JPH0369375B2 - - Google Patents
Info
- Publication number
- JPH0369375B2 JPH0369375B2 JP16761484A JP16761484A JPH0369375B2 JP H0369375 B2 JPH0369375 B2 JP H0369375B2 JP 16761484 A JP16761484 A JP 16761484A JP 16761484 A JP16761484 A JP 16761484A JP H0369375 B2 JPH0369375 B2 JP H0369375B2
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- starch
- pva
- polymerization
- vinyl
- 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.)
- Expired
Links
- 229920000642 polymer Polymers 0.000 claims description 47
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 30
- 229920002472 Starch Polymers 0.000 claims description 27
- 235000019698 starch Nutrition 0.000 claims description 26
- 229920001400 block copolymer Polymers 0.000 claims description 20
- 239000008107 starch Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 16
- 229920000881 Modified starch Polymers 0.000 claims description 10
- 229920002401 polyacrylamide Polymers 0.000 claims description 10
- 235000019426 modified starch Nutrition 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 description 27
- 125000003396 thiol group Chemical group [H]S* 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 12
- -1 thiol acids Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920002261 Corn starch Polymers 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000008120 corn starch Substances 0.000 description 9
- 229940099112 cornstarch Drugs 0.000 description 9
- 239000000178 monomer Substances 0.000 description 8
- 238000007127 saponification reaction Methods 0.000 description 8
- 229920001567 vinyl ester resin Polymers 0.000 description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004368 Modified starch Substances 0.000 description 5
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000003999 initiator Substances 0.000 description 4
- 229920001290 polyvinyl ester Polymers 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011437 continuous method Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- DUYAAUVXQSMXQP-UHFFFAOYSA-N ethanethioic S-acid Chemical compound CC(S)=O DUYAAUVXQSMXQP-UHFFFAOYSA-N 0.000 description 2
