures the starch / resin composite molding processing material, which is a product, and / or secondary processing such as calender molding to manufacture the raw material of the final product using intermediate particles as the raw material. It consists of a device containing B.
澱粉・樹脂複合中間粒体製造装置部Ａは、澱粉と溶融した低融点添加剤の澱粉混合物を形成するため加熱撹拌する高温撹拌機１と、澱粉と熱可塑性樹脂の粒状体と低融点及び高融点添加剤を含む澱粉・樹脂複合材料から該複合中間粒体を形成するため冷却し撹拌する冷却撹拌機２と、造粒した澱粉・樹脂複合中間粒体をストックし、澱粉・樹脂複合成形加工材料を連続的に製造可能にするように原材料とする複合中間粒体の供給バッファとすることができるストックタンク兼供給装置３を含む製造装置である。 The starch / resin composite intermediate granule production apparatus A includes a high-temperature stirrer 1 that heats and stirs to form a starch mixture of starch and a melted low melting point additive, and granules of starch and thermoplastic resin with low melting point and high melting point. A cooling stirrer 2 that cools and stirs to form the composite intermediate granules from a starch / resin composite material containing a melting point additive, and a starch / resin composite intermediate granules are stocked and processed for starch / resin composite molding. It is a manufacturing apparatus including a stock tank and a supplying apparatus 3 that can serve as a supply buffer for composite intermediate particles as a raw material so that the material can be continuously produced.
また、澱粉・樹脂複合成形加工材料製造装置部Ｂは、該装置部Ａにおいて製造され、貯蔵された複合中間粒体を原材料として連続的に供給できるように構成されたストックタンク兼供給装置３から澱粉・樹脂複合中間粒体を供給し、加熱混練され、流動性の澱粉・樹脂複合材料にして押し出す二軸押出機４と、混練され溶融状態にある熱可塑性樹脂を更にシリンダ温度を高くし、溶融熱可塑性樹脂澱粉複合成形材料として安定的に押し出す一軸押出機５を少なくとも含む構成とした製造装置部からなる。
澱粉・樹脂複合成形加工材料製造装置部Ｂを単独の製造装置とし、原材料として澱粉・樹脂複合中間粒体を別途準備し、バッチで製造する装置とすることもできる。
Further, the starch / resin composite molding processing material manufacturing apparatus B is provided from the stock tank / supplying apparatus 3 configured so that the composite intermediate particles manufactured and stored in the apparatus A can be continuously supplied as raw materials. A twin-screw extruder 4 that supplies a starch-resin composite intermediate granule and heat-kneads it to make a fluid starch-resin composite material and extrudes it, and a thermoplastic resin that is kneaded and melted to further raise the cylinder temperature. It comprises a manufacturing equipment section including at least a uniaxial extruder 5 that stably extrudes as a molten thermoplastic resin starch composite molding material.
It is also possible to use the starch / resin composite molding processing material manufacturing apparatus B as a single manufacturing apparatus, and separately prepare a starch / resin composite intermediate granule as a raw material to manufacture the starch / resin composite intermediate particles in a batch.
本発明で用いる前記装置は、さらに、シート状に押し出しし、該シートをカレンダ成形により、シートの厚さ制御、表面層の形成制御を行なうことができるローラ圧延装置、ストランド状に押し出しし、切断するか又はシート状に押し出しし、賽の目上に切断することにより、ペレット化するための切断装置等を含むことができる。 The apparatus used in the present invention is further extruded into a sheet, a roller rolling apparatus capable of controlling the thickness of the sheet and the formation of a surface layer by calendering, extruding into a strand, and cutting. It can also include a cutting device for pelletizing by rolling or extruding into a sheet and cutting on the grain.
（澱粉・樹脂複合中間粒体の製造）
本発明の澱粉・樹脂複合成形加工材料の製造において澱粉・樹脂複合中間粒体は、図１に示す装置Ａ部により製造することができる。
(Manufacture of starch / resin composite intermediate particles)
In the production of the starch / resin composite molding processing material of the present invention, the starch / resin composite intermediate granules can be produced by the apparatus A part shown in FIG.
澱粉・樹脂複合中間粒体の製造では、澱粉及び、低融点添加剤の少なくとも１種以上を高温撹拌機中で熱可塑性樹脂の溶融温度より低い、低融点添加剤が溶融する温度以上の温度で加熱撹拌しながら混合し、澱粉と溶融させた低融点添加剤の混合物となるように加熱撹拌を制御する。 In the production of starch-resin composite intermediate granules, at least one of starch and low melting point additive is placed in a high temperature stirrer at a temperature lower than the melting temperature of the thermoplastic resin and higher than the melting temperature of the low melting point additive. Mix while heating and stirring, and control the heating and stirring so that the mixture of starch and the melted low melting point additive is obtained.
その後、熱可塑性樹脂、脂肪酸金属塩等の高融点添加剤を添加し、必要ならば、成形加工材料に求める物性、性質を有するようにその他の添加剤を加え、さらに加熱撹拌して混合し、流動性の澱粉・樹脂複合材料を形成する。 After that, a refractory additive such as a thermoplastic resin or a metal fatty acid salt is added, and if necessary, other additives are added so as to have the desired physical properties and properties of the molding material, and the mixture is further heated and stirred to mix. Form a fluid starch / resin composite material.
次いで、形成した流動性の澱粉・樹脂複合材料を、冷却撹拌機に移し、冷却撹拌機中で冷却撹拌しながら、主として高融点添加剤を再固化する。 Next, the formed fluid starch / resin composite material is transferred to a cooling stirrer, and the refractory additive is mainly resolidified while cooling and stirring in the cooling stirrer.
高融点添加剤を主として再固化することにより熱可塑性樹脂の粒状体をコア部とし、そのコア部の表面に少なくとも低融点添加剤を含有する澱粉を含む粉粒体の被覆層を形成した澱粉・樹脂複合中間粒体を形成できる。 A starch in which a granular material of a thermoplastic resin is formed as a core portion by mainly resolidifying a high melting point additive, and a coating layer of a powder or granular material containing starch containing at least a low melting point additive is formed on the surface of the core portion. Resin composite intermediate particles can be formed.
（高温撹拌機による加熱撹拌処理）
（１）澱粉と低融点添加剤の加熱撹拌処理
加熱撹拌処理では、高温撹拌機中で澱粉と低融点添加剤を加熱撹拌することで、加熱混合するものであって、以下のように行う。
先ず、高温撹拌機１は高温撹拌機中に澱粉と、グリセリン系脂肪酸エステルなどの低融点添加剤を混合投入し、加熱撹拌する。
その加熱撹拌処理は、加熱温度を低融点添加剤の融点温度以上に設定し、低融点添加剤を溶融させ、低融点添加剤が溶融状態を維持できる温度、例えば、低融点添加剤の融点温度より１０〜２０℃高く設定、あるいは高融点添加剤の融点温度以上の温度に設定し、回転数及び撹拌時間を制御することで澱粉の粉体と溶融した低融点添加剤とが絡み、付着され低融点添加剤が付着され含有された澱粉の流動性の澱粉混合物が形成できるように、製造効率を考え、温度、回転数及び撹拌時間などを制御し、処理する。
(Heating and stirring with a high temperature stirrer)
(1) Heat-stirring treatment of starch and low-melting point additive In the heat-stirring treatment, starch and low-melting point additive are heated and mixed by heating and stirring in a high-temperature stirrer, and are carried out as follows.
First, the high-temperature stirrer 1 mixes and charges starch and a low-melting point additive such as a glycerin-based fatty acid ester into the high-temperature stirrer, and heats and stirs the mixture.
In the heating and stirring treatment, the heating temperature is set to be equal to or higher than the melting point temperature of the low melting point additive, the low melting point additive is melted, and the temperature at which the low melting point additive can maintain the molten state, for example, the melting point temperature of the low melting point additive. By setting the temperature higher than 10 to 20 ° C or higher than the melting point temperature of the high melting point additive and controlling the rotation speed and stirring time, the starch powder and the melted low melting point additive are entangled and adhered. The temperature, rotation speed, stirring time, etc. are controlled and processed in consideration of production efficiency so that a fluid starch mixture of the starch containing the low melting point additive can be formed.
