JP6850125B2 - Starch composite intermediate granules - Google Patents
Starch composite intermediate granules Download PDFInfo
- Publication number
- JP6850125B2 JP6850125B2 JP2016255264A JP2016255264A JP6850125B2 JP 6850125 B2 JP6850125 B2 JP 6850125B2 JP 2016255264 A JP2016255264 A JP 2016255264A JP 2016255264 A JP2016255264 A JP 2016255264A JP 6850125 B2 JP6850125 B2 JP 6850125B2
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- JP
- Japan
- Prior art keywords
- starch
- resin composite
- molding
- melting point
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920002472 Starch Polymers 0.000 title claims description 373
- 239000008107 starch Substances 0.000 title claims description 373
- 235000019698 starch Nutrition 0.000 title claims description 373
- 239000008187 granular material Substances 0.000 title claims description 171
- 239000002131 composite material Substances 0.000 title claims description 54
- 239000000805 composite resin Substances 0.000 claims description 247
- 239000000463 material Substances 0.000 claims description 184
- 238000000465 moulding Methods 0.000 claims description 148
- 239000000654 additive Substances 0.000 claims description 137
- 238000002844 melting Methods 0.000 claims description 131
- 230000008018 melting Effects 0.000 claims description 128
- 230000000996 additive effect Effects 0.000 claims description 117
- 238000012545 processing Methods 0.000 claims description 65
- 239000002994 raw material Substances 0.000 claims description 65
- 229920005992 thermoplastic resin Polymers 0.000 claims description 57
- 239000000203 mixture Substances 0.000 claims description 41
- 239000000047 product Substances 0.000 claims description 36
- 239000012778 molding material Substances 0.000 claims description 35
- -1 glycerin fatty acid ester Chemical class 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 28
- 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
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 14
- 239000011247 coating layer Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
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- 229920001155 polypropylene Polymers 0.000 claims description 12
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 10
- 238000001746 injection moulding Methods 0.000 claims description 10
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 10
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 235000019359 magnesium stearate Nutrition 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
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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
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
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- 239000003607 modifier Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000543 intermediate Substances 0.000 description 151
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- 150000004665 fatty acids Chemical class 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 229920002261 Corn starch Polymers 0.000 description 6
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- 235000013305 food Nutrition 0.000 description 6
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- 229920000881 Modified starch Polymers 0.000 description 5
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- 239000000057 synthetic resin Substances 0.000 description 5
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
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- 235000019426 modified starch Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 239000000853 adhesive Substances 0.000 description 3
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- 238000013329 compounding Methods 0.000 description 3
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- 238000004383 yellowing Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
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- 238000010924 continuous production Methods 0.000 description 2
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- 239000012467 final product Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
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- 239000000344 soap Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- TURGQPDWYFJEDY-UHFFFAOYSA-N 1-hydroperoxypropane Chemical compound CCCOO TURGQPDWYFJEDY-UHFFFAOYSA-N 0.000 description 1
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 244000056139 Brassica cretica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
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- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- 244000046052 Phaseolus vulgaris Species 0.000 description 1
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- 240000005893 Pteridium aquilinum Species 0.000 description 1
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- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
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- 240000008042 Zea mays Species 0.000 description 1
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- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、澱粉・樹脂複合中間粒体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を製造するための澱粉・樹脂複合中間粒体に関する。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成形に適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を製造するための澱粉複合中間粒体に関する。 The present invention relates to a starch / resin composite intermediate granule, 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 intermediate granule for producing a starch / resin composite molding processing material containing starch as a main component, which can be biodecomposed or disintegrated in a short period of time when it is disposed of. In particular, we manufacture starch / resin composite molding materials with less variation that have physical properties and molding processability suitable for plastic molding such as vacuum molding, extrusion molding, injection molding (injection molding), inflation molding, and blow molding (injection molding). Concerning starch composite intermediate granules for
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 as food and drink containers, various packaging materials such as sheets and films, cushioning materials, daily necessities, agricultural products, and other industrial materials. 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, and as a new material that is friendly to the natural environment, natural materials are attracting attention and warming. As a means of solving 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。 Starch is a typical example of a biomass material. 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. (
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 the composite of 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 little 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、均一で均質な、物性が優れ、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、澱粉を５０重量部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安定して効率よく製造することができる原材料又は組成物を提供することを目的とするものであって、澱粉・樹脂複合成形加工材料を確実に形成できる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、しかも各種成形加工法における成形加工性に優れ、安価で、ストックすることができる、澱粉・樹脂複合中間粒体を提供する。 INDUSTRIAL APPLICABILITY The present invention is a composite molding of a starch / resin, which is uniform and homogeneous, has excellent physical properties, is also excellent in molding processability and workability in various molding methods, and has little variation even if it contains 50 parts by weight or more of starch. The purpose is to provide a raw material or composition capable of stably and efficiently producing a processed material, and as a raw material capable of reliably forming a starch / resin composite molding processed material, in terms of workability and quantitativeness. Provided are a starch / resin composite intermediate granules which are excellent, have morphological stability, are excellent in molding processability in various molding processing methods, are inexpensive, and can be stocked.
本発明は、より具体的には、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で被覆した澱粉・樹脂複合中間粒体を提供する。 More specifically, the present invention is a starch-resin composite in which a granular material of a thermoplastic resin is used as a core portion, and the surface of the core portion is coated with a coating layer of a powder or granular material containing starch containing a low melting point additive. Provides intermediate granules.
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・樹脂複合中間粒体は、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・樹脂複合中間粒体であって、澱粉を高濃度で含有しても均一で均質な、さらに形態安定性を有し、しかも澱粉・樹脂複合成形加工材料として各種成形加工法における成形加工性、作業性に優れた物性、性状を得ることができるものである。 As a result of diligent studies to solve the above problems, the present inventors have made the starch-resin composite intermediate granules of the present invention a granular material of a thermoplastic resin as a core portion, and the surface of the core portion is low. A starch-resin composite intermediate granule having a coating layer of a powder or granular material containing starch containing a melting point additive, which is uniform and homogeneous even when a high concentration of starch is contained, and has morphological stability. Moreover, as a starch / resin composite molding processing material, it is possible to obtain physical properties and properties having excellent molding workability and workability in various molding processing methods.
そして、高温撹拌機中での加熱撹拌、混合と、冷却撹拌機中で高融点添加剤の溶融温度よりも低い、低融点添加剤の溶融温度より高い融点温度の近傍の温度まで冷却、撹拌する工程により簡単かつ安価に製造することができる。しかも、該形成された澱粉・樹脂複合中間粒体を直ちに排出し、ストックすることを含む製造方法によって、成形加工材料の原材料として複合粒体の形態でストックすることが可能な澱粉・樹脂複合中間粒体である。 Then, the mixture is heated and stirred in a high temperature stirrer, and cooled and stirred in a cooling stirrer to a temperature near the melting point temperature, which is lower than the melting temperature of the high melting point additive and higher than the melting temperature of the low melting point additive. It can be manufactured easily and inexpensively by the process. Moreover, the starch / resin composite intermediate can be stocked in the form of composite granules as a raw material for a molding processing material by a manufacturing method including immediately discharging and stocking the formed starch / resin composite intermediate particles. It is a granule.