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- MVYVKSBVZFBBPL-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)NC(=O)C=C MVYVKSBVZFBBPL-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical group N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- MJPVYTKZYZPIQA-UHFFFAOYSA-N 3-thiophen-2-ylpropanoic acid Chemical compound OC(=O)CCC1=CC=CS1 MJPVYTKZYZPIQA-UHFFFAOYSA-N 0.000 description 1
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004153 Potassium bromate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- FBYFHODQAUBIOO-UHFFFAOYSA-N carboxyethyl ether Natural products OC(=O)C(C)OC(C)C(O)=O FBYFHODQAUBIOO-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- YRVUCYWJQFRCOB-UHFFFAOYSA-N n-butylprop-2-enamide Chemical compound CCCCNC(=O)C=C YRVUCYWJQFRCOB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 235000019396 potassium bromate Nutrition 0.000 description 1
- 229940094037 potassium bromate Drugs 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229920003170 water-soluble synthetic polymer Polymers 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
Ａ 産業上の利用分野
本発明は相溶性の極めてすぐれた高分子組成物
に関する。さらに詳しくは、(A)天然産でんぷんま
たは各種化工でんぷんの中から選ばれた少くとも
１種のでんぷん及び(B)ポリビニルアルコール系重
合体を一成分とし、アクリルアミド系重合体を他
成分とするブロツク共重合体とを含有することを
特徴とする、水溶性あるいは固体状態において相
溶性の極めてすぐれた高分子組成物に関する。
Ｂ 従来の技術
従来、典型的な天然水溶性高分子としてのでん
ぷん及び水溶性合成高分子としてのボリビニルア
ルコール系重合体（以下PVA系重合体と略記す
る）はその水溶性を生かして多くの工業分野、例
えば接着剤、繊維や紙のサイジング剤、コーテイ
ング剤、フイルム、繊維などの成形素材等に各々
単独に使用されるのみならず、両者を混合して使
用する場合が非常に多い。しかし両者は一般に相
溶性が悪く、加工及び成形操作の面だけでなく加
工処理や成形物自体の物性面にも種々の好ましか
らざる影響を与えている。たとえば繊維サイジン
グではでんぷん類とPVA系重合体の混合水溶液
が使用されるがこの混合水溶液は放置するとすみ
やかに二層に分離を起して極めて不都合である。
従つて、使用に際しては水溶性を絶えず撹拌して
二層分離を起こさないように操作しなければなら
ない。しかしこのようにして塗布しても次の乾燥
工程において両者は相分離し、PVA系重合体の
性能上の有利性が充分に生かされていないという
問題があつた。
これに対してでんぷん類とPVA系重合体の相
溶性を改良する試みもなされており、でんぷん側
の改良としては生でんぷんに各種変性を施こすこ
とにより生でんぷんの場合よりも相溶性を向上し
ようとするものである。一方PVA系重合体側の
改良もいくつかなされており、ポリビニルアルコ
ールグラフト変性でんぷんや長鎖アルキル基変性
ポリビニルアルコールを単独もしくは未変性の
PVA系重合体と併用することにより相溶性の向
上を図ろうとするものである。これらの試みは一
応の成果はみられるものの必ずしも相溶性が充分
でなかつたり、あるいは経済性の面での不利等か
ら満足できるものではない。
Ｃ 発明が解決しようとする問題点
本発明者らはかかる状況に鑑み鋭意検討した結
果、PVA系重合体を一成分とし、アクリルアミ
ド系重合体を他成分とするブロツク共重合体が、
生でんぷんをはじめ各種の化工でんぷんと極めて
よく相溶することを見出し本発明を完成するに到
つたものである。
Ｄ 問題を解決する為の手段
本発明の高分子組成物の１成分である、PVA