加熱撹拌処理では、高温撹拌機を、例えば、加熱温度１１０〜１６０℃、回転数５〜５０Ｈｚに設定し、撹拌時間を制御して、低融点添加剤の成分を溶融状態にし、高温撹拌機中で澱粉と低融点添加剤を撹拌、混合する。この処理により澱粉に溶融した低融点添加剤を付着させ、含有し、低融点添加剤を含有した澱粉混合物を形成する。その際、澱粉に低融点添加材がくまなく絡めている状態となる。本発明の加熱撹拌処理では、製造時間、製造効率を考慮して温度は１００℃以上とすることが好ましい。温度と時間の調整により澱粉が黄変するのを避けるようにすることが好ましい。また、黄変、製造効率に問題なく手早く均等に混ぜるため、撹拌状態、回転数及び剪断力などを調整して行なうことが好ましい。 In the heat stirring process, the high temperature stirrer is set to, for example, a heating temperature of 110 to 160 ° C. and a rotation speed of 5 to 50 Hz, and the stirring time is controlled to melt the components of the low melting point additive in the high temperature stirrer. Stir and mix the starch and low melting point additive in. By this treatment, a melted low melting point additive is attached to and contained in the starch to form a starch mixture containing the low melting point additive. At that time, the low melting point additive is entwined all over the starch. In the heat-stirring treatment of the present invention, the temperature is preferably 100 ° C. or higher in consideration of the production time and production efficiency. It is preferable to avoid yellowing of starch by adjusting the temperature and time. Further, in order to mix quickly and evenly without any problem of yellowing and production efficiency, it is preferable to adjust the stirring state, the number of rotations, the shearing force and the like.
（２）澱粉・樹脂複合材料の形成
高温撹拌機で撹拌澱粉と溶融した低融点添加剤の混合物とした後、熱可塑性樹脂の粒状体及び少なくとも１種以上の脂肪酸金属塩等の高融点添加剤をさらに添加し、加熱撹拌する。
(2) Formation of starch / resin composite material After making a mixture of starch and a molten low melting point additive with a high temperature stirrer, a high melting point additive such as a granular material of a thermoplastic resin and at least one fatty acid metal salt Is further added and heated and stirred.
本発明では、加熱撹拌時の温度を高融点添加剤が溶融する温度以上、熱可塑性樹脂の溶融温度以下に高温撹拌機の温度を設定、例えば、加熱撹拌温度として、当初から高融点添加剤の溶融温度以上に設定し、加熱温度を固定して行なうこともでき、例えば、１１０〜１６０℃に設定し、少なくとも２種類の、低融点及び高融点添加剤が溶融した状態にして撹拌混合する。そして低融点及び高融点添加剤が溶融した状態下、回転数及び撹拌時間を制御しつつ加熱撹拌することで、澱粉及び熱可塑性樹脂の粒状体と、溶融した低融点及び高融点添加剤とが撹拌混合され、均一に分散された流動性の澱粉・樹脂複合材料の混合物を形成する。 In the present invention, the temperature at the time of heating and stirring is set to be equal to or higher than the temperature at which the high melting point additive melts and below the melting temperature of the thermoplastic resin. For example, the heating and stirring temperature is set to the temperature at which the high melting point additive is melted from the beginning. It can be set to a melting temperature or higher and the heating temperature is fixed. For example, it is set to 110 to 160 ° C., and at least two kinds of low melting point and high melting point additives are melted and mixed by stirring. Then, under the molten state of the low melting point and high melting point additives, by heating and stirring while controlling the rotation speed and the stirring time, the granules of starch and the thermoplastic resin and the melted low melting point and high melting point additives can be obtained. It is agitated and mixed to form a uniformly dispersed mixture of fluid starch / resin composite material.
（冷却撹拌機による冷却撹拌処理）
高温撹拌機中で得られた流動性の澱粉・樹脂複合材料の混合物は、冷却撹拌機に移され、低融点添加剤成分の溶融温度以上であって、その融点温度近傍まで冷却撹拌機中で撹拌しながら冷却され、主として溶融した高融点添加剤の添加剤成分が再固化されるように冷却撹拌する。
(Cooling and stirring treatment with a cooling stirrer)
The mixture of the fluid starch / resin composite material obtained in the high temperature stirrer is transferred to the cooling stirrer, and is kept above the melting temperature of the low melting point additive component in the cooling stirrer until near the melting point temperature. It is cooled with stirring, and is cooled and stirred so that the additive component of the melted high melting point additive is resolidified.
澱粉・樹脂複合材料は、冷却撹拌機中で冷却しながら撹拌することにより流動性の澱粉・樹脂複合材料の温度が低下し、少なくとも脂肪酸金属塩などの高融点添加剤成分が冷却され、溶融温度以下になることにより再固化するように冷却撹拌する。その際、流動性の澱粉・樹脂複合材料の混合物中の高融点添加剤が冷却撹拌されることにより熱可塑性樹脂の粒状体の表面に付着した状態に固化し、また流動性のある低融点添加剤を含有した澱粉が、再固化する少なくとも高融点添加剤を介して熱可塑性樹脂の粒状体に付着することにより、熱可塑性樹脂の粒状体をコア部とし、そのコア部の表面に少なくとも低融点添加剤を含有する澱粉を含む粉粒体の被覆層が形成され、図２ａに示すように澱粉・樹脂複合中間粒体となる。その澱粉・樹脂複合中間粒体は、その断面を模式的に示すと図３に示す構造のものである。 By stirring the starch / resin composite material while cooling it in a cooling stirrer, the temperature of the fluid starch / resin composite material is lowered, and at least the refractory additive component such as a fatty acid metal salt is cooled, and the melting temperature is reached. Cool and stir so that it solidifies as follows. At that time, the high melting point additive in the mixture of the fluid starch / resin composite material is cooled and stirred to solidify in a state of being attached to the surface of the granular material of the thermoplastic resin, and the low melting point addition with fluidity is added. The starch containing the agent adheres to the granular material of the thermoplastic resin via at least the high melting point additive that resolidifies, so that the granular material of the thermoplastic resin becomes the core portion, and at least the low melting point is applied to the surface of the core portion. A coating layer of a powder or granular material containing starch containing an additive is formed, and as shown in FIG. 2a, a starch / resin composite intermediate particle is formed. The starch / resin composite intermediate granule has a structure shown in FIG. 3 when its cross section is schematically shown.
澱粉・樹脂複合中間粒体は、性質や形状が異なる成分材料を原材料とする材料を、加熱混合して流動性の複合材料混合物とし、該混合物を撹拌しながら冷却し、流動性の複合材料混合物が温度の低下により、溶融した添加剤成分が溶融温度以下になることにより、固化するという、単純な操作により簡単に、撹拌製造工程への原材料の安定供給を可能にする、取り扱い性のよい澱粉・樹脂複合中間粒体が造粒化し、形成されたものである。 In the starch / resin composite intermediate granules, materials made of component materials having different properties and shapes are heated and mixed to form a fluid composite material mixture, and the mixture is cooled with stirring to obtain a fluid composite material mixture. However, as the temperature drops, the molten additive component becomes solidified when it falls below the melting temperature, which is a simple operation that enables the stable supply of raw materials to the stirring manufacturing process. -The resin composite intermediate granules are granulated and formed.
本発明では、従来、成形加工材料の製造に際し、性状や形状が異なる成分の原材料を、それぞれ、製造工程に個別又はバッチで供給していたのを、取り扱い性のよい複合中間粒体という複合形態の原材料として成形加工材料の製造工程に投入できるようになり、澱粉・樹脂複合成形加工材料の製造において原材料の安定供給及び定量化を可能にすることができる。 In the present invention, in the production of a molded material, raw materials having components having different properties and shapes are conventionally supplied to the production process individually or in batches, which is a composite form called a composite intermediate granule with good handleability. It becomes possible to put it into the manufacturing process of the molding processed material as a raw material of the above, and it is possible to stably supply and quantify the raw material in the manufacturing of the starch / resin composite molding processed material.