より詳細には、本発明の澱粉・樹脂複合中間粒体は、５０重量部以上の澱粉と、グリセリン系エステル等の低融点添加剤を含む原材料を加熱撹拌することで、澱粉と溶融状態にある低融点添加剤を混合し、澱粉に絡ませ、付着させ、澱粉に含有させる。その後、さらに少なくとも熱可塑性樹脂の粒状体及び脂肪酸金属塩等の高融点添加剤を添加し、加熱混合撹拌して流動性の澱粉・樹脂複合材料とする。 More specifically, the starch-resin composite intermediate granules of the present invention are in a molten state with starch by heating and stirring a raw material containing 50 parts by weight or more of starch and a low melting point additive such as a glycerin-based ester. The low melting point additive is mixed, entwined with starch, adhered and contained in starch. After that, at least a granular material of a thermoplastic resin and a refractory additive such as a fatty acid metal salt are added, and the mixture is heated, mixed and stirred to obtain a fluid starch / resin composite material.
そして、流動性の澱粉・樹脂複合材料を撹拌しつつ、冷却撹拌機中で、低融点添加剤の溶融温度よりも高い所定の温度まで冷却撹拌して降温し、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、粒状体の熱可塑性樹脂をコア部とし、そのコア部の表面に、脂肪酸金属塩等の高融点添加剤の再固化及び澱粉表面に低融点添加剤を濡らすように分散し付着され含有する澱粉が存在することで、熱可塑性樹脂をコア部とし、その表面を少なくとも含有する澱粉を含む粉粒体の被覆層で被覆された構造を有する澱粉・樹脂複合中間粒体の形態の澱粉・樹脂複合中間粒体を形成するものである。 Then, while stirring the fluidized starch / resin composite material, the temperature is lowered by cooling and stirring to a predetermined temperature higher than the melting temperature of the low melting point additive in a cooling stirrer, and at least the high melting point addition in the molten state is added. By resolidifying the agent, a granular thermoplastic resin is used as the core part, and the surface of the core part is resolidified with a high melting point additive such as a fatty acid metal salt, and the surface of the starch is wetted with a low melting point additive. A starch-resin composite intermediate granule having a structure in which a thermoplastic resin is used as a core portion and the surface thereof is covered with a coating layer of a powder or granular material containing at least the starch due to the presence of the starch that is dispersed, adhered and contained. It forms a starch-resin composite intermediate granule in the form of.
本発明の、バラツキの少ない優れた澱粉・樹脂複合成形加工材料を製造することができる中間原材料である澱粉・樹脂複合中間粒体を提供することができ、上記目的を達成するに至った。 It was possible to provide a starch / resin composite intermediate granule, which is an intermediate raw material capable of producing an excellent starch / resin composite molding processed material having little variation of the present invention, and achieved the above object.
そして、本発明の澱粉・樹脂複合中間粒体を用いることにより、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、均一で均質なバラツキの少ない、流動安定性、各種成形加工法で用いることができる成形加工性、取り扱い性、作業性に優れた、澱粉・樹脂複合成形加工材料を安定して安価に得ることができる。 Then, by using the starch / resin composite intermediate granules of the present invention, which could not be obtained in the past, even if starch is contained in a high concentration, it is uniform and uniform with little variation, flow stability, and various molding processes. A starch / resin composite molding material having excellent moldability, handleability, and workability that can be used in the method can be stably obtained at low cost.
本発明の澱粉・樹脂複合中間粒体は、比較的粒体の大きさが均一なものを形成することができ、流動性が良好で、安定供給が可能で定量化が容易になる。また、成形加工用の、澱粉の粉落ちがほとんどない成形材料の原材料の調製が可能になった。 The starch-resin composite intermediate granules of the present invention can form relatively uniform granule sizes, have good fluidity, can be stably supplied, and can be easily quantified. In addition, it has become possible to prepare raw materials for molding materials for molding with almost no starch falling off.
本発明の澱粉・樹脂複合中間粒体は、澱粉・樹脂複合中間粒体を形成することによって、取り扱い性、材料の品質の均一性及び貯蔵安定性に優れた澱粉・樹脂複合中間粒体を提供でき、形状の異なる原料を原料として安定供給することを可能にするものである。 The starch / resin composite intermediate granules of the present invention provide a starch / resin composite intermediate granules having excellent handleability, material quality uniformity, and storage stability by forming the starch / resin composite intermediate granules. It is possible to stably supply raw materials having different shapes as raw materials.
具体的には、澱粉・樹脂複合中間粒体を形成することによりバイオマス、例えば、工業用トウモロコシ（デントコーン）澱粉を５０重量％以上添加されていても粉粒状バイオマスと熱可塑性樹脂の粒状体の澱粉・樹脂複合材料、あるいは、さらに、分散剤、相溶化剤などの添加剤を含む、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であっても、取り扱い性がよく、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、バラツキの少ない澱粉・樹脂複合成形加工材料を形成することができる。さらに、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、カレンダー成形などの成形に適した成形加工性に優れた澱粉・樹脂複合成形材料を提供できる。 Specifically, by forming a starch / resin composite intermediate granule, even if 50% by weight or more of biomass, for example, industrial corn (dent corn) starch is added, the starch is a granular starch of powdery biomass and a thermoplastic resin. -Even if it is a molding material made of a resin composite material or a composite material made of raw materials having different shapes and forms, including additives such as a dispersant and a compatibilizer, it is easy to handle and is a raw material. It enables stable supply to the manufacturing process, homogenizes and homogenizes sheet-like materials, and can form starch / resin composite molding processed materials with little variation. Further, it is possible to provide a starch / resin composite molding material having excellent molding processability suitable for molding such as extrusion molding, T-die extrusion molding, vacuum molding, injection molding, inflation molding and calendar molding.
本発明は、５０重量部以上の澱粉が配合されていても形成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技術を駆使すること、及び材料配合だけではなく、加工条件などを工夫することで、澱粉・樹脂複合中間粒体として成形加工性が向上し、機械的特性を改善させることができ、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ができる。 The present invention makes full use of a compounding technique such as an additive that brings the interface between starch and a thermoplastic tree closer to the molding processability and the bias of mechanical properties of the material to be formed even when starch of 50 parts by weight or more is blended. By devising not only the material composition but also the processing conditions, the molding processability of the starch / resin composite intermediate granules can be improved, the mechanical properties can be improved, the generation of starch odor can be suppressed, and the color fades. Can be suppressed.
本発明の澱粉・樹脂複合中間粒体を用いて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、二酸化炭素削減効果、例えば、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得られることが明らかになった。
For the sheet produced using the starch-resin composite intermediate granules of the present invention, all raw materials including starch are selected from the positive list, and LCA is carried out in the environmental impact assessment to reduce carbon dioxide, for example. It was revealed that a carbon dioxide reduction effect of 32% can be obtained as compared with the life cycle of polypropylene sheet.
本発明の澱粉・樹脂複合中間粒体を用いて成形加工材料を製造することにより、包装資材として利用した際、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、ゴミの減容化に貢献できる。また、環境影響評価において二酸化炭素削減効果が得られる。このように、澱粉・樹脂複合材料として石油系プラスチックの代替材料として一層、好適な環境対応型の材料として用いることができるものであり、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った。 By producing a molding processing material using the starch / resin composite intermediate granules of the present invention, when it is used as a packaging material, it has sufficient product strength when used, but it can be crushed with a light force after use, so that it is dust. Can contribute to volume reduction. In addition, a carbon dioxide reduction effect can be obtained in the environmental impact assessment. As described above, as a starch / resin composite material, it can be used as a more suitable environment-friendly material as a substitute material for petroleum-based plastics, and various food containers and packaging materials, cushioning materials, daily necessities, and agriculture. It has become fully applicable to commercial products.