系重合体成分とアクリルアミド系重合体成分とか
らなるブロツク共重合体は、種々の任意の方法に
より製造することができるが、本発明の実施例に
示す如く、末端にチオール酸エステル基を有する
ポリビニルエステル系重合体をけん化することに
より得られる末端にメルカプト基を有するPVA
系重合体の存在下に、ラジカル重合可能な、アク
リルアミド系モノマーをラジカル重合して製造す
る方法が最も好ましい。その製造法は特開昭59−
187003号（特願昭58−61746号）、特開昭59−
189113号（特願昭58−62673号）の明細書に述べ
たとおりであるが、その詳細な方法を以下に記
す。
まず第１に、末端にメルカプト基を有する
PVA系重合体はチオール酸の存在下にビニルエ
ステル類モノマーを主体とするビニルモノマーを
重合して得た末端にチオール酸エステル基を有す
るポリビニルエステル系重合体を常法によりけん
化して得られる。
ここで使用するチオール酸は−COSH基を有す
る有機チオール酸を包含する。例えばチオール酢
酸、チオールプロピオン酸、チオール酪酸、チオ
ール吉草酸等があげられるが、中でもチオール酢
酸が分解性もよく最も好ましい。
ビニルエステルはラジカル重合可能なビニルエ
ステルであれば使用できる。例えばギ酸ビニル、
酢酸ビニル、プロピオン酸ビニル、パーサテイツ
ク酸ビニル、ラウリル酸ビニル、ステアリン酸ビ
ニル等があげられるが、中でも酢酸ビニルが最も
重合性がよく、好ましい。
チオール酸の存在下の酢酸ビニル等のビニルエ
ステル類を主体とするビニルモノマーの重合はラ
ジカル重合開始剤の存在下、塊状重合法、溶液重
合法、パール重合法、乳化重合法などいずれの方
法でも行なうことができるが、メタノールを溶媒
とする溶液重合法が工業的には最も有利である。
重合中に存在させるチオール酸の重合系への添加
量、添加方法には特に制限はなく、目的とする
PVA系重合体の物性値によつて適宜決定さるべ
きものである。重合方式としては回分式、半連続
式、連続式等公知の方式を採用しうる。
ラジカル重合開始剤としては２，2′−アゾビス
イソブチロニトリル、過酸化ベンゾイル、過酸化
カーボネート等公知のラジカル重合開始剤が使用
できるが、２，2′−アゾビスイソブチロニトリル
等のアゾ系開始剤が取扱いやすく好ましい。また
放射線、電子線等も使用することができる。重合
温度は使用する開始剤の種類により適当な温度を
採用することが望ましいが、通常30〜90℃の範囲
から選ばれる。所定時間重合した後未重合のビニ
ルエステル類を通常の方法で除去することにより
末端にチオール酸エステル基を有するポリビニル
エステル系重合体がえられる。
このようにして得られたポリビニルエステル系
重合体は常法によりけん化されるが、通常重合体
をアルコール溶液とりわけメタノール溶液として
実施するのが有利である。アルコールは無水物の
みならず少量の含水系のものを目的に応じて用い
られ、また酢酸メチル、酢酸エチルなどの有機溶
媒を任意に含有せしめてもよい。けん化温度は通
常10〜70℃の範囲から選ばれる。けん化触媒とし
ては水酸化ナトリウム、水酸化カリウム、ナトリ
ウムメチラート、カリウムメチラート等のアルカ
リ性触媒が好ましく、該触媒の使用量はけん化度
の大小および水分量等により適宜決められるが、
ビニルエステル単位に対しモル比で0.001以上、
好ましくは0.002以上用いることが望ましい。一
方アルカリ量が多くなりすぎると残存アルカリを
ポリマー中より除去することが困難となり、ポリ
マーが着色する等好ましくなく、モル比で0.2以
下にすることが望ましい。
このけん化反応により末端にチオール酸エステ
ル基を有するポリビニルエステル系重合体の末端
のチオール酸エステルと主鎖のビニルエステル結
合がけん化され、ポリマー末端はメルカプト基
に、主鎖はビニルアルコールになるが、主鎖のビ
ニルエステル単位のけん化度は使用目的に応じて
変えられるが、20モル％以上、好ましくは50モル
％以上、更に好ましくは70モル％以上であれば特
に制限はない。けん化反応後析出した重合体は、
例えばメタノールで洗浄する等公知の方法で精製
し、残存アルカリ、酢酸のアルカリ金属塩等の不
純物を除去して乾燥することにより通常白色粉末
としてえることができる。
なお本発明で言うところのPVA系重合体とは、
ビニルアルコール単位を20モル％以上、好ましく
は50モル％以上、更に好ましくは70モル％以上含
有する重合体をさすものであり、他の単量体成分
として、たとえば酢酸ビニル、ギ酸ビニル、プロ
ピオン酸ビニル、バーサテイツク酸ビニル、エチ
レン、プロピレン、（メタ）アクリル酸及びその
塩、イタコン酸、マレイン酸、フマル酸及びそれ
らの塩、２−アクリルアミドプロパンスルホン酸
及びその塩、（メタ）アクリルアミドプロピルト
リメチルアンモニウムクロリド等を含むことは何
等さしつかえない。重合度は10以上3500以下の範
囲にあるものであれば特に制限はない。
