JP5441441B2 - グラフト変性澱粉の水性組成物及びこれを用いた硬化性組成物 - Google Patents
グラフト変性澱粉の水性組成物及びこれを用いた硬化性組成物 Download PDFInfo
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- JP5441441B2 JP5441441B2 JP2009043582A JP2009043582A JP5441441B2 JP 5441441 B2 JP5441441 B2 JP 5441441B2 JP 2009043582 A JP2009043582 A JP 2009043582A JP 2009043582 A JP2009043582 A JP 2009043582A JP 5441441 B2 JP5441441 B2 JP 5441441B2
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- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000004804 polysaccharides Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
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- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 229940014800 succinic anhydride Drugs 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
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Description
サンプル容器:銀製密閉容器
リファレンス:蒸留水
測定温度:5℃〜105℃
昇温速度:4℃/分
サンプル容器:銀製密閉容器
リファレンス:蒸留水
測定温度:5℃〜105℃
昇温速度:4℃/分
冷却管、温度計、撹拌機及び滴下ロートを備えた反応容器に、イオン交換水100質量部及び酸化澱粉(王子コーンスターチ株式会社製、商品名「王子エースA」、水分含量12.5質量%)57.1質量部を仕込み、攪拌して澱粉スラリーとした。温度を95℃まで昇温して30分間攪拌し、澱粉スラリーを透明な糊化澱粉水溶液とした(糊化度99%)。温度を55℃まで冷却した後、酸化澱粉(糊化度0%)57.1質量部、及び、イオン交換水350質量部を投入した。ここに、アクリル酸ブチル100質量部、界面活性剤(株式会社ADEKA社製「アデカリアソープSR−10」)0.4質量部、イオン交換水60質量部を混合したモノマー乳化物を5時間かけて滴下した。同時に、35%過酸化水素水5質量部とイオン交換水20質量部を混合した酸化剤水溶液、二酸化チオ尿素5.6質量部をイオン交換水300質量部に溶解した還元剤水溶液を5時間かけて反応容器に滴下した。滴下終了後、さらに55℃で2時間攪拌した後、常温まで冷却し、グラフト変性澱粉の水分散体を得た。
参考例1において、澱粉スラリーを95℃まで昇温した時点で無水オクテニルコハク酸7質量部を反応容器に投入し、澱粉スラリーの糊化と同時に付加反応を行った。それ以外は参考例1と同様にして、実施例2のグラフト変性澱粉の水分散体を得た。
実施例2におけるアクリル酸ブチル100質量部を、アクリル酸ブチル90質量部、トリメトキシシリルプロピルメタクリレート10質量部の混合物とした以外は実施例2と同様にして、実施例3のグラフト変性澱粉の水分散体を得た。
実施例2における二酸化チオ尿素5.6質量部をアスコルビン酸4.5質量部としたこと以外は実施例2と同様にして、実施例4のグラフト変性澱粉の水分散体を得た。
実施例2における澱粉スラリーの昇温を65℃としたこと以外は実施例2と同様の操作を行なった。しかし、モノマー乳化物の重合により、反応物に沈降分離が発生し、グラフト変性澱粉の水性分散体を得ることはできなかった。
実施例2における温度55℃に冷却後に投入する酸化澱粉を温度60℃で投入し、60℃で30分攪拌後に55℃まで冷却したこと以外は実施例2と同様にして、比較例2のグラフト変性澱粉の水分散体を得た。
実施例2において、反応容器にイオン交換水190質量部及び酸化澱粉108.6質量部を仕込み、攪拌して澱粉スラリーとした。温度を95℃まで昇温し、無水オクテニルコハク酸13.3質量部を反応容器に投入した。95℃で30分間攪拌した後、温度を55℃まで冷却し、酸化澱粉5.7質量部、及び、イオン交換水260質量部を投入した。それ以外は実施例2と同様にして、比較例3のグラフト変性澱粉の水分散体を得た。