（澱粉・樹脂複合中間粒体）
上記の本発明の澱粉・樹脂複合中間粒体について、以下にさらに詳しく説明する。
本発明の澱粉・樹脂複合中間粒体は、澱粉が５０重量％以上含有されていても、均一性、均質性に優れたバラツキの少ない澱粉・樹脂複合成形加工材料を得るために欠かせないものであって、澱粉・樹脂複合成形加工材料の製造工程の原材料として位置付けられるものである。本発明の澱粉・樹脂複合中間粒体は、澱粉・樹脂複合成形加工材料を製造する工程中で簡単、確実に製造でき、あるいは、別途、製造され、原材料として供給し、製造工程で用いることができる形態安定性に優れた複合中間粒体である。
そして、澱粉・樹脂複合中間粒体を澱粉・樹脂複合成形加工材料の製造工程に原材料として用いることで、該成形加工材料を安定的に製造することを可能にすることができるものである。
(Starch / resin composite intermediate granules)
The starch / resin composite intermediate particles of the present invention described above will be described in more detail below.
The starch / resin composite intermediate granules of the present invention are indispensable for obtaining a starch / resin composite molding processing material having excellent uniformity and homogeneity and less variation even if the starch is contained in an amount of 50% by weight or more. Therefore, it is positioned as a raw material in the manufacturing process of a starch / resin composite molding processing material. The starch / resin composite intermediate granules of the present invention can be easily and surely manufactured in the process of manufacturing the starch / resin composite molding processing material, or can be separately manufactured, supplied as a raw material, and used in the manufacturing process. It is a composite intermediate granule with excellent morphological stability.
Then, by using the starch / resin composite intermediate granules as a raw material in the manufacturing process of the starch / resin composite molding processing material, it is possible to stably manufacture the molding processing material.
本発明に係る澱粉・樹脂複合中間粒体は、より詳細には、澱粉と、低融点添加剤とを加熱撹拌して低融点添加剤を溶融し、澱粉と混合させ、溶融した低融点添加剤を澱粉に絡ませ、付着させ、低融点添加剤を含有する澱粉を形成する。その後、熱可塑性樹脂の粒状体と高融点添加剤を含む複合原材料をさらに添加して加熱撹拌し、高融点添加剤を溶融させ混合し、澱粉、熱可塑性樹脂の粒状体並びに溶融状態の低融点及び高融点添加剤を含む組成物を均一分散させ、流動性の澱粉・樹脂複合材料とする。その後、流動性の澱粉・樹脂複合材料を冷却撹拌し、溶融状態の主として高融点添加剤を再固化することにより、熱可塑性樹脂をコア部とし、その表面に低融点添加剤を含む澱粉を含む粉粒体の被覆層を有する澱粉・樹脂複合中間粒体として製造されたものである。 More specifically, the starch / resin composite intermediate granules according to the present invention are prepared by heating and stirring starch and a low melting point additive to melt the low melting point additive, mixing it with starch, and melting the low melting point additive. Is entwined with starch and adhered to form starch containing a low melting point additive. Then, the composite raw material containing the thermoplastic resin granules and the high melting point additive is further added and heated and stirred to melt and mix the high melting point additive to melt and mix the starch, the thermoplastic resin granules and the low melting point in the molten state. And the composition containing the high melting point additive is uniformly dispersed to prepare a fluid starch / resin composite material. After that, the fluid starch / resin composite material is cooled and stirred, and the molten mainly high melting point additive is resolidified to form a thermoplastic resin as a core portion, and the surface thereof contains starch containing a low melting point additive. It is produced as a starch-resin composite intermediate particle having a coating layer of a powder or granular material.
（澱粉）
本発明の澱粉・樹脂複合中間粒体は、特殊な手段、設備を使用することなく、成分原料を加熱撹拌し、その後、冷却撹拌することにより安定した品質の成分組成の複合中間粒体として得られるものである。本発明において澱粉・樹脂複合中間粒体を形成するため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が用いることができ、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)
The starch-resin composite intermediate granules of the present invention can be obtained as a composite intermediate granule having a stable quality component composition by heating and stirring the component raw materials and then cooling and stirring without using special means and equipment. Is something that can be done. As the raw material starch used as a biomass material for forming a starch-resin composite intermediate granule in the present invention, inexpensively available raw starch can be used, for example, corn starch, bean starch, tapioca starch, potato starch, and the like. Examples thereof include wheat starch, 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。
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 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, xanthogen acetic acid 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.
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。
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。
(Polymer material)
In the present invention, the components of the starch / resin composite molding processing 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.
As the thermoplastic resin used in the present invention, polyolefin resins such as polyethylene and polypropylene, polystyrene, polyamide, polyester, ethylene / vinyl acetate copolymer, alkylene / acrylate or methacrylate copolymer and other thermoplastics are used. 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、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、深物の成形が困難となり、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 and 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 is large as the obtained starch / resin composite molding material, and it becomes difficult to homogenize the biomass molding material, so that a homogeneous composite molding material can be obtained. It becomes difficult. Moreover, it is necessary to increase the amount of the additive. As a result, the mechanical properties are significantly deteriorated, uneven thickness, tearing and the like occur during molding, it becomes difficult to mold thin and deep objects, texture cannot be obtained, and molding processing becomes difficult.
一方、熱可塑性樹脂が５０重量％以上だと、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、プラスチック成形加工材料としての物性、性質が強く出て、成形は可能であるが、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、充填剤が多く、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なくなる。
本発明の澱粉・樹脂複合中間粒体が形成されなくなると、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ても、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なくなる。
On the other hand, when the thermoplastic resin content is 50% by weight or more, the starch is positioned as a modifier for the thermoplastic resin, for example, as a filler, and the obtained starch / resin composite molding material has physical properties as a plastic molding material. Although the properties are strong and molding is possible, it is difficult to reduce the volume, the contribution to the reduction of greenhouse gas emissions is reduced, and it becomes difficult to obtain a starch / resin composite molding processed material as a biomass raw material. .. Moreover, since there are many fillers, the physical properties of the molded material and the uniformity and homogeneity of the composite material fluctuate greatly, and a stable material cannot be obtained.
When the starch-resin composite intermediate granules of the present invention are no longer formed, even if a molded material is produced from a material having the same composition of each component of the raw material, the physical properties of the molded material and the uniformity and homogeneity of the composite material are maintained. Fluctuations are large and stable materials cannot be obtained.
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樹脂を挙げることができる。 Examples of the biodegradable material 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 resins 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 granular material to be a core portion 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より小さい場合は、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、均質性が劣り、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した。 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 exceeds or is smaller than the size of this major axis, the balance of the amount of adhered granules becomes unbalanced, and all of them are uniform and homogeneous as starch / resin composite intermediate granules of starch and thermoplastic resin. Is inferior, and further, 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. , The average particle size in the above range was used.