冷却撹拌操作による造粒工程は、温度、回転数及び撹拌時間などを制御し、添加剤成分を再固化することにより熱可塑性樹脂の粒状体の表面に澱粉を含む粉粒体の被覆層が形成される状態を確認しながら、最適温度下に冷却撹拌することで造粒化し、形成された粒体の形態、形状を維持し取り出すことが可能になる。 In the granulation process by cooling and stirring operation, the temperature, rotation speed, stirring time, etc. are controlled, and the additive component is resolidified to form a coating layer of powder or granular material containing starch on the surface of the granular material of the thermoplastic resin. By cooling and stirring at an optimum temperature while confirming the state of being formed, it becomes possible to granulate, maintain the shape and shape of the formed granules, and take them out.
本発明は、澱粉・樹脂複合中間粒体を、造粒された粒体の外観をみながら、外観の仕上がりのよい状態を確認でき、低融点添加剤成分の固化が進まない温度域で冷却撹拌機から排出してストックタンク中に落下させ、澱粉・樹脂複合中間粒体形状の中間原料として取
り出され、ストックされる。これにより、粉落ちのほとんどない、形態安定性の優れた澱粉・樹脂複合中間粒体を得ることができる。
In the present invention, the starch / resin composite intermediate granules can be confirmed to have a good appearance while observing the appearance of the granulated granules, and the low melting point additive component is cooled and stirred in a temperature range where solidification does not proceed. It is discharged from the machine, dropped into a stock tank, taken out as an intermediate raw material in the form of a starch / resin composite intermediate particle, and stocked. As a result, it is possible to obtain a starch-resin composite intermediate granule having excellent morphological stability with almost no powder falling off.
複合中間粒体の形成状況を温度、回転数及び撹拌時間などを制御し、添加剤の成分を再固化することにより熱可塑性樹脂の粒状体の表面に澱粉を含む粉粒体の被覆層が形成される状態を観察し、確認することにより、形成された粒体の形態、形状を維持し、粉落ちのほとんどない、形態安定性の優れた澱粉・樹脂複合中間粒体を得ることができる。 By controlling the formation status of the composite intermediate particles such as temperature, rotation speed, stirring time, etc. and resolidifying the components of the additive, a coating layer of the powder or granular material containing starch is formed on the surface of the granular material of the thermoplastic resin. By observing and confirming the state of being formed, it is possible to obtain a starch / resin composite intermediate granule having excellent morphological stability while maintaining the morphology and shape of the formed granules and having almost no powder falling off.
複合中間粒体の形成に過程で低融点添加剤と高融点添加剤の添加量が少ない場合、澱粉と熱可塑性樹脂の粒状体との親和性が低下するためか澱粉が付着して被膜層ができず、粉状のままあるいは被覆層からの澱粉の脱落が生じ、複合中間粒体と粉状体との混合物（図２ｂ参照）となり、押出ができなかった。また、複合中間粒体を低融点添加剤の溶融温度より十分に高い温度で排出すると、表面被覆層の粉粒体が流動変形し得るため、落下時の衝撃で粒体の形状、形態が変形し、型崩れを生じ、かつ粒体が塊状になり、流動安定性が低下する。 If the amount of low melting point additive and high melting point additive added is small in the process of forming the composite intermediate granules, the starch adheres to the coating layer, probably because the affinity between the starch and the granular material of the thermoplastic resin decreases. It could not be extruded because it remained in powder form or starch was shed from the coating layer, resulting in a mixture of composite intermediate particles and powder (see FIG. 2b). Further, when the composite intermediate particles are discharged at a temperature sufficiently higher than the melting temperature of the low melting point additive, the powder particles of the surface coating layer may be fluidly deformed, so that the shape and shape of the particles are deformed by the impact at the time of dropping. However, it loses its shape and the granules become lumpy, resulting in reduced flow stability.
この加熱、冷却撹拌工程により澱粉・樹脂複合中間粒体を製造する方法は、バッチ式で製造することもできる。一方、澱粉・樹脂複合成形加工材料の製造は、成分材料を複合中間粒体という形態の原材料として連続的に混練し押し出することを可能にするので、澱粉・樹脂複合中間粒体の製造方法において、複合中間粒体をストックタンクに排出する工程は、複合中間粒体製造工程を澱粉・樹脂複合成形加工材料の製造方法に組み入れるバッファとなり、澱粉・樹脂複合成形加工材料を連続的に一貫して製造することを可能にする。 The method for producing the starch / resin composite intermediate granules by this heating / cooling / stirring step can also be produced in a batch system. On the other hand, the production of the starch / resin composite molding processed material enables the component material to be continuously kneaded and extruded as a raw material in the form of a composite intermediate granule, and therefore, in the method for producing a starch / resin composite intermediate granule. , The process of discharging the composite intermediate granules to the stock tank serves as a buffer for incorporating the composite intermediate granule manufacturing process into the manufacturing method of the starch / resin composite molded material, and continuously and consistently the starch / resin composite molded material. Makes it possible to manufacture.
本発明は、粉落ちのない、形態安定性のよい澱粉・樹脂複合中間粒体を原材料とする成形加工材料を製造するものであり、品質にバラツキの少ない澱粉・樹脂複合成形材料を安定的に得ることができる。そして、均一で均質な澱粉・樹脂複合材料として安定的に安価に調製することが可能になり、バイオマス複合材料を安定的に提供することができる。 The present invention is for producing a molding processing material using a starch / resin composite intermediate granule as a raw material, which does not cause powder to fall off and has good morphological stability, and stably produces a starch / resin composite molding material with little variation in quality. Obtainable. Then, it becomes possible to stably and inexpensively prepare a uniform and homogeneous starch / resin composite material, and it is possible to stably provide a biomass composite material.
（澱粉・樹脂複合成形加工材料の製造）
本発明の澱粉・樹脂複合成形加工材料は、上記澱粉・樹脂複合中間粒体を製造し、各成分材料が併存した集合体の澱粉・樹脂複合材料を原材料として製造される。澱粉・樹脂複合中間粒体を原材料として各種成形加工法に適用できる澱粉・樹脂複合成形加工材料を製造するには、澱粉・樹脂複合中間粒体を製造する工程を、該澱粉・樹脂複合成形加工材料の製造工程中に組み込むことで澱粉・樹脂複合成形加工材料の中間原材料としてストックすることを可能にする製造ラインとするか、あるいは、澱粉・樹脂複合成形加工材料の製造工程とは別に複合中間粒体の製造ラインとして設けることで、澱粉・樹脂複合中間粒体を原材料として安定して供給することで、性質や形状の異なる原材料の安定供給を実現し、バラツキの少ない澱粉・樹脂複合成形加工材料の連続的に供給できるものである。
(Manufacturing of starch / resin composite molding processing material)
The starch / resin composite molding processing material of the present invention is produced by producing the above-mentioned starch / resin composite intermediate granules, and using the starch / resin composite material of an aggregate in which each component material coexists as a raw material. In order to produce a starch / resin composite molding process material that can be applied to various molding methods using starch / resin composite intermediate particles as a raw material, the step of producing the starch / resin composite intermediate particles is performed by the starch / resin composite molding process. It will be a production line that can be stocked as an intermediate raw material for starch / resin composite molding processing materials by incorporating it into the manufacturing process of the material, or it will be a composite intermediate separately from the manufacturing process of the starch / resin composite molding processing material. By providing it as a production line for granules, stable supply of starch / resin composite intermediate granules as raw materials realizes stable supply of raw materials with different properties and shapes, and starch / resin composite molding processing with little variation. It is a material that can be continuously supplied.
製造された澱粉・樹脂複合成形加工材料は、さらに、シート状又はフィルム状に成形されたり、ブロー成形されたり、あるいは真空成形され、最終製品の成形加工材料として利用することもできる。 The produced starch / resin composite molding material can be further molded into a sheet or film, blow-molded, or vacuum-formed, and can be used as a molding material for a final product.