次に、末端にメルカプト基を有するPVA系重
合体の存在下に、ラジカル重合可能なアクリルア
ミド系モノマーのラジカル重合を行なう方法につ
いて述べる。重合方法としては、通常公知の方
法、たとえばバルク重合、溶液重合、パール重
合、および乳化重合などが採用されうるが、
PVA系重合体を溶解しうる溶剤、たとえば水や
ジメチルスルホキシドを主体とする媒体中で重合
を行なうのが好ましい。また重合プロセスとして
は回分法、半回分法、連続法のいずれも採用する
ことができる。
ブロツク共重合体を得るためのラジカル重合
は、通常のラジカル重合開始剤、たとえは２，
2′−アゾビスイソブチロニトリル、ベンゾイルパ
ーオキサイド、ラウロイルパーオキサイド、ジイ
ソプロピルパーオキシカーボネート、過硫酸カリ
ウム、過硫酸アンモニウム等の中から重合系に合
つたものを使用し、行なうことによつて達成され
るが、水系での重合の場合、PVA系重合体末端
のメルカプト基と臭素酸カリウム、過硫酸カリウ
ム、過硫酸アンモニウム、過酸化水素等の酸化剤
によるレドツクス開始も可能であり、この中でも
臭素酸カリウムは、通常の重合条件下では単独で
はラジカルを発生せず、PVA系重合体末端のメ
ルカプト基とのレドツクス反応によつてのみ分
解、ラジカルを発生することから、本発明のブロ
ツク共重合体を合成する上で特に好ましい開始剤
である。
本発明の末端にメルカプト基を有するPVA系
重合体の存在下にラジカル重合を行なうに際し、
重合性が酸性であることが重要であり、望まし
い。これはメルカプト基が塩基性下においては、
モノマーの二重結合へイオン的に付加、消失する
速度が大きく、重合効率が著しく低下するためで
あり、水系の重合であれば、全ての重合操作をPH
４以下で実施することが望ましい。
また本発明のブロツク共重合体の１成分である
アクリルアミド系重合体とは、（メタ）アクリル
アミドおよびＮ，N′−ジメチルアクリルアミド、
Ｎ−ブチルアクリルアミド、Ｎ−メチロールアク
リルアミド、（メタ）アクリルアミドプロピルト
リメチルアンモニウムクロリド、２−アクリルア
ミド−２−メチルプロパンスルホン酸およびその
塩の如き、（メタ）アクリルアミド誘導体の少な
くとも一種の単量体を重合単位として含有するも
のであれば良く、その他に（メタ）アクリル酸、
（メタ）アクリル酸エステル類、（メタ）アクリロ
ニトリル、エチレン、酢酸ビニル等のビニルエス
テル類、塩化ビニル等のハロゲン化ビニル等のラ
ジカル重合可能なモノマーを重合単位として含有
することは何ら差し支えない。
本発明のブロツク共重合体中のPVA系重合体
成分とアクリルアミド系重合体成分との重量比率
は特に制限はないが、
0.05≦（PVA系重合体）／（アクリルアミド系重
合体）≦20
さらに好ましくは、
0.1≦（PVA系重合体）／（アクリルアミド系重
合体）≦10
である。
本発明の高分子組成物の他成分であるでんぷん
類は天然産でんぷんまたは各種化工でんぷんの中
から選ばれる少くとも１種のでんぷんであり、た
とえばコーンスターチ、小麦でんぷん、さつまい
もでんぷん、じやがいもでんぷん、タピオカでん
ぷん、酸化でんぷん、可溶性でんぷん、デキスト
リン、ジアルデヒドでんぷん、各種エステルでん
ぷん（酢酸エステル、硝酸エステル、リン酸エス
テル等）、各種エーテル化でんぷん（メチルエー
テル、カルボキシメチルエーテル、カルボキシエ
チルエーテル等）である。
本発明の高分子組成物は(A)天然産でんぷんまた
は各種化工でんぷんの中から選ばれた少くとも１
種のでんぷん及び(B)PVA系重合体を一成分とし、
アクリルアミド系重合体を他成分とするブロツク
共重合体とを含有することが必須であり、(A)／(B)
の混合比率には特に制限はないが、重量比率で
１／99≦(A)／(B)≦99／１、更に好ましくは１／10
≦(A)／(B)≦99／１の範囲にあるのが望ましい。
また相溶性を損なわない範囲において他の成分
たとえば通常の未変性ポリビニルアルコールやセ
ルロース系誘導体等の高分子化合物、可塑剤、着
色剤、フイラー、塩類、ホウ酸又はホウ砂、界面
活性剤など種々の添加剤を加えてもよい。
Ｅ 作用及び発明の効果
このようにPVA系重合体を一成分とし、アク
リルアミド系重合体を他成分とするブロツク共重
合体がでんぷん類と極めて相溶性の良好な高分子
組成物を与える作用機構の詳細は明らかではない
が、でんぷん類と相溶性の良好なアクリルアミド
系重合体部分がミクロに相分離したでんぷんに吸
着し凝集を防止しているものと思われる。
また通常ポリビニルアルコールと天然産でんぷ
ん併用系にて使用する場合天然産でんぷんは高温
高圧の糊化を必要とするが、本発明の高分子組成
物に於ては、いかなる高圧クツカーをも必要とせ
ず、常圧90〜95℃で撹拌溶解することにより充分
糊化し相溶性及び安定性の良い糊液のできること
も特徴の１つである。
そして本発明の高分子組成物は水溶液での安定
性が良好でかつ固体状態での相溶性もよいため乾
燥したときに極めて透明性の良好なフイルムを与