（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、添加剤が澱粉や熱可塑性樹脂に絡まり、付着し、澱粉と熱可塑性樹脂を付着し易く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。
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、機械的強度などが優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。
(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 or the thermoplastic resin and adheres to the starch. And to make it easier for the thermoplastic resin to adhere, and to allow the starch and thermoplastic resin granules to retain the properties of the fluid starch-resin composite material, further cooling and stirring, at least high. When the melting point additive is resolidified, it is necessary to add an additive that can act as an adhesive that enables stable formation of the starch / resin composite intermediate granules.
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 process material having excellent molding processability, mechanical strength, etc. and having little variation 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融点温度を有し、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る、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 point 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 is simultaneously present in the starch / resin composite intermediate granules and that can fulfill at least the above-mentioned properties and functions, is melted at a relatively low temperature, is entangled with starch, and is attached and added. 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-based fatty acid ester is 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。そして、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. Then, 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 the coating layer of the powder or granular material containing the starch contained in the starch to form the 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、添加剤との親和性を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。
The high melting point 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 the intermediate granules. 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 the affinity with the additive, but starch / resin composite molding processing is uniform and uniform in the processing machine using starch / resin composite intermediate particles as raw materials. In order to use it as a material, the composite raw material is dispersed, and when melt-kneaded as a starch / resin composite material, it is uniformly dispersed, and moreover, the friction with the processing machine is reduced, the fluidity in the processing machine is increased, and the external slipperiness is enhanced. Additives capable of imparting sex are preferably used.
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。 In the present invention, an additive that is simultaneously present in the starch / resin composite intermediate granules and is melted at a relatively high temperature, which can fulfill at least the above-mentioned properties and functions, is defined as a "high melting point additive". ..
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、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, improving the dispersibility during melt-kneading, and imparting slipperiness includes fatty acid metal salts, hydrocarbon-based additives, and higher grade additives. Alcohol-based, aliphatic amide-based, fatty acid esters and the like 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種類が使用できる。
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.
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、加工機中で複合中間粒体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、溶融押出を可能にするとともに、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 above-mentioned low melting point and high melting point additives, 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 starch / resin composite intermediate granules of the present invention are automatically formed. Then, by using the formed starch / resin composite intermediate granules as a raw material and melting or melt-kneading the composite intermediate granules in a processing machine, a uniform and homogeneous composite material can be obtained, and melt extrusion is possible. By adding the 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）
本発明の澱粉・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ができる。
(Other additives)
By using the starch / resin composite intermediate granules of the present invention, it is possible to obtain a uniform and uniform starch / resin composite molding processing material with little variation, and it has molding workability in various molding processing methods and has workability. In order to obtain excellent materials, 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 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・樹脂複合中間粒体を経て生産品である澱粉・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、顔料などの着色剤も使用できる。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。 Examples of the additive used for producing the starch / resin composite molding processing material, which is a product produced through the starch / resin composite intermediate granules of the present invention, include titanium oxide, carbon black, dye, pigment, etc., as required. Colorants can also be used. In addition, if necessary, additives such as elastomer, antioxidant, cross-linking agent, ultraviolet absorber, and foaming agent can be appropriately added.
本発明の澱粉・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。本発明の粒体の大きさは、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。 The shape and size of the starch-resin composite intermediate particles of the present invention 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 of the present invention 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・樹脂複合中間粒体は、上述したとおり高温撹拌機で形成された流動性の澱粉・樹脂複合材料を冷却撹拌機中で再固化させることによ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表面を被覆された被覆層を有する形態のものを得ることができる。 In the starch / resin composite intermediate granules of the present invention, as described above, the fluid starch / resin composite material formed by the high temperature stirrer is resolidified in the cooling stirrer to form the core part of the thermoplastic resin of the granules. A form having a coating layer whose surface is coated with a powder or granular material containing starch as a main component can be obtained.
本発明の澱粉・樹脂複合中間粒体は、澱粉・樹脂複合成形加工材料を製造するため溶融混練するまでは澱粉・樹脂複合中間粒体の形崩れを起こさない程度の、及び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に形成することができる。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、均一性、均質性、成形加工性、作業性及び定量性の改善に繋がる。 Since the starch / resin composite intermediate granules of the present invention are used to produce a starch / resin composite molding process material, the starch / resin composite intermediate granules do not lose their shape until they are melt-kneaded, and the starch does not peel off. It has morphological stability attached by the adhesive force of the above, and can be formed in 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 the uniformity, homogeneity, molding workability, workability and quantitativeness are improved. Connect.
（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、本発明の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、又は本発明の澱粉・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、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を用いることにより行なわれる。
(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 of the present invention is used as a raw material, or the starch of the present invention is produced. -Assembled as a method of continuously and consistently manufacturing starch / resin composite molding processed materials, which are products, using resin composite intermediate particles as raw materials, and starch / resin composite molding processed materials shown in FIG. 1 are continuously consistently manufactured. This is done by using a manufacturing device.
澱粉・樹脂複合成形加工材料連続一貫製造装置は、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、前記製造された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、及び又はカレンダー成形等の二次加工し、最終製品の原材料を製造する澱粉・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 starch / resin composite molding processing material continuous integrated manufacturing apparatus includes the starch / resin composite intermediate particle manufacturing apparatus unit A capable of producing and storing the starch / resin composite intermediate granules capable of producing the molding processing material, and the above-mentioned Using the manufactured composite intermediate granules as a raw material, a starch / resin composite molding process that is a product is manufactured, and / or secondary processing such as calendar molding is performed to manufacture a raw material for the final product. It is composed of an apparatus including a material manufacturing apparatus section B.
本発明の澱粉・樹脂複合中間粒体の製造は、澱粉・樹脂複合成形加工材料連続一貫製造装置の澱粉・樹脂複合中間粒体製造装置部Ａに示す各装置からなる製造装置を独立した装置として、又は例示したように連続一貫装置の一部に組み込んだ装置により製造するものであって、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を含む製造装置を用いて製造される。
In the production of the starch / resin composite intermediate granules of the present invention, the production apparatus consisting of each apparatus shown in the starch / resin composite intermediate granule production apparatus A of the continuous integrated production apparatus for the starch / resin composite molding processing material is used as an independent apparatus. , Or, as illustrated, a
そして、澱粉・樹脂複合成形加工材料は、該澱粉・樹脂複合中間粒体を製造する装置部Ａにおいて製造され、貯蔵された澱粉・樹脂複合中間粒体を原材料として供給する該ストックタンク兼供給装置３と、原材料を加熱混練し、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部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押し出す一軸押出機５とを少なくとも含む構成とした澱粉・樹脂複合成形加工材料製造装置部Ｂにより製造することができ、該澱粉・樹脂複合成形加工材料製造装置部を澱粉・樹脂複合中間粒体を製造する装置部Ａに続けて配置し連続一貫製造装置を構成するか又は、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。
Then, the starch / resin composite molding processing material is produced in the apparatus unit A that manufactures the starch / resin composite intermediate granules, and the stock tank / supply device that supplies the stored starch / resin composite intermediate granules as a raw material. 3. The twin-screw extruder 4 in which the raw materials are heat-kneaded and extruded into a fluid starch / resin composite material, and the thermoplastic resin portion in the kneaded and melted state is further raised in cylinder temperature to further raise the cylinder temperature to melt thermoplastic resin starch. It can be manufactured by the starch / resin composite molding processing material manufacturing equipment unit B having a configuration including at least a
本発明で用いる澱粉・樹脂複合成形加工材料連続一貫製造装置は、さらに、シート状に押し出しし、該シートをカレンダー成形により、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６や、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 starch / resin composite molding material continuous integrated manufacturing apparatus used in the present invention is further extruded into a sheet, and the sheet can be roller-rolled by calendar forming to control the thickness of the sheet and the formation of the surface layer. The
（澱粉・樹脂複合中間粒体の製造）
本発明の澱粉・樹脂複合中間粒体は、図１に示す高温撹拌機と冷却撹拌機を含む装置部Ａにより製造することができる。
(Manufacture of starch / resin composite intermediate particles)
The starch / resin composite intermediate granules of the present invention can be produced by the apparatus unit A including the high temperature stirrer and the cooling stirrer shown in FIG.