実施例2において、反応容器にイオン交換水10質量部及び酸化澱粉5.7質量部を仕込み、攪拌して澱粉スラリーとした。温度を95℃まで昇温し、無水オクテニルコハク酸0.7質量部を反応容器に投入した。95℃で30分間攪拌した後、温度を55℃まで冷却し、酸化澱粉108.6質量部、及び、イオン交換水440質量部を投入した。それ以外は実施例2と同様の操作を行なった。しかし、モノマー乳化物の重合により、反応物に沈降分離が発生し、グラフト変性澱粉の水性分散体を得ることはできなかった。
実施例2における無水オクテニルコハク酸を無水コハク酸に変更したこと以外は実施例2と同様にして、比較例5のグラフト変性澱粉の水分散体を得た。
実施例2におけるモノマー乳化物をアクリル酸ブチル4質量部、界面活性剤0.016質量部、イオン交換水2.4質量部を混合したモノマー乳化物とした以外は実施例2と同様にして、比較例6のグラフト変性澱粉の水分散体を得た。
実施例2において、反応容器にイオン交換水200質量部及び酸化澱粉114.2質量部を仕込み、攪拌して澱粉スラリーとした。温度を60℃まで昇温して糊化澱粉水溶液(糊化度58%)とし、温度60℃で無水オクテニルコハク酸を投入して付加反応を行った。温度55℃まで冷却後、糊化度0%の酸化澱粉を用いず、イオン交換水250質量部のみ添加した以外は実施例2と同様の操作を行なった。しかし、モノマー乳化物の重合により、反応物に沈降分離が発生し、グラフト変性澱粉の水性分散体を得ることはできなかった。
ガラス板にポリエチレンシートを貼り、その上にシリコンで枠を作成した。その枠にグラフト変性澱粉の水分散体を乾燥フィルムの膜厚が約0.4mmとなる量を流し込み、23℃、湿度65%RHで7日間乾燥させた。色相、クラック、歪の有無を目視で観察した。
作成したフィルム0.2質量部を110℃で5時間乾燥し、フィルムの乾燥質量を測定した。作成したフィルム0.2質量部をイオン交換水50質量部に1日浸漬した。1日後フィルムを取り出し、110℃で5時間乾燥して、水浸漬後のフィルムの乾燥質量を測定した。水溶出率は以下の式(3)で計算した。
グラフト変性澱粉中の澱粉由来の成分の糊化度(α化度)は、上に述べた条件で、示差走査熱量計を用いて糊化吸熱ピークのエンタルピーを測定し、式(2)により算出した。
実施例2で得られたグラフト変性澱粉の水分散体100質量部(固形分で20質量部)に対し、硬化剤として、ヘキサメチレンジイソシアネートを4質量部添加し、硬化性組成物を得た。得られた硬化性組成物について、上で述べた方法と同様の方法で、フィルム性能を測定した。フィルムの色は無色で、クラックや歪みもなく、また水溶出率も4.0%と非常に低い値が得られた。
Claims (9)
- 水性媒体中、少なくとも1種の(A)α化度が80%以上のα化澱粉に、炭素数4〜30の直鎖若しくは分岐鎖のアルキル基またはアルケニル基を有する無水ジカルボン酸化合物を付加した変性澱粉、及び、少なくとも1種の(B)α化度が20%以下の澱粉の存在下で、エチレン性不飽和モノマーを乳化重合することによって得られるグラフト変性澱粉の水性組成物であり、グラフト変性澱粉がエチレン性不飽和モノマーからなるポリマー成分に対して40〜2000質量%の澱粉由来の成分を有し、澱粉由来の成分のα化度が80%以下であり、(A)α化度が80%以上のα化澱粉と(B)α化度が20%以下の澱粉の比が10:90〜90:10であるグラフト変性澱粉の水性組成物。
- エチレン性不飽和モノマーの使用量が(A)α化度が80%以上のα化澱粉と(B)α化度が20%以下の澱粉の総量に対して5質量%〜250質量%であることを特徴とする請求項1に記載のグラフト変性澱粉の水性組成物。
- 無水ジカルボン酸化合物の(A)α化度が80%以上のα化澱粉に対する添加量が0.1質量%〜30質量%である請求項2に記載のグラフト変性澱粉の水性組成物。
- 無水ジカルボン酸化合物が無水オクテニルコハク酸であることを特徴とする請求項1〜3のいずれかに記載のグラフト変性澱粉の水性組成物。
- レドックス開始剤を用いて、エチレン性不飽和モノマーを乳化重合することによって得られる請求項1〜4のいずれかに記載のグラフト変性澱粉の水性組成物。
- レドックス開始剤の還元剤が二酸化チオ尿素または亜ジチオン酸ナトリウムであることを特徴とする請求項5に記載のグラフト変性澱粉の水性組成物。
- エチレン性不飽和モノマーが、澱粉の水酸基と反応可能な反応基を有するエチレン性不飽和モノマーを含むことを特徴とする請求項1〜6のいずれかに記載のグラフト変性澱粉の水性組成物。
- 請求項1〜7のいずれかに記載のグラフト変性澱粉の水性組成物、及び水酸基またはカルボキシル基と反応可能な官能基を有する硬化剤との混合物であることを特徴とする硬化性組成物。
- 請求項1〜7のいずれかに記載のグラフト変性澱粉の水性組成物又は請求項8に記載の硬化性組成物を乾燥して得られるフィルム。
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