える。これらの性質はでんぷんとして酸化でんぷ
んのような化工でんぷんを用いた場合のみならず
元来相溶性が極めて悪いとされるコーンスターチ
を用いたときにも充分に認められる。
このように本発明の高分子組成物は相溶性のよ
いことを生かして種々の用途に用い得るが、たと
えば接着剤、繊維、紙のサイジング剤、コーテイ
ング剤等の加工剤、フイルム、繊維等の成形素材
等があげられる。
以下実施例を挙げて本発明の高分子組成物に関
し、液の相溶性、安定性について更に詳しく説明
する。なお実施例中の「％」及び「部」はいずれ
も「重量％」及び「重量部」を示す。
ブロツク共重合体の調整例
末端にメルカプト基を有するポリビニルアルコ
ール（けん化度＝98.9モル％、〔HS〕＝1.46×
10-5eq／ｇ）50部に蒸溜水800部を加えて煮沸溶
解した後、室温まで冷却し、1N−H2SO4でPHを
3.0に調整した。次いでアクリルアミドモノマー
47.5部及びアクリル酸モノマー2.5部を加えて溶
解し、チツ素置換した後70℃に昇温して、蒸溜水
20部にK2S2O80.38部を溶解した開始剤水溶液を
添加して重合を開始した。３時間、70℃で撹拌重
合した後、室温まで冷却し、ポリビニルアルコー
ル−ポリ（アクリルアミド−アクリル酸）ブロツ
ク共重合体水溶液を得た。PHを5.0に調整し、濃
度は10.5％、20℃での粘度は5600cpであつた。
このブロツク共重合体をブロツク共重合体Ａと
表記する。以下同様の方法でブロツク共重合体Ｂ
〜Ｆを調整した。組成、濃度、粘度を表１にまと
めて記す。
A. Industrial Application Field The present invention relates to a polymer composition with extremely excellent compatibility. More specifically, the block contains (A) at least one type of starch selected from naturally occurring starches or various modified starches, and (B) a polyvinyl alcohol polymer as one component and an acrylamide polymer as the other component. The present invention relates to a polymer composition that is characterized by containing a copolymer and has extremely excellent compatibility in water solubility or solid state. B. Prior Art Conventionally, starch, which is a typical natural water-soluble polymer, and polyvinyl alcohol polymer (hereinafter abbreviated as PVA polymer), which is a typical water-soluble synthetic polymer, have been used in many ways due to their water solubility. In the industrial field, for example, adhesives, sizing agents for fibers and paper, coating agents, films, molding materials for fibers, etc., they are not only used individually, but also often used as a mixture of the two. However, the two generally have poor compatibility and have various undesirable effects not only on processing and molding operations but also on processing and physical properties of the molded product itself. For example, in fiber sizing, a mixed aqueous solution of starches and PVA polymers is used, but when this mixed aqueous solution is left to stand, it quickly separates into two layers, which is extremely inconvenient.