本発明の澱粉・樹脂複合中間粒体は、はじめに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になるように加熱撹拌を制御する。 In the starch-resin composite intermediate granules of the present invention, first, 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 temperature at which the low melting point additive melts. Mix while heating and stirring with, 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、さらに加熱撹拌し混合し、流動性の澱粉・樹脂複合材料を形成する。
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、溶融した添加剤を再固化する。
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主として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製造する。
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 physical properties and properties required for the molding material, and the mixture is further heated, stirred and mixed to flow. Form a sex starch / resin composite material.
Next, the formed fluid starch / resin composite material is transferred to a cooling stirrer, and the melted additive is resolidified while cooling and stirring in the cooling stirrer.
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 mainly containing a low melting point additive is formed on the surface of the core portion. Manufacture resin composite intermediate particles.
（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
本発明の加熱撹拌処理では、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、澱粉と溶融した低融点添加剤を加熱混合するものであって、以下のように行う。
(Heating and stirring with a high temperature stirrer)
(1) Heat-stirring treatment of starch and low-melting-melting additive In the heating-stirring treatment of the present invention, starch and low-melting-melting additive are heated and mixed by heating and stirring starch and low-melting-melting additive in a high-temperature stirrer. It is to be done as follows.
先ず、高温撹拌機１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、加熱撹拌し、昇温させる。
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、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。
First, starch and a low melting point additive such as a glycerin-based fatty acid ester are mixed and charged into the high-
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 by 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 the low melting point is obtained. The temperature, rotation speed, stirring time, etc. are controlled and treated in consideration of production efficiency so that a fluid starch mixture of the starch containing the additive is formed.
本発明の加熱撹拌処理では、高温撹拌機を、例えば、加熱温度１１０〜１６０℃、回転数５〜５０Ｈｚに設定し、回転数、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。 In the heating and stirring treatment of the present invention, 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 rotation speed and the stirring time are controlled to melt the components of the low melting point additive. And stir and mix the starch and low melting point additive in a high temperature stirrer. 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.
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 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。
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。
(2) Formation of starch / resin composite material After making a mixture of starch and melted low melting point additive with a high temperature stirrer, granules of thermoplastic resin and high melting point additive such as at least one fatty acid metal salt are added. Add more and heat and stir.
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. 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, in a state where the low melting point and high melting point additives are melted, 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、その溶融温度近傍まで冷却撹拌機中で撹拌しながら冷却され、溶融した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 temperature. It is cooled with stirring, and the mixture is cooled and stirred so that the molten additive component 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、主として脂肪酸金属塩などの高融点添加剤の成分が溶融温度以下になることにより再固化され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に示すような澱粉・樹脂複合中間粒体を形成する。この澱粉・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 the components of the refractory additive such as fatty acid metal salt are mainly kept below the melting temperature. It is cooled and stirred so that it is solidified by becoming solidified. At that time, the high melting point additive in the mixture of the fluid starch / resin composite material is cooled and stirred to solidify into 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. By adhering the agent-containing starch to the thermoplastic resin granules via at least a high melting point additive that resolidifies, the thermoplastic resin granules become 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 a starch containing an additive is formed, and a starch / resin composite intermediate particle body as shown in FIG. 2a is formed. The starch / resin composite intermediate granule has the structure shown in FIG. 3 when its cross section is schematically shown.
本発明の澱粉・樹脂複合中間粒体は、性質や形状が異なる混合し難い成分材料の原料を加熱混合した後、流動性の複合材料を撹拌しながら冷却し、流動性複合材料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、固化し、澱粉・樹脂複合中間粒体が形成でき、冷却撹拌という単純な操作により簡単に、造粒化できるものである。 In the starch / resin composite intermediate granules of the present invention, raw materials of difficult-to-mix component materials having different properties and shapes are heated and mixed, and then the fluid composite material is cooled while stirring, so that the temperature of the fluid composite material is lowered. As a result, when the melted additive component becomes lower than the melting temperature, it can be solidified to form a starch / resin composite intermediate granule, and can be easily granulated by a simple operation of cooling and stirring.
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製造工程に投入することができ、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。 Conventionally, in the production of molding materials, component raw materials having different properties and shapes have been supplied individually or in batches to the manufacturing process, respectively, as a raw material in a composite form called a composite intermediate granule with good handleability in the manufacturing process. It is possible to stably supply and quantify raw materials in the production of starch / resin composite molding processed materials.
この澱粉・樹脂中間粒体は、冷却撹拌操作による造粒工程において、温度、回転数及び撹拌時間などを制御し、溶融状態の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、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できる。複合中間粒体の形成する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。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。 The starch / resin intermediate granules are made of thermoplastic resin granules by controlling the temperature, rotation speed, stirring time, etc. in the granulation process by cooling and stirring operation, and resolidifying the components of the additive in the molten state. By observing and confirming the state in which a coating layer of powder or granular material containing starch is formed on the surface, granulation is performed by cooling and stirring at an optimum temperature, and the shape and shape of the formed granular material are maintained. Can be taken out. If the amount of the low melting point additive and the 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 is lowered. 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). 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 can be fluidly deformed, so that the shape and shape of the particles are deformed by the impact at the time of dropping. It loses its shape and the granules become lumpy, which reduces the flow stability.
本発明は、その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しながら、低融点添加剤の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。こうして得られた澱粉・樹脂複合中間粒体は、粉落ちのほとんどない、形態安定性の優れた複合中間粒体であり、この澱粉・樹脂複合中間粒体を原材料とすることにより高品質な澱粉・樹脂複合成形加工材料を形成することができる。 In the present invention, while observing the appearance of the granulated granules and confirming that the appearance is in good condition, the components of the low melting point additive are discharged from the cooling stirrer in a temperature range where solidification does not proceed and stocked. It is dropped into a tank, taken out as an intermediate raw material in the form of a starch / resin composite intermediate particle, and stocked. The starch / resin composite intermediate granules thus obtained are composite intermediate granules having excellent morphological stability with almost no powder falling off, and by using this starch / resin composite intermediate granules as a raw material, high-quality starch is produced. -A resin composite molding processing material can be formed.