具体的には、本発明のストックされた、熱可塑性樹脂をコア部とし、その外側に低融点添加剤を含有する澱粉の粉粒体の被覆層で覆われた構造を有する澱粉・樹脂複合材料の均一な粒体として存在する澱粉・樹脂複合中間粒体から、各種成形加工法に用いることができる澱粉・樹脂複合成形加工材料を製造するため、通常のプラスチックの成形加工技術のように、例えば、ヘンシエルミキサー、タンブラー型混合機、バーバリミキサー、ニーダーミキサーなどの混合機により澱粉や添加剤等を混合する必要なく、澱粉・樹脂複合中間粒体を直接二軸押出機に投入、供給するだけで、通常のプラスチック成形加工と同様に回転数、撹拌時間及び温度などの制御を行い、加熱混練することにより澱粉と熱可塑性樹脂を均一に混練、混合することができる。 Specifically, a starch-resin composite material having a structure in which the stocked thermoplastic resin of the present invention is used as a core portion and the outside thereof is covered with a coating layer of a powder or granular material of starch containing a low melting point additive. In order to produce a starch / resin composite molding processing material that can be used in various molding processing methods from the starch / resin composite intermediate granules existing as uniform particles of, for example, as in ordinary plastic molding processing technology, for example. , Hensiel mixer, tumbler type mixer, barbary mixer, kneader mixer, etc., without the need to mix starch and additives, just put the starch / resin composite intermediate granules directly into the twin-screw extruder and supply them. Therefore, the starch and the thermoplastic resin can be uniformly kneaded and mixed by controlling the rotation speed, stirring time, temperature, and the like in the same manner as in the normal plastic molding process and heating and kneading.
澱粉・樹脂複合中間粒体を二軸押出機中で加熱混練する処理に際し、加熱加工温度（シリンダ温度）を１００℃〜１９０℃、熱可塑性樹脂が溶融する温度以下の温度、添加剤の融点以上の温度に設定し、加熱混練する。それにより澱粉・樹脂複合中間粒体を流動性の澱粉・樹脂複合成形加工材料を形成する前段階として、剪断と温度上昇を抑えつつ、安定した材料の定量送り及び材料を十分に撹拌混練することができる。これにより、材料の劣化、退色させずに均一に混練することができ、均一で均質なバラツキの少ない澱粉・樹脂複合成形加工材料とすることができる。 When the starch / resin composite intermediate granules are heated and kneaded in a twin-screw extruder, the heat processing temperature (cylinder temperature) is 100 ° C to 190 ° C, the temperature is below the temperature at which the thermoplastic resin melts, and above the melting point of the additive. Set to the temperature of and heat and knead. As a preparatory step for forming a fluid starch / resin composite molding process material from the starch / resin composite intermediate granules, stable fixed quantity feeding of the material and sufficient stirring and kneading of the material while suppressing shearing and temperature rise are performed. Can be done. As a result, the material can be kneaded uniformly without deterioration or fading, and a starch / resin composite molded material that is uniform and has little variation can be obtained.
本発明では、澱粉・樹脂複合中間粒体を十分な加熱混練の後、プラスチックの溶融押出工程と同様、流動性のある澱粉・樹脂複合材料を一軸押出機により熱可塑性樹脂の溶融温度以上、１５０〜２２０℃に温度設定し、押出圧力を適宜設定し、熱可塑性樹脂を溶融押出することにより安定した押出温度、押出圧力下で、均一で均質なバラツキの少ない澱粉・樹脂複合成形加工材料を得ることができる。 In the present invention, after the starch / resin composite intermediate granules are sufficiently heated and kneaded, the fluid starch / resin composite material is extruded by a uniaxial extruder at a temperature equal to or higher than the melting temperature of the thermoplastic resin, 150 as in the melt extrusion step of plastics. By setting the temperature to ~ 220 ° C., setting the extrusion pressure appropriately, and melt-extruding the thermoplastic resin, a uniform and uniform starch / resin composite molding material with little variation can be obtained under a stable extrusion temperature and extrusion pressure. be able to.
押出に際し、押出機による成形品の製造、Ｔダイ押出機によるシートの製造、インフレーション成形機によるフィルムの製造、カレンダ成形機によるシートの製造、インジェクション成形機による成形品の製造などの成形加工技術及び成形加工機が採用でき、各種成形加工法に適した優れた成形加工性を備えた澱粉・樹脂複合成形加工材料が得られる。 For extrusion, molding technology such as manufacturing of molded products by an extruder, sheet manufacturing by a T-die extruder, film manufacturing by an inflation molding machine, sheet manufacturing by a calender molding machine, and molding by an injection molding machine. A molding machine can be adopted, and a starch / resin composite molding material having excellent molding processability suitable for various molding methods can be obtained.
本発明では、澱粉・樹脂複合中間粒体を原材料とし、Ｔダイスを用い、１５０〜２２０℃に温度設定し、澱粉・樹脂複合成形加工材料をシート状物として押出し、シート状成形加工材料を得ることができる。成形温度が２２０℃を越えた場合は、ヤケの発生や分解の発生が起きる。著しい場合は、茶色又は黒色に変色し、シリンダ内の焼き付きにより成形機を損傷する。また、１５０℃未満の成形温度域では澱粉・樹脂複合成形加工材料が未溶融状態で吐出され、好ましくない。著しい場合は、シリンダとスクリュー間の剪断力が高まり、圧力上昇とともに、トラブルの原因となる。 In the present invention, a starch / resin composite intermediate granule is used as a raw material, a temperature is set to 150 to 220 ° C. using a T die, and the starch / resin composite molding material is extruded as a sheet to obtain a sheet molding material. be able to. If the molding temperature exceeds 220 ° C., discoloration or decomposition occurs. In significant cases, the color changes to brown or black, and seizure in the cylinder damages the molding machine. Further, in the molding temperature range of less than 150 ° C., the starch / resin composite molding processing material is discharged in an unmelted state, which is not preferable. In a remarkable case, the shearing force between the cylinder and the screw increases, which causes a trouble as well as an increase in pressure.
押出機によりシート状に押し出し成形した澱粉・樹脂複合成形加工材料シートは、押し出された後、直ちに、引取りロールの温度を６０℃以下に設定し、所定の厚さに成形したシートを冷却し、原反シートとして引取り、巻き取られるか、あるいは、澱粉・樹脂複合成形加工材料の原反シートをロールに冷却機能を持たせてロール表面を冷却して行なう三本圧延ロールの間を通過させ、圧延ロールによりシート化しつつ冷却して厚み０．１〜２．０ｍｍの澱粉・樹脂複合成形加工シートを得、各種成形加工法の原材料シートとして又は該シートを粉砕又はカットして粒状体を得ることによりインジェクション成形、インフレーション成形、ブロー成形に適した原材料ペレットの成形加工材料とすることができる。 The starch / resin composite molded material sheet extruded into a sheet by an extruder is extruded, and immediately after being extruded, the temperature of the take-up roll is set to 60 ° C. or lower, and the sheet formed to a predetermined thickness is cooled. , It is taken up as a raw sheet and wound up, or the raw sheet of a starch / resin composite molding process material is passed between three rolling rolls which are made by giving a cooling function to the roll and cooling the roll surface. Then, the sheet is formed into a sheet by a rolling roll and cooled to obtain a starch / resin composite molded sheet having a thickness of 0.1 to 2.0 mm, which is used as a raw material sheet for various molding methods or the sheet is crushed or cut to form granules. By obtaining it, it can be used as a molding processing material for raw material pellets suitable for injection molding, inflation molding, and blow molding.