Therefore, during use, the aqueous solution must be constantly stirred to avoid separation of the two layers. However, even when applied in this manner, there is a problem in that the two phases separate in the subsequent drying process, and the performance advantages of the PVA polymer are not fully utilized. In response to this, attempts have been made to improve the compatibility between starches and PVA polymers, and to improve the starch side, it is possible to improve the compatibility compared to raw starch by applying various modifications to raw starch. That is. On the other hand, several improvements have been made on the PVA polymer side, and polyvinyl alcohol graft-modified starch and long-chain alkyl group-modified polyvinyl alcohol have been used alone or unmodified.
The aim is to improve compatibility by using it in combination with a PVA polymer. Although these attempts have shown some success, they are not always satisfactory due to insufficient compatibility or economical disadvantages. C Problems to be Solved by the Invention As a result of intensive studies in view of the above situation, the present inventors found that a block copolymer containing a PVA polymer as one component and an acrylamide polymer as the other component,
The present invention was completed by discovering that it is extremely compatible with raw starch and various modified starches. D Means for solving the problem PVA, which is one component of the polymer composition of the present invention
A block copolymer consisting of an acrylamide-based polymer component and an acrylamide-based polymer component can be produced by various arbitrary methods. PVA with a mercapto group at the end obtained by saponifying an ester polymer
The most preferred method is to radically polymerize an acrylamide monomer capable of radical polymerization in the presence of a polymer. The manufacturing method was published in 1983.
No. 187003 (Japanese Patent Application No. 1983-61746), Japanese Patent Application No. 1983-
The method is as described in the specification of No. 189113 (Japanese Patent Application No. 58-62673), and the detailed method is described below. First of all, it has a mercapto group at the end.
PVA-based polymers are obtained by polymerizing vinyl monomers, mainly vinyl ester monomers, in the presence of thiolic acid, and saponifying a polyvinyl ester-based polymer having thiol acid ester groups at the terminals by a conventional method. The thiol acids used herein include organic thiol acids having a -COSH group. Examples include thiol acetic acid, thiol propionic acid, thiol butyric acid, and thiol valeric acid, among which thiol acetic acid is the most preferred because of its good degradability. Any vinyl ester that can be radically polymerized can be used. For example, vinyl formate,
Examples include vinyl acetate, vinyl propionate, vinyl persate, vinyl laurate, and vinyl stearate, among which vinyl acetate has the best polymerizability and is preferred. Polymerization of vinyl monomers mainly consisting of vinyl esters such as vinyl acetate in the presence of thiol acid can be carried out by any method such as bulk polymerization, solution polymerization, pearl polymerization, or emulsion polymerization in the presence of a radical polymerization initiator. However, solution polymerization using methanol as a solvent is industrially most advantageous.
There are no particular restrictions on the amount or method of addition of thiol acid to the polymerization system, and it can be added to the polymerization system depending on the purpose.
It should be determined appropriately depending on the physical property values of the PVA polymer. As the polymerization method, known methods such as a batch method, a semi-continuous method, and a continuous method can be employed. As the radical polymerization initiator, known radical polymerization initiators such as 2,2'-azobisisobutyronitrile, benzoyl peroxide, and carbonate peroxide can be used. Azo initiators are preferred because they are easy to handle. Furthermore, radiation, electron beams, etc. can also be used. The polymerization temperature is desirably selected depending on the type of initiator used, but is usually selected from the range of 30 to 90°C. After polymerization for a predetermined period of time, unpolymerized vinyl esters are removed by a conventional method to obtain a polyvinyl ester polymer having a thiol acid ester group at the end. The polyvinyl ester polymer thus obtained is saponified by conventional methods, but it is usually advantageous to carry out the saponification of the polymer as an alcohol solution, particularly a methanol solution. Not only anhydrous alcohols but also alcohols containing a small amount of water can be used depending on the purpose, and organic solvents such as methyl acetate and ethyl acetate may be optionally contained. The saponification temperature is usually selected from the range of 10 to 70°C. As the saponification catalyst, alkaline catalysts such as sodium hydroxide, potassium hydroxide, sodium methylate, potassium methylate, etc. are preferable, and the amount of the catalyst used is determined as appropriate depending on the degree of saponification, water content, etc.