加熱、冷却撹拌工程により製造される澱粉・樹脂複合中間粒体は、バッチ式で製造されるものであり、一方、澱粉・樹脂複合成形加工材料の製造では、該中間粒体を連続的に混練し押し出す原材料であるので、この澱粉・樹脂複合中間粒体をストックタンクに貯蔵することは、該中間粒体を澱粉・樹脂複合成形加工材料の製造に組み入れるバッファ量となり、バラツキの少ない澱粉・樹脂複合成形加工材料を連続的に一貫して製造できるように利用できるものである。 The starch / resin composite intermediate granules produced by the heating and cooling stirring steps are produced in a batch manner, while in the production of the starch / resin composite molding processed material, the intermediate granules are continuously kneaded. Since it is a raw material to be extruded, storing the starch / resin composite intermediate granules in a stock tank provides a buffer amount for incorporating the intermediate granules into the production of the starch / resin composite molding processing material, and the starch / resin with little variation. It can be used so that the composite molded material can be continuously and consistently produced.
本発明により、上記のように簡単かつ少ない操作により粉落ちのない、形態安定性のよい澱粉・樹脂複合中間粒体を製造することができ、品質にバラツキの少ない澱粉・樹脂複合成形加工材料を得るための中間原料として用いることができ、均一で均質な澱粉・樹脂複合成形加工材料を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の安定的な利用、提供ができる。 INDUSTRIAL APPLICABILITY According to the present invention, a starch / resin composite intermediate granule having good morphological stability without powder falling can be produced by a simple and few operations as described above, and a starch / resin composite molding processing material having little variation in quality can be produced. It can be used as an intermediate raw material for obtaining, and it becomes possible to stably and inexpensively prepare a uniform and homogeneous starch / resin composite molding processed material, and it is possible to stably use and 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・樹脂複合中間粒体を製造する方法により製造された澱粉・樹脂複合中間粒体は、各成分材料が併存した集合体の澱粉・樹脂複合材料であることから、各種成形加工法の澱粉・樹脂複合成形加工材料を澱粉・樹脂複合中間粒体を原材料として製造するには、澱粉・樹脂複合中間粒体を製造する方法を、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、性質や形状の異なる原材料の安定供給を可能にし、バラツキの少ない澱粉・樹脂複合成形加工材料の連続的な製造を可能するための原材料として澱粉・樹脂複合中間粒体を供給でき、利用できる。
澱粉・樹脂複合中間粒体から製造された澱粉・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。
(Manufacturing of starch / resin composite molding processing material)
Since the starch / resin composite intermediate granules produced by the method for producing the starch / resin composite intermediate particles of the present invention are aggregate starch / resin composite materials in which each component material coexists, various molding processing methods are used. In order to produce the starch / resin composite molding processing material of the above using the starch / resin composite intermediate granules as a raw material, a method of producing the starch / resin composite intermediate granules is performed during the production process of the starch / resin composite molding processing material. As a production line that enables stocking as an intermediate raw material for starch / resin composite molding processing materials by incorporating it, or as a production line for composite intermediate grains separately from the production process for starch / resin composite molding processing materials. By providing it, it is possible to stably supply raw materials with different properties and shapes, and it is possible to supply starch / resin composite intermediate particles as raw materials for continuous production of starch / resin composite molding processing materials with little variation. Available.
The starch / resin composite molding material produced from the starch / resin composite intermediate granules is further molded into a sheet or film, blow molded, or vacuum formed and used as a molding material for the final product. You can also do it.
具体的には、本発明のストックされた澱粉・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、供給し、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、混合することが可能になる。 Specifically, in order to produce a starch / resin composite molding processing material that can be used in various molding processing methods from the stocked starch / resin composite intermediate particles of the present invention, it is similar to a normal plastic molding processing technique. In addition, for example, the starch / resin composite intermediate granules are directly put into the twin-screw extruder without the need to mix starch and additives with a mixer such as a Hensiel mixer, a tumbler type mixer, a barbary mixer, or a kneader mixer. The starch and the thermoplastic resin can be uniformly kneaded and mixed by supplying the mixture, controlling the rotation speed, stirring time, temperature, and the like in the same manner as in normal plastic molding, and heating and kneading.
本発明の澱粉・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、添加剤の溶融温度以上の温度に設定し、加熱混練し、流動性の澱粉・樹脂複合成形加工材料の溶融樹脂澱粉複合混合物を形成する前段階として、剪断と温度上昇を抑えつつ、十分に撹拌混練する。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を製造できる。 In the process of heating and kneading the starch-resin composite intermediate granules of the present invention in a twin-screw extruder, the heat processing temperature (cylinder temperature) is 100 ° C to 190 ° C, the temperature below the temperature at which the thermoplastic resin melts, and the additive. As a preliminary step to form a molten resin starch composite mixture of a fluid starch / resin composite molding process material, the temperature is set to a temperature equal to or higher than the melting temperature of the above, and the mixture is sufficiently stirred and kneaded while suppressing shearing and temperature rise. .. 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 produced.
そして、本発明の澱粉・樹脂複合中間粒体は、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℃、押出圧力を適宜設定し、熱可塑性樹脂を安定状態で溶融押出することにより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製造するために利用できる。 Then, the starch / resin composite intermediate granules of the present invention are subjected to sufficient heating and kneading, and then the fluid starch / resin composite material is extruded by a uniaxial extruder to exceed the melting temperature of the thermoplastic resin in the same manner as in the melt extrusion step of plastics. , 150 to 220 ° C., the extrusion pressure is appropriately set, and the thermoplastic resin is melt-extruded in a stable state, so that it can be used for producing a uniform and uniform starch / resin composite molded material with little variation.
本発明では、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、カレンダー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を採用し、各種成形加工法に適した澱粉・樹脂複合成形加工材料を製造するのに利用できる。 In the present invention, upon extrusion, manufacturing of a molded product by an extruder, production of a sheet by a T-die extruder, production of a film by an inflation molding machine, production of a sheet by a calendar molding machine, production of a molded product by an injection molding machine, etc. It can be used to manufacture starch / resin composite molding processing materials suitable for various molding processing methods by adopting molding processing technology and molding processing machines.
例えば、本発明の澱粉・樹脂複合中間粒体は、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のに利用できる。 For example, the starch / resin composite intermediate granule of the present invention is obtained by setting the temperature to 150 to 220 ° C. using a T-die and extruding the starch / resin composite molded material as a sheet to obtain a sheet-shaped molded material. Can be used for.
得られたシート状物は、押し出された後、直ちに、圧延ローラによりシート化しつつ冷却して澱粉・樹脂複合成形加工材料シートとし、冷却された厚み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を製造するために用いることができる。 Immediately after being extruded, the obtained sheet-like material is cooled while being sheeted by a rolling roller to form a starch / resin composite molded material sheet, and the cooled starch / resin composite having a thickness of 0.1 to 2.0 mm is obtained. To obtain a molded sheet and use it as a raw material sheet for various molding methods, or to crush or cut the sheet to obtain granules to produce a molded material for raw material pellets suitable for injection molding, inflation molding, and blow molding. Can be used for.
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、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、引取り、巻き取ることにより原反ロールとするか、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、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こともできる。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こともできる。 For a starch / resin composite molded material sheet that has been extruded into a sheet by an extruder, the temperature of the take-up roll is set to 60 ° C. or lower, and the sheet formed to a predetermined thickness is cooled, taken up, and wound up. The raw fabric sheet of the starch / resin composite molding processing material is made into a raw fabric roll by, or the raw fabric sheet of the starch / resin composite molding processing material is passed between three rolling rolls in which the surface is cooled by giving the roll a cooling function, and the thickness is increased by the rolling roll. It can also be a controlled, molded material sheet with a surface skin layer formed. Alternatively, it can be a molded material sheet without a surface skin layer.