本発明において、シート状物の澱粉・樹脂複合成形加工材料原反ロールを圧延ロールにより厚みを制御された、表面スキン層を形成した成形加工材料シートとするため、あるいは表面スキン層のない成形加工材料シートとするため、冷却はロールに冷却機能を持たせてその表面を冷却して行なう三本圧延ロールの間を通過させ、厚さと表面スキン層の有無及び厚みを制御し、さらにシート表面温度の温度制御をすることにより所望の成形加工材料シート又は粉砕又はカット可能な成形加工材料シートとすることができる。また、圧延ロールによってシートに成形することで、澱粉・樹脂複合成形加工材料シートの厚さが均一になり、均質なペレットとすることができる。加えて圧延ロールの作用によってシートの表裏に平滑なスキン層を形成することにより、ペレット化後の水分吸収を減じた材料ができる。 In the present invention, in order to make a sheet-like starch / resin composite molding material raw fabric sheet into a molding material sheet having a surface skin layer whose thickness is controlled by a rolling roll, or molding without a surface skin layer. In order to make a material sheet, cooling is performed by giving the roll a cooling function and passing it between three rolling rolls that cool the surface, control the thickness and the presence / absence and thickness of the surface skin layer, and further control the sheet surface temperature. By controlling the temperature of the above, a desired molded material sheet or a molded material sheet that can be crushed or cut can be obtained. Further, by molding into a sheet by a rolling roll, the thickness of the starch / resin composite molding processing material sheet becomes uniform, and uniform pellets can be obtained. In addition, by forming a smooth skin layer on the front and back of the sheet by the action of the rolling roll, a material with reduced water absorption after pelletization can be obtained.
以下、本発明の複合成形加工材料について実施例により、さらに詳しく説明するが、本発明はその要旨を超えない限り、以下の実施例に制限されるものではない。
得られた澱粉・樹脂複合成形加工材料の評価として、成形加工性材料として、比重、引張伸度を測定し、均一、均質性を比重と引張伸度の変動に着目し、評価した。なお比重、引張伸度を測定するため以下に説明する試験法により測定した。
その評価方法は、以下の要領で行った。
Hereinafter, the composite molded material of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist of the present invention is not exceeded.
As an evaluation of the obtained starch / resin composite molding processed material, the specific gravity and tensile elongation were measured as the molding processable material, and the uniformity and homogeneity were evaluated by paying attention to the fluctuation of the specific gravity and the tensile elongation. In order to measure the specific gravity and the tensile elongation, the measurement was performed by the test method described below.
The evaluation method was as follows.
（実施形態）
本発明の澱粉・樹脂複合中間粒体及び澱粉・樹脂複合成型加工材料を製造するための使用原料及び試料作成方法は、以下のとおりである。
（澱粉・樹脂複合成形加工材料の製造）
本発明の澱粉・樹脂複合中間粒体及び澱粉・樹脂複合成形加工材料を製造するため配合した原材料は、以下のとおりである。
(Embodiment)
The raw materials used and the sample preparation method for producing the starch / resin composite intermediate granules and the starch / resin composite molding processing material of the present invention are as follows.
(Manufacturing of starch / resin composite molding processing material)
The raw materials blended for producing the starch / resin composite intermediate granules and the starch / resin composite molding processing material of the present invention are as follows.
澱粉 ： コーンスターチ ５０〜７０重量％
低融点添加剤： グリセリン脂肪酸エステル、グリセリンモノステアレート ０．１〜１０．０重量％
高融点添加剤： ステアリン酸金属塩 ステアリン酸亜鉛、ステアリン酸マグネシウム
１．０〜１５重量％
熱可塑性樹脂： ポリプロピレンペレット ２０〜４０重量％
上記した各原材料を表１の配合割合にしたがって用いた。
Starch: Cornstarch 50-70% by weight
Low melting point additives: Glycerin fatty acid ester, glycerin monostearate 0.1 to 10.0% by weight
Melting point additive: metal stearate salt zinc stearate, magnesium stearate 1.0 to 15% by weight
Thermoplastic resin: Polypropylene pellets 20-40% by weight
Each of the above raw materials was used according to the blending ratio in Table 1.
（１）加熱撹拌１
高温撹拌機を１１０〜１６０℃、回転数５〜５０Ｈｚに設定し、澱粉としてコーンスターチ５０〜７０重量％と低融点添加剤としてグリセリンモノステアレート０．１〜１０．０重量％を配合し、材料を加熱撹拌、混合する。グリセリンモノステアレートの融点以上の温度で加熱撹拌して溶融し、コーンスターチに溶融したグリセリンモノステアレートを絡ませ、グリセリンモノステアレートが付着し、含有する澱粉にする。
(1) Heating and stirring 1
The high temperature stirrer is set at 110 to 160 ° C. and the rotation speed is 5 to 50 Hz, and 50 to 70% by weight of cornstarch is blended as starch and 0.1 to 10.0% by weight of glycerin monostearate is blended as a low melting point additive. Is heated, stirred and mixed. The starch is melted by heating and stirring at a temperature equal to or higher than the melting point of glycerin monostearate, and the melted glycerin monostearate is entangled with cornstarch to form a starch containing glycerin monostearate.
（２）加熱撹拌２
高温撹拌機中で十分に混合し、コーンスターチを澱粉・樹脂複合材料とするため、ポリプロピレン２０〜４０重量％、高融点添加剤としてステアリン酸金属塩であるステアリン酸亜鉛０．５〜５．０重量％、ステアリン酸マグネシウム０．５〜１０．０重量％、及びその他必要な添加剤、例えば、白色顔料、相溶化剤を投入し、撹拌しながら、１１０〜１６０℃まで昇温し、上記ステアリン酸の金属石鹸を溶融し、流動性の澱粉・樹脂複合材料の混合物が形成されるまで混合撹拌する。
(2) Heating and stirring 2
Mix well in a high temperature stirrer to make corn starch a starch / resin composite material, 20-40% by weight of polypropylene, 0.5-5.0 weight of zinc stearate, a metal stearate salt as a refractory additive. %, Stearic acid 0.5 to 10.0% by weight, and other necessary additives such as white pigment and compatibilizer are added, and the temperature is raised to 110 to 160 ° C. with stirring. The metal soap of Stearic Acid is melted and mixed and stirred until a mixture of fluid starch / resin composite material is formed.
（３）冷却撹拌
次いで、澱粉・樹脂複合中間粒体を形成するため、流動性の澱粉・樹脂複合材料の混合物を形成した後、高温撹拌機から排出し、冷却撹拌機中に移し、１１０〜１６０℃の澱粉・樹脂複合材料の混合物を６０〜１００℃に冷却しながら回転数５〜４０Ｈｚで冷却撹拌し、降温させ、熱可塑性樹脂であるポリプロピレンの粒状体をコア部とし、そのコア部表面にグリセリンモノステアレートを付着し含有する澱粉を含む粉粒体が付着し被覆した澱粉・樹脂複合中間粒体が形成されるのを確認するまで低融点添加剤のグリセリンモノステアレートの融点以上の温度で冷却撹拌する。
(3) Cooling and Stirring Next, in order to form a starch / resin composite intermediate granule, a mixture of a fluid starch / resin composite material is formed, discharged from a high temperature stirrer, transferred to a cooling stirrer, and 110 to 10 A mixture of a starch / resin composite material at 160 ° C. is cooled and stirred at a rotation speed of 5 to 40 Hz while being cooled to 60 to 100 ° C., and the temperature is lowered. A granular material of polypropylene, which is a thermoplastic resin, is used as a core portion, and the surface of the core portion is used. The melting point of the low melting point additive glycerin monostearate is higher than the melting point of the low melting point additive until it is confirmed that the powder or granular material containing the starch containing glycerin monostearate adheres to the mixture and the coated starch / resin composite intermediate granules are formed. Cool and stir at temperature.