0.001 or more in molar ratio to vinyl ester units,
It is preferable to use 0.002 or more. On the other hand, if the amount of alkali is too large, it will be difficult to remove the residual alkali from the polymer and the polymer will be colored, which is undesirable, so it is desirable that the molar ratio is 0.2 or less. Through this saponification reaction, the terminal thiol acid ester and the vinyl ester bond in the main chain of the polyvinyl ester polymer having a thiol acid ester group at the end are saponified, and the polymer terminal becomes a mercapto group and the main chain becomes vinyl alcohol. The degree of saponification of the vinyl ester unit in the main chain can be varied depending on the purpose of use, but is not particularly limited as long as it is 20 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more. The polymer precipitated after the saponification reaction is
It can usually be obtained as a white powder by purifying it by a known method such as washing with methanol, removing impurities such as residual alkali and alkali metal salts of acetic acid, and drying. The PVA polymer referred to in the present invention is
It refers to a polymer containing 20 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more of vinyl alcohol units, and other monomer components include vinyl acetate, vinyl formate, propionic acid, etc. Vinyl, vinyl versatate, ethylene, propylene, (meth)acrylic acid and its salts, itaconic acid, maleic acid, fumaric acid and their salts, 2-acrylamidopropanesulfonic acid and its salts, (meth)acrylamidopropyltrimethylammonium chloride There is nothing wrong with including such things. The degree of polymerization is not particularly limited as long as it is in the range of 10 or more and 3500 or less. Next, a method for radical polymerization of a radically polymerizable acrylamide monomer in the presence of a PVA polymer having a mercapto group at its terminal will be described. As the polymerization method, commonly known methods such as bulk polymerization, solution polymerization, pearl polymerization, and emulsion polymerization can be adopted, but
It is preferable to carry out the polymerization in a solvent capable of dissolving the PVA polymer, such as a medium mainly consisting of water or dimethyl sulfoxide. Further, as the polymerization process, any of a batch method, a semi-batch method, and a continuous method can be adopted. Radical polymerization to obtain a block copolymer is carried out using a conventional radical polymerization initiator, such as 2,
This can be achieved by using one suitable for the polymerization system from among 2'-azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxycarbonate, potassium persulfate, ammonium persulfate, etc. However, in the case of polymerization in an aqueous system, it is also possible to initiate redox with the mercapto group at the end of the PVA polymer and an oxidizing agent such as potassium bromate, potassium persulfate, ammonium persulfate, or hydrogen peroxide. does not generate radicals by itself under normal polymerization conditions, but decomposes and generates radicals only through a redox reaction with the mercapto group at the end of the PVA-based polymer. Therefore, the block copolymer of the present invention can be synthesized. It is a particularly preferred initiator for this purpose. When performing radical polymerization in the presence of the PVA polymer having a mercapto group at the terminal of the present invention,
It is important and desirable that the polymerizability is acidic. This is because when the mercapto group is basic,
This is because the rate of ionic addition and disappearance of monomer double bonds is high, resulting in a significant drop in polymerization efficiency.