澱粉・樹脂複合成形材料シートの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、所望の成形加工シート又は粉砕又はカット可能な成形加工材料シートを得ることができる。また、圧延ロールによってシート状に成形するので、澱粉樹脂シートの厚さが均一になり、均質なペレットを得る。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ずることができるものを製造するのに利用できる。
By controlling the thickness of the starch / resin composite molding material sheet, the presence / absence and thickness of the surface skin layer, and further controlling the temperature of the sheet surface temperature, a desired molding processing sheet or a molding processing material sheet that can be pulverized or cut can be obtained. be able to. Further, since the starch resin sheet is formed into a sheet by a rolling roll, the thickness of the starch resin sheet becomes uniform, and uniform pellets can be obtained. In addition, by forming a smooth skin layer on the front and back surfaces of the sheet by the action of a rolling roll, it can be used to produce a product capable of reducing water absorption after pelletization.
以下、本発明の澱粉・樹脂複合中間粒体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。 Hereinafter, the starch / resin composite intermediate particles 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.
（実施形態）
本発明の澱粉・樹脂複合中間粒体及び澱粉・樹脂複合成形加工材料を製造するための実施例及び比較例における使用原料及び試料作成方法は、以下のとおりである。
（澱粉・樹脂複合中間粒体の製造）
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形成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 in Examples and Comparative Examples for producing the starch / resin composite intermediate granules and the starch / resin composite molding processed material of the present invention are as follows.
(Manufacture of starch / resin composite intermediate particles)
The raw materials blended to form 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 obtain starch containing glycerin monostearate.
（２）加熱撹拌２
高温撹拌機中で十分に混合し、乾燥した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２０．０〜４０．０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
In order to use the dried corn starch as a starch / resin composite material after mixing thoroughly in a high-temperature stirrer, 20.0 to 40.0% by weight of polypropylene and zinc stearate, which is a metal stearate salt as a refractory additive, are used. 5 to 5.0% by weight, 0.5 to 10% by weight of magnesium stearate, 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 stearic acid metal soap is melted and mixed and stirred until a mixture of a 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・樹脂複合中間粒体の形成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, and then the mixture is discharged from a high temperature stirrer, transferred to a cooling stirrer, and transferred to 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 temperature above the melting point of the low melting point additive glycerin monostearate until the formation of the starch-resin composite intermediate granules coated with the glycerin monostearate attached to the powder or granular material containing the starch is confirmed. Cool and stir with.
（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 the stock tank After it is confirmed that the starch / resin composite intermediate particles are formed by cooling and stirring, a low melting point is added to prevent the starch / resin composite intermediate particles from being destroyed and the powder from peeling off. While maintaining a temperature equal to or higher than the melting temperature of the glycerin monostearate of the agent, the starch / resin composite intermediate particles are immediately discharged into 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 coating layer of the powder or granular material containing the core portion of the thermoplastic resin and starch containing at least the low melting point additive glycerin monostearate is the high melting point additive zinc stearate and magnesium. It is formed as a stable starch-resin composite intermediate granule that is attached by resolidification and is in a tightly bound state without dropping or peeling of the powder or 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、複合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を製造し、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 granules of the present invention was carried out as follows. As the intermediate raw material, the presence or absence of powder falling off at the time of discharging the composite intermediate granules 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, a manufactured starch / resin composite molding material is manufactured, and the specific gravity and tensile elongation of the manufactured starch / resin composite molding material and the degree of variation thereof are determined. Intermediate granules were evaluated.
（澱粉・樹脂複合成形加工材料の製造）
澱粉・樹脂複合中間粒体を評価するため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。
(Manufacturing of starch / resin composite molding processing material)
A twin-screw kneaded plasticized uniaxial extruder was used to evaluate the starch-resin composite intermediate granules, and a starch-resin composite molding material was produced as follows.
（澱粉・樹脂複合中間粒体の混練）
澱粉複合中間粒子をストックタンクから二軸混練可塑化押出機に投入し、シリンダ温度１２０〜１９０℃、樹脂圧１〜４ＭＰａに設定し、混練する。
(Kneading of starch / resin composite intermediate particles)
The starch composite intermediate particles are put into a twin-screw kneading plasticizer from a stock tank, and the cylinder temperature is set to 120 to 190 ° C. and the resin pressure is set to 1 to 4 MPa for kneading.
（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・樹脂複合溶融ポリプロピレンを押し出した。
(Molding of starch / resin composite molding processing material)
In order to produce a starch / resin composite molding material, the polypropylene / resin composite molding material prepared by kneading and plasticizing in the twin-screw extruder of the first stage is set to the set temperature of the heating zone and the polypropylene melting temperature. It was supplied to the second-stage uniaxial extruder set at 160 to 210 ° C. and a resin pressure of 3 to 20 MPa to extrude a starch / resin composite molten polypropylene.
（澱粉・樹脂複合成形加工材料の作成）
本発明の中間粒体から形成した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。
その評価方法は、以下の要領で行った。
(Creation of starch / resin composite molding processing material)
The following post-treatment was carried out in order to evaluate the influence on the moldability and workability of the molding material formed from the intermediate particles of the present invention.
The evaluation method was as follows.
（試験シート作成）
澱粉・溶融ポリプロピレン複合成形加工材料をシート状物として製造するため、Ｔ−ダイ押出機を使用して、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０．７ｍｍ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でカレンダー圧延処理して、シートの厚みを制御し、あるいは、シート表面にスキン層を形成し、つやのあるシートを製造することもできる。
さらに、押出成形により製造された澱粉・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タイズ化するため、さいの目状に裁断した。
(Creating a test sheet)
In order to manufacture the starch / molten polypropylene composite molding process material as a sheet, extrude it into a sheet using a T-die extruder, set the temperature of the take-up roll to 40 to 60 ° C, and set the temperature to a predetermined thickness. The sheet formed to 0.7 mm was cooled, taken up, and wound on a paper tube.
Further, if necessary, a calendar rolling process may be performed with three cooling rolls to control the thickness of the sheet, or a skin layer may be formed on the surface of the sheet to produce a glossy sheet.
Further, in order to utilize the starch / resin composite molding processed material produced by extrusion molding as a raw material for various molding processing methods, a molded sheet having a thickness control or a surface layer was cut into diced shapes in order to pelletize.
成形した澱粉・樹脂複合成形加工材料原反シートの長さ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）材料の比重関して、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。
A sheet piece (2 x 20 cm) was sampled and extracted from 10 locations per 100 m of the length of the molded starch / resin composite molding processing material raw fabric sheet.
(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 material sheet 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 material 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.
（容器の試験成形）
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。
(Test molding of container)
A sheet molded to confirm the moldability of the above sheet manufactured from a starch / resin composite molding processing material is used as a vacuum pressure air machine; FVS-500P type manufactured by Wakisaka Engineering Co., Ltd., and molding conditions: setting. After heating to a temperature of 450 ° C., the product was formed into a conical cup by a vacuum pressure air blower.