（４）ストックタンクへの排出
冷却撹拌により澱粉・樹脂複合中間粒体が形成されたことが確認された後、澱粉・樹脂
複合中間粒体の破壊、粉体の剥離、脱落を防止するため低融点添加剤のグリセリンモノステアレートの溶融温度以上の温度を維持しつつ、直ちに、澱粉・樹脂複合中間粒体を連続製造工程内に配置したストックタンクに排出し、中間原材料として貯蔵する。貯蔵される複合中間粒体は、熱可塑性樹脂のコア部と、少なくとも低融点添加剤のグリセリンモノステアレートを含有する澱粉を含む粉粒体の被覆層が、高融点添加剤のステアリン酸亜鉛及びステアリン酸マグネシウムの再固化により付着された、密接に結合した状態にある、粉粒体の脱落又は剥離のない安定した澱粉・樹脂複合中間粒体として形成される。
(4) Discharge to stock tank After it is confirmed that starch / resin composite intermediate particles are formed by cooling and stirring, it is low to prevent the starch / resin composite intermediate particles from breaking, peeling off, and falling off. While maintaining a temperature equal to or higher than the melting temperature of the melting point additive glycerin monostearate, the starch / resin composite intermediate particles are immediately discharged to a stock tank arranged in the continuous production process and stored as an intermediate raw material. In the composite intermediate particles to be stored, the core portion of the thermoplastic resin and the coating layer of the powder or granular material containing starch containing at least the low melting point additive glycerin monostearate are formed of the high melting point additive zinc stearate and It is formed as a stable starch-resin composite intermediate granule that is attached by resolidification of magnesium stearate and is in a tightly bound state without dropping or peeling of the granular material.
（澱粉・樹脂複合中間粒体の評価）
本発明の澱粉・樹脂複合中間粒体の評価方法は、以下の要領で行った。中間原材料として、中間粒体を排出時の粉落ちの有無、及び熱可塑性樹脂をコアとし、表面が澱粉で被覆された粒体の形成割合を観察し、形態安定性を評価した。
粉落ちの有無：ほとんど粉落ちなし〇、粉落ち生じる×、
さらに、得られた澱粉・樹脂複合中間粒体を原材料とし、製造した澱粉・樹脂複合成形加工材料の比重及び引張伸度並びにそのバラツキの程度により中間粒体を評価した。
(Evaluation of starch / resin composite intermediate particles)
The method for evaluating the starch / resin composite intermediate particles of the present invention was carried out as follows. As the intermediate raw material, the presence or absence of powder falling off when the intermediate granules were discharged, and the formation ratio of the granules whose surface was coated with starch with the thermoplastic resin as the core were observed to evaluate the morphological stability.
Presence or absence of powder falling: Almost no powder falling 〇, powder falling occurs ×,
Further, using the obtained starch / resin composite intermediate granules as a raw material, the intermediate granules were evaluated based on the specific gravity and tensile elongation of the produced starch / resin composite molded material and the degree of variation thereof.
（５）澱粉・樹脂複合成形加工材料の製造
澱粉・樹脂複合中間粒子を原材料としてストックタンクから二軸混練可塑化一軸押出機を用い、澱粉・樹脂複合成形加工材料を次のように製造した。
（５−１）澱粉・樹脂複合中間粒体の混練
澱粉・樹脂複合中間粒体をストックタンクから二軸混練可塑化押出機に連続投入し、シリンダ温度１２０〜１９０℃、樹脂圧１〜４ＭＰａに設定し、混練する。混練、可塑化する。
（５−２）澱粉・樹脂複合成形加工材料の成形
澱粉・樹脂複合成形加工材料を製造するため、上記１段目の二軸押出機中で混練、可塑化して調製された澱粉・樹脂複合成形加工材料を、加熱帯域の設定温度をポリプロピレンの溶融温度以上の１６０〜２１０℃、樹脂圧３〜２０ＭＰａに設定した２段目の一軸押出機に供給し、澱粉複合溶融ポリプロピレンを押し出した。
(5) Production of Starch / Resin Composite Molding Material A starch / resin composite molding material was produced from a stock tank using starch / resin composite intermediate particles as a raw material using a twin-screw kneading plasticized uniaxial extruder as follows.
(5-1) Kneading of Starch / Resin Composite Intermediate Granules Starch / resin composite intermediate granules are continuously charged from a stock tank into a twin-screw kneading plasticizing extruder to a cylinder temperature of 120 to 190 ° C. and a resin pressure of 1 to 4 MPa. Set and knead. Knead and plasticize.
(5-2) Molding of Stand / Resin Composite Molding Material In order to produce a starch / resin composite molding material, the starch / resin composite molding prepared by kneading and plasticizing in the twin-screw extruder of the first stage described above. The processing material was supplied to a second-stage uniaxial extruder in which the set temperature of the heating zone was set to 160 to 210 ° C., which is higher than the melting temperature of polypropylene, and the resin pressure was set to 3 to 20 MPa, and the starch composite molten polypropylene was extruded.
（６）澱粉・樹脂複合成形加工材料の後処理
本発明の形成した澱粉・樹脂成形加工材料の成形加工性、作業性に対する影響評価を行なうため次のような後処理を行なった。
（６−１）シートの作成
澱粉・樹脂複合溶融ポリプロピレン成形材料をシート状物として製造する場合は、Ｔ−ダイ押出機（ＬＡＢ ＴＥＣＨエンジニアリング社製）を使用して、シート状に押し出し、引取りロールの温度を４０〜６０℃に設定し、所定の厚さ０．７ mmに成形したシートを冷却し、引取り、紙管に巻き取った。
また、必要に応じて冷却三本ロール（上ロール：５０℃、中ロール：９５℃、下ロール：９０℃）でカレンダ圧延処理して、シートの厚みを制御し、あるいは、シート表面にスキン層の厚みを制御して形成し、つやのあるシートを製造することもできる。
さらに、溶融押出により形成された澱粉・樹脂複合成形加工材料を各種成形加工法の原材料として利用するため、厚み制御した又は表面層を有する成形したシートをペレット化するため、さいの目状に裁断した。
その評価方法は、以下の要領で行った。
(6) Post-treatment of starch / resin composite molding material The following post-treatment was carried out in order to evaluate the influence on the moldability and workability of the starch / resin molding material formed by the present invention.
(6-1) Preparation of sheet When the starch / resin composite molten polypropylene molding material is produced as a sheet, it is extruded into a sheet using a T-die extruder (manufactured by LAB TECH Engineering) and picked up. The temperature of the roll was set to 40 to 60 ° C., the sheet formed to a predetermined thickness of 0.7 mm was cooled, taken up, and wound on a paper tube.
In addition, if necessary, calendar rolling treatment is performed with three cooling rolls (upper roll: 50 ° C., middle roll: 95 ° C., lower roll: 90 ° C.) to control the thickness of the sheet, or a skin layer on the sheet surface. It is also possible to produce a glossy sheet by controlling the thickness of the sheet.
Further, in order to utilize the starch / resin composite molding processed material formed by melt extrusion as a raw material for various molding processing methods, a molded sheet having a thickness control or a surface layer was pelletized and cut into diced shapes.
The evaluation method was as follows.
成形した澱粉・樹脂複合成形加工材料の原反シートの長さ１００ｍあたり１０箇所からシート片（２×２０ｃｍ）をサンプリング抽出し、
（ａ）材料の比重に関しては、上記サンプリングシート片をJIS K7112に従って３回測定し、平均値を求め、その平均値を測定値とする。長手方向の位置を異にするシート片について同様に測定し、平均値を求め各位置における測定値とする。材料の原反シートの各測定値の平均値を求め、各測定値と平均値の変動値を求め、原反シートの比重の測定値の変動幅によりバラツキを確認した。
（ｂ）材料の引張伸度に関して、上記サンプリングシート片をJIS K 7161に従って、シート片を引張り、クリープ現象が起きる前までの最大引張伸度を３回測定し、平均値を求め、その平均値を測定値とする。長手方向の位置を異にするシート片について同様に測定し、平均値を求め各位置における測定値とする。材料の原反シートの各測定値の平均値を求め、各測定値と平均値の変動値を求め、原反シートの該最大引張伸度の測定値の変動幅によりバラツキを確認した。
Sheet pieces (2 x 20 cm) were sampled and extracted from 10 locations per 100 m in length of the raw sheet of the molded starch / resin composite molding process material.
(A) Regarding the specific gravity of the material, the sampling sheet piece is measured three times according to JIS K7112, an average value is obtained, and the average value is used as the measured value. The sheet pieces having different positions in the longitudinal direction are measured in the same manner, and the average value is calculated and used as the measured value at each position. The average value of each measured value of the raw fabric sheet of the material was obtained, the fluctuation value of each measured value and the average value was obtained, and the variation was confirmed by the fluctuation range of the measured value of the specific gravity of the raw fabric sheet.