（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。
(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. The starch / resin composite intermediate granules and the starch / resin composite molding processing material of Examples 1 to 5 were produced.
製造した澱粉・樹脂複合成形加工材料を、上記の試料作成に従って評価用試料として澱粉・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、調製した試験試料を用いて、上記した評価項目に従い材料の物性及び成形することを通じて澱粉・樹脂複合中間粒体及び澱粉・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は、引張伸度、比重のバラツキを評価した。 The produced starch / resin composite molding processed material is used as an evaluation sample according to the above sample preparation, and the starch / resin composite intermediate granules and the starch / resin composite molding processed material are produced, and the above-mentioned evaluation is performed using the prepared test sample. The physical properties of the material and the molding processability of the starch / resin composite intermediate granules and the starch / resin composite molding process material through molding according to the items, and the uniformity and homogeneity of the material important as the composite molding material, are stretched. The variation in specific gravity was evaluated.
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と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試験結果は、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, and a deep-throttled container could be formed. 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 test results for the produced composite intermediate particles and composite molding processed materials.
表１に示すとおり、実施例１ないし実施例３では、形態安定性のある、安定した組成の中間粒体が製造でき、それ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、及び容器の成形もでき、深絞りも可能な材料を製造することができた。
As shown in Table 1, in Examples 1 to 3, intermediate granules having a stable composition with morphological stability can be produced, and the starch / resin composite molding processed material produced by melt-extruding the intermediate particles as a raw material is , A composite molding material having an average tensile elongation measured by the above test method in the range of 36 to 160% and an average specific gravity in the range of 1.08 to 1.21 in one rod of the material of each example. The variation of the measured value of the tensile elongation for each has a fluctuation range of 34 to 39%, 73 to 77%, and 148 to 164%, respectively, in Examples 1 to 3, respectively, and even if the fluctuation range is large, ± Within 7%, the measured value of specific gravity is ± 0, which is stable and has excellent physical properties with little variation.
Regarding the molding processability by each molding processing method using the manufactured material, it was possible to produce a material that can be made into a sheet, can be molded into a container, and can be deep-drawn.
これに対し、比較例に示したとおり本発明の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１．２４、測定値が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 particles of the present invention can be formed into a sheet, but cannot be molded, or the material is not slippery and cannot be extruded, or is composite. The intermediate granules are 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 measured value fluctuates. The tensile elongation has a fluctuation range of 7 to 21%, a fluctuation range of ± 50%, an average specific gravity of 1.24, and a measured value of 1.19 to 1.26. The mechanical properties such as are deteriorated or the mechanical properties are poor, or the specific gravity varies and is not stable. Further, in terms of moldability, the material could be formed into a sheet, but the surface of the sheet was sticky, or the material was powdery or lumpy and could not be molded. Moreover, the container could not be molded.
本発明の澱粉・樹脂複合中間粒体を原材料として製造された澱粉・樹脂複合成形加工材料を製造した場合の方が優れた物性、性状及び成形性のものが得られることが確認され、澱粉・樹脂複合中間粒体を原材料とする方が澱粉・樹脂複合成形加工材料として優れていることが明らかとなった。 It was confirmed that when the starch / resin composite molded material produced by using the starch / resin composite intermediate granules of the present invention as a raw material, excellent physical properties, properties and moldability can be obtained, and the starch / resin composite molding material can be obtained. It was clarified that using the resin composite intermediate granules as a raw material is superior as a starch / resin composite molding processing material.
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 were significantly changed to 0.5, 0.5; 5.0 and 10.0% by weight, respectively, to granulate each additive. The effect on moldability was 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 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 molding, and Example 1 is performed. 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、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、含有量により、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生じることも分かる。 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. Furthermore, it can be seen that depending on the content, there are cases where sheet formation and molding processability of the container cannot be expected and cases where it can be achieved.
実施例と比較例によれば、本発明の澱粉・樹脂複合中間粒体を原材料として用いた複合成形加工材料の方が、Ｔ−ダイ押出機によるシート成形など可能であり、成形加工性が優位にあることが分かり、本発明の澱粉・樹脂複合中間粒体を原材料とする澱粉・樹脂複合成形加工材料は、物性等が優れたものが得られる。従来法や極端な成分組成を原材料とする澱粉・樹脂複合成形加工材料では同じ成分系であっても中間体ができない、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ていることが確認され、本発明の中間粒体を形成し、澱粉・樹脂複合成形加工材料を製造する方法が優れていることが確認できた。 According to Examples and Comparative Examples, the composite molding process material using the starch / resin composite intermediate granules of the present invention as a raw material is capable of sheet molding by a T-die extruder and has superior molding processability. As the raw material of the starch / resin composite intermediate granules of the present invention, the starch / resin composite molded material having excellent physical properties can be obtained. Because intermediates cannot be formed, specific gravity is not stable, starch flutters, or there is no slipperiness during extrusion with conventional methods or starch / resin composite molded materials using extreme component compositions as raw materials, even if they have the same component system. It was confirmed that the molding processability was hindered, such as excessive pressure being applied and the sheet could not be formed, the bleeding becoming extremely sticky when the sheet was formed, the intermediates sticking to each other, the granules becoming too large, and the molding machine could not be supplied. It was confirmed that the method for forming the intermediate granules of the present invention and producing the starch / resin composite molding processed material is excellent.
本発明により得られる澱粉・樹脂複合中間粒体は、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、カレンダー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に採用でき、各種成形加工法に適した澱粉・樹脂複合成形加工材料を製造するのに有用なものである。
The starch-resin composite intermediate granules obtained by the present invention are derived from a biomass material that can replace conventional petroleum-based plastics, and are manufactured by an extruder, a sheet by a T-die extruder, and a film by an inflation molding machine. Manufactures starch / resin composite molding materials that can be used in various molding processing technologies such as manufacturing of sheets, manufacturing of sheets by calendar molding machines, manufacturing of molded products by injection molding machines, and molding processing machines, and are suitable for various molding methods. It is useful for.
Claims (8)
上記の澱粉・樹脂複合中間粒体が、澱粉５０重量％以上、熱可塑性樹脂の粒状体２０重量％以上５０重量％未満、低融点添加剤成分０．１〜１０重量％、および、高融点添加剤成分１．０〜１５重量％を含み、
上記の低融点添加剤はグリセリン脂肪酸エステルであり、上記の高融点添加剤はステアリン酸金属塩である、
澱粉・樹脂複合成形加工材料を製造するための澱粉・樹脂複合中間粒体。 A starch-resin composite intermediate granule formed from a composite material composition containing starch, a low melting point additive, a high melting point additive having a higher melting point than the low melting point additive, and a granular thermoplastic resin. A granular material thermoplastic resin is used as a core portion, and a coating layer of a powder or granular material containing starch containing at least a low melting point additive, which is attached to the surface of the core portion of the granular material by a high melting point additive, is provided.
The starch / resin composite intermediate granules contain 50% by weight or more of starch, 20% by weight or more and less than 50% by weight of granular materials of thermoplastic resin, 0.1 to 10% by weight of low melting point additive component, and addition of high melting point. Contains 1.0 to 15% by weight of the agent component
The low melting point additive is a glycerin fatty acid ester, and the high melting point additive is a metal stearic acid salt.
Starch / resin composite intermediate granules for producing starch / resin composite molding processing materials.
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