(B) Regarding the tensile elongation of the material, the sampling sheet piece is pulled according to JIS K 7161, the maximum tensile elongation before the creep phenomenon occurs is measured three times, the average value is calculated, and the average value is obtained. Is the measured value. The sheet pieces having different positions in the longitudinal direction are measured in the same manner, and the average value is calculated and used as the measured value at each position. The average value of each measured value of the raw fabric sheet of the material was obtained, the fluctuation value of each measured value and the average value was obtained, and the variation was confirmed by the fluctuation range of the measured value of the maximum tensile elongation of the raw fabric sheet.
（６−２）容器の成形
澱粉・樹脂複合成形加工材料から製造された上記シートの成形性を確認するために成形したシートを、真空圧空機；（株）脇坂エンジニアリング社製、ＦＶＳ−５００Ｐ型を用いて、成形条件：設定温度４５０℃に加熱した後、円錐カップとなるように真空圧空機により成形した。
(6-2) Molding of container A sheet molded to confirm the moldability of the above sheet manufactured from a starch / resin composite molding processing material is a vacuum pressure air machine; FVS-500P type manufactured by Wakisaka Engineering Co., Ltd. Molding conditions: After heating to a set temperature of 450 ° C., molding was performed by a vacuum pressure air machine so as to form a conical cup.
（実施例１〜７及び比較例１〜５）
澱粉・樹脂複合成形加工材料の原材料として、上記実施態様において示したような製造条件の成分組成に従い原料を準備し、各製造工程の製造条件に従い工程処理し、それぞれ、実施例１〜７及び比較例１〜５の澱粉・樹脂複合中間粒体及び澱粉・樹脂複合成形加工材料を製造した。
実施例及び比較例に従って製造した澱粉・樹脂複合中間粒体についてそれぞれ評価方法に従って評価した。また、実施例及び比較例に従って製造した澱粉・樹脂複合成形加工材料を、評価溶試料とし、評価方法に従って澱粉・樹脂複合成型加工材料の成形加工性を、及び複合成形材料として重要な材料の均一性及び均質性について、引張伸度、比重のバラツキを評価した。
(Examples 1 to 7 and Comparative Examples 1 to 5)
As a raw material for a starch / resin composite molding processing material, a raw material is prepared according to the component composition of the production conditions as shown in the above embodiment, and the process is processed according to the production conditions of each production process, respectively, and compared with Examples 1 to 7. The starch / resin composite intermediate granules and the starch / resin composite molding processing material of Examples 1 to 5 were produced.
The starch / resin composite intermediate particles produced according to Examples and Comparative Examples were each evaluated according to the evaluation method. Further, the starch / resin composite molding processed material produced according to Examples and Comparative Examples is used as an evaluation melt sample, and the molding processability of the starch / resin composite molding processed material is determined according to the evaluation method, and the material important as the composite molding material is uniform. Variations in tensile elongation and specific gravity were evaluated for properties and homogeneity.
シートの成形加工性については、上記Ｔ−ダイ一軸押出機（ＬＡＢ ＴＥＣＨエンジニアリング社製）でシートが成形できるかを確認した。成形したシートを真空圧空機；（株）脇坂エンジニアリング社製、ＦＶＳ−５００Ｐ型により円錐カップになるように真空圧空成形して深絞りの容器が成形できるかを確認した。またインジェクション成形機で容器が成形できるかについても評価した。
その原料の成分組成及び製造された複合中間粒体及び複合成形加工材料についての評価結果は、表１のとおりである。
Regarding the moldability of the sheet, it was confirmed whether the sheet could be molded by the above T-die uniaxial extruder (manufactured by LAB TECH Engineering Co., Ltd.). It was confirmed whether the molded sheet could be vacuum-compressed air-formed with an FVS-500P mold manufactured by Wakisaka Engineering Co., Ltd. so as to form a conical cup to form a deep-throttled container. We also evaluated whether the container could be molded with an injection molding machine.
Table 1 shows the composition of the raw materials and the evaluation results of the produced composite intermediate particles and the composite molded material.
表１に示すとおり、実施例１ないし実施例３の澱粉・樹脂複合中間粒体及びその複合中間粒体を原材料として溶融押出して製造された澱粉・樹脂複合成形加工材料は、各実施例の材料の１ロッドの中で上記試験法により測定した平均引張伸度が３６〜１６０％、平均比重が１．０８〜１．２１の範囲の複合成形材料であって、実施例毎の引張伸度の測定値のバラツキは、実施例１〜３、それぞれ、３４〜３９％、７３〜７７％及び１４８〜１６４％の変動幅を有するものであり、変動幅が大きくても±７％以内、比重の測定値は、±０と変動幅がなく、バラツキの少ない優れた物性を有するものである。その製造した材料を用いた各成形加工法による成形加工性についても、シート化、及び容器の真空成形もでき、深絞りも可能な材料であり、各成形加工法による成形加工性も有するものであった。 As shown in Table 1, the starch / resin composite intermediate granules of Examples 1 to 3 and the starch / resin composite molding processed material produced by melt-extrusion using the composite intermediate granules as raw materials are the materials of each example. A composite molding material having an average tensile elongation of 36 to 160% and an average specific gravity in the range of 1.08 to 1.21 measured by the above test method in one rod of the above, and having a tensile elongation of each example. The variation of the measured values has fluctuation ranges of 34 to 39%, 73 to 77%, and 148 to 164%, respectively, in Examples 1 to 3, and even if the fluctuation range is large, it is within ± 7% and the specific gravity. The measured value is ± 0, which has no fluctuation range and has excellent physical properties with little variation. Regarding the molding processability by each molding method using the manufactured material, it is a material that can be made into a sheet and vacuum formed in a container, and can be deep-drawn, and has the molding processability by each molding method. there were.
これに対し、比較例に示したとおり複合中間粒体を経ない澱粉・樹脂複合成形加工材料
では、シート化できるが、成形できないか、材料に滑性がなく押出できず、又は複合中間粒体が大きすぎ、シート化することができないか、あるいは成形加工材料として溶融押出して製造された複合成形加工材料が１ロッドの中での平均引張伸度が１５％、測定値の変動は７〜２１％、変動幅が±５０％、平均比重が１．１９〜１．２６の変動幅を有し、１ロット内でばらついた値を示すなど、引張伸度等の機械的物性が低下する又は機械的物性が悪く、あるいは比重がバラツキ、安定しない。また、成形加工性の点でも、シート化はできても、シート表面がべたついている、あるいは材料が粉のまま又は塊状となり、成形加工できないなどの材料であった。また、容器の成形はできなかった。
On the other hand, as shown in the comparative example, the starch / resin composite molded material that does not pass through the composite intermediate granules can be formed into a sheet, but cannot be molded, or the material is not slippery and cannot be extruded, or the composite intermediate granules. Is too large to be made into a sheet, or the composite molded material produced by melt extrusion as a molding material has an average tensile elongation of 15% in one rod, and the fluctuation of the measured value is 7 to 21. %, The fluctuation range is ± 50%, the average specific gravity has a fluctuation range of 1.19 to 1.26, and the values vary within one lot. Mechanical properties such as tensile elongation deteriorate or the machine The physical characteristics are poor, or the specific gravity varies, and it is not stable. Further, in terms of molding processability, even if the sheet can be formed, the sheet surface is sticky, or the material is powdery or lumpy and cannot be molded. Moreover, the container could not be molded.
本発明の澱粉・樹脂複合中間粒体を製造した後、該複合中間粒体を原材料とした澱粉・樹脂複合成形加工材料の方が優れた物性、性状及び成形加工性などバラツキの少ない澱粉・樹脂複合成形加工材料が得られることが明らかとなった。 After producing the starch / resin composite intermediate granules of the present invention, the starch / resin composite molding processed material using the composite intermediate granules as a raw material has superior physical properties, properties, and molding processability, and the starch / resin has less variation. It was clarified that a composite molding processed material can be obtained.
実施例、比較例は、表１のとおりの配合組成の澱粉・樹脂複合成形加工材料の組成物とした。実施例２で用いた澱粉・樹脂複合成形加工材料の配合組成のうち、実施例４、５では、主としてモノグリセリッドの配合量を、０．１重量％；１０．０重量％に大幅に変更、実施例６、７では、ステアリン酸亜鉛及びステアリン酸マグネシウムの配合量をそれぞれ、０．５、０．５；５．０、１０．０重量％に大幅に変更して各添加剤の造粒化、成形加工性への影響について確認した。 In Examples and Comparative Examples, the composition of the starch / resin composite molded material having the composition as shown in Table 1 was used. Of the blending composition of the starch / resin composite molding processing material used in Example 2, in Examples 4 and 5, the blending amount of mainly monoglyceride was significantly changed to 0.1% by weight; 10.0% by weight. In Examples 6 and 7, the blending amounts of zinc stearate and magnesium stearate were significantly changed to 0.5, 0.5; 5.0 and 10.0% by weight, respectively, to granulate each additive. The effects on the conversion and molding processability were confirmed.
製造された澱粉・樹脂複合成形加工材料から実施例１と同様の方法で、ペレット、シートを製造するとともに、そのシートを真空圧空成形で実施例１と同じ寸法の容器に成形し、実施例１と同様に成形加工性の評価をした。また、引張伸度、比重について、上記で説明した測定法に従い測定し、評価した。さらに、比較例として、澱粉とポリプロピレンの配合量、モノグリセリッドの配合量及びステアリン酸金属石鹸の配合量をそれぞれ変更し、表１に示すように形成された成形品を評価しつつ、添加する量の範囲を広げ、組成物を調製し、同様の測定を行ない評価した。
その結果を表１に示す。
Pellets and sheets are produced from the produced starch / resin composite molding processing material by the same method as in Example 1, and the sheets are formed into a container having the same dimensions as in Example 1 by vacuum pressure air molding. The molding processability was evaluated in the same manner as in the above. In addition, the tensile elongation and specific gravity were measured and evaluated according to the measuring method described above. Further, as a comparative example, the blending amount of starch and polypropylene, the blending amount of monoglyceride, and the blending amount of metal stearate soap are changed, respectively, and the molded product formed as shown in Table 1 is evaluated and added. The range of amounts was expanded, compositions were prepared, and similar measurements were made for evaluation.
The results are shown in Table 1.
実施例と比較例を比較して分かるように低融点添加剤のモノグリセリッド、高融点添加剤のステアリン酸亜鉛、ステアリン酸マグネシウムを添加する量によって造粒化できる場合とできない場合が生じることが分かる。さらに、添加量により、シート化及びその容器の成形加工性が期待できない場合とできる場合があることが分かる。 As can be seen by comparing Examples and Comparative Examples, granulation may or may not be possible depending on the amount of the low melting point additive monoglyceride, the high melting point additive zinc stearate, and magnesium stearate. I understand. Further, it can be seen that depending on the amount of addition, there are cases where sheet formation and molding processability of the container cannot be expected, and cases where it can be achieved.
Ｔ−ダイ押出機によるシート成形などが発明の効果であり、添加剤の添加量の増加により成形加工性が阻害されていることが分かる。 It can be seen that sheet molding by a T-die extruder is an effect of the invention, and molding processability is hindered by an increase in the amount of additives added.
実施例と比較例によれば、本発明の複合成形加工材料は、Ｔ−ダイ押出機によるシート成形など各種成形加工法による成形加工が可能であり、成形加工性において優位性がある。 According to Examples and Comparative Examples, the composite molding material of the present invention can be molded by various molding methods such as sheet molding by a T-die extruder, and has an advantage in molding processability.
本発明の澱粉・樹脂複合中間粒体を原材料とした澱粉・樹脂複合成形加工材料は、均一、均質な物性等にバラツキの少ない優れたものが得られる。従来法や極端な成分組成を用いた澱粉・樹脂複合成形加工材料は同じ成分系であっても、表１にまとめたとおり中間体が形成できない、比重が安定しない、澱粉が舞ってしまうあるいは押出時、滑性がないため圧力が掛かりすぎシート化できない、シート化した際ブリードが激しくべたつく、又は中間粒体同士がくっつき、粒体が大きくなりすぎ、成形機に供給できないなど成形加工性が阻害されることが確認され、本発明の中間粒体を形成した澱粉・樹脂複合成形加工材料が優れた物性、性状を有することが確認できた。 The starch / resin composite molding processed material using the starch / resin composite intermediate granules of the present invention as a raw material can be obtained as an excellent material having uniform and homogeneous physical properties with little variation. Even if the starch / resin composite molding material using the conventional method or extreme component composition has the same component system, as shown in Table 1, intermediates cannot be formed, the specific gravity is not stable, starch flies or is extruded. At times, because there is no slipperiness, too much pressure is applied to form a sheet, the bleeding becomes extremely sticky when the sheet is formed, or intermediate grains stick to each other, the grains become too large, and the molding processability is hindered. It was confirmed that the starch / resin composite molded material on which the intermediate granules of the present invention were formed had excellent physical properties and properties.
本発明の澱粉・樹脂複合中間粒体を介した澱粉・樹脂複合成形加工材料は、従来の石油系プラスチックに代替し得るバイオマス材料由来の、押出機による成形品の製造、Ｔダイ押出機によるシートの製造、インフレーション成形機によるフィルムの製造、カレンダ成形機によるシートの製造、インジェクション成形機による成形品の製造などの各種成形加工技術及び成形加工機の材料に採用でき、広範な成形加工技術で利用できる澱粉・樹脂複合成形加工材料として有用である。 The starch / resin composite molding processed material via the starch / resin composite intermediate granules of the present invention is derived from a biomass material that can replace conventional petroleum-based plastics, and is produced by an extruder and a sheet by a T-die extruder. It can be used in various molding processing technologies such as manufacturing, film manufacturing by inflation molding machine, sheet manufacturing by calender molding machine, molding product manufacturing by injection molding machine, and material of molding machine, and is used in a wide range of molding processing technology. It is useful as a possible starch / resin composite molding processing material.
Claims (12)
JIS K 7161により測定した引張伸度が３６〜１６０％の範囲のものであり、引張伸度の測定値の変動幅が±７％以内、
JIS K7112により測定した比重が１．０８〜１．２１の範囲のものであり、比重の測定値の変動幅が±０．０１以内であって、
低融点添加剤はグリセリン脂肪酸エステルであり、高融点添加剤はステアリン酸金属塩である、
上記澱粉・樹脂複合成形加工材料。 50-70% by weight starch, 20-40% by weight thermoplastic resin, 0.1-10% by weight low melting point additive with a melting point of 60-100 ° C., and 1-15% by weight melting point 100. It contains a high melting point additive of ° C. to 150 ° C., has a core portion of a granular material of a thermoplastic resin, and contains at least a low melting point additive attached to the surface of the core portion of the granular material by at least the high melting point additive. A starch / resin composite molding processing material obtained by melt-excipient resin using a starch / resin composite intermediate granule as a raw material, which comprises a coating layer of powder or granular material containing starch.
The tensile elongation measured according to JIS K 7161 is in the range of 36 to 160%, and the fluctuation range of the measured tensile elongation is within ± 7%.
The specific gravity measured according to JIS K7112 is in the range of 1.08 to 1.21, and the fluctuation range of the measured value of the specific gravity is within ± 0.01 .
The low melting point additive is a glycerin fatty acid ester and the high melting point additive is a metal stearate salt.
The starch / resin composite molding processing material.
、酸化防止剤、紫外線吸収剤、流動促進剤の群から選択される少なくとも１種の添加剤をさらに含む、請求項１〜５のいずれか１項に記載の澱粉・樹脂複合成形加工材料。 At least one starch / resin composite molding process material selected from the group of compatibilizers, colorants, excipients, disintegrants, modifiers, wetting agents, antioxidants, UV absorbers, and flow promoters. The starch / resin composite molding processing material according to any one of claims 1 to 5 , further comprising the additive of.
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