It is desirable to carry out at 4 or less. Furthermore, the acrylamide polymer that is one component of the block copolymer of the present invention includes (meth)acrylamide and N,N'-dimethylacrylamide,
A polymer unit containing at least one monomer of (meth)acrylamide derivatives such as N-butylacrylamide, N-methylolacrylamide, (meth)acrylamidopropyltrimethylammonium chloride, 2-acrylamido-2-methylpropanesulfonic acid and salts thereof. In addition, (meth)acrylic acid,
There is no problem in containing radically polymerizable monomers such as (meth)acrylic acid esters, (meth)acrylonitrile, ethylene, vinyl esters such as vinyl acetate, and vinyl halides such as vinyl chloride as polymerized units. The weight ratio of the PVA polymer component and the acrylamide polymer component in the block copolymer of the present invention is not particularly limited, but is more preferably 0.05≦(PVA polymer)/(acrylamide polymer)≦20. is 0.1≦(PVA polymer)/(acrylamide polymer)≦10. Starch, which is another component of the polymer composition of the present invention, is at least one type of starch selected from naturally occurring starches or various modified starches, such as corn starch, wheat starch, sweet potato starch, and potato starch. , tapioca starch, oxidized starch, soluble starch, dextrin, dialdehyde starch, various ester starches (acetate ester, nitrate ester, phosphate ester, etc.), various etherified starches (methyl ether, carboxymethyl ether, carboxyethyl ether, etc.) be. The polymer composition of the present invention comprises (A) at least one selected from naturally occurring starches and various modified starches;
Seed starch and (B) PVA polymer as one component,
It is essential to contain a block copolymer containing an acrylamide polymer as another component, and (A)/(B)
There is no particular restriction on the mixing ratio, but the weight ratio is 1/99≦(A)/(B)≦99/1, more preferably 1/10.
It is desirable that the range is ≦(A)/(B)≦99/1. In addition, other components such as ordinary unmodified polyvinyl alcohol, polymeric compounds such as cellulose derivatives, plasticizers, colorants, fillers, salts, boric acid or borax, surfactants, etc. may be added to the extent that compatibility is not impaired. Additives may also be added. E. Effects of the invention As described above, the mechanism of action of a block copolymer containing a PVA polymer as one component and an acrylamide polymer as the other component provides a polymer composition having extremely good compatibility with starches. Although the details are not clear, it is thought that the acrylamide polymer portion, which has good compatibility with starch, adsorbs to the microscopically phase-separated starch and prevents agglomeration. Furthermore, when using a combination of polyvinyl alcohol and naturally produced starch, naturally produced starch requires gelatinization at high temperature and high pressure, but with the polymer composition of the present invention, no high pressure maker is required. One of the features is that by stirring and dissolving at normal pressure of 90 to 95°C, it can be sufficiently gelatinized and a size liquid with good compatibility and stability can be produced. Since the polymer composition of the present invention has good stability in an aqueous solution and good compatibility in a solid state, it provides a film with extremely good transparency when dried. These properties are fully observed not only when a modified starch such as oxidized starch is used as the starch, but also when corn starch, which is originally considered to have extremely poor compatibility, is used. As described above, the polymer composition of the present invention can be used for various purposes by taking advantage of its good compatibility. Examples include molding materials. The liquid compatibility and stability of the polymer composition of the present invention will be explained in more detail with reference to Examples below. Note that "%" and "parts" in the examples indicate "% by weight" and "parts by weight." Preparation example of block copolymer Polyvinyl alcohol having a mercapto group at the end (saponification degree = 98.9 mol%, [HS] = 1.46 ×
Add 800 parts of distilled water to 50 parts (10 -5 eq/g), dissolve by boiling, cool to room temperature, and adjust the pH with 1N-H 2 SO 4.
Adjusted to 3.0. Then acrylamide monomer
47.5 parts and 2.5 parts of acrylic acid monomer were added and dissolved, and after nitrogen substitution, the temperature was raised to 70℃, and distilled water was added.
An aqueous initiator solution containing 0.38 parts of K 2 S 2 O 8 dissolved in 20 parts was added to initiate polymerization. After stirring and polymerizing at 70°C for 3 hours, the mixture was cooled to room temperature to obtain an aqueous solution of polyvinyl alcohol-poly(acrylamide-acrylic acid) block copolymer. The pH was adjusted to 5.0, the concentration was 10.5%, and the viscosity at 20°C was 5600 cp. This block copolymer is referred to as block copolymer A. Block copolymer B was then prepared in the same manner.
~F was adjusted. The composition, concentration, and viscosity are summarized in Table 1.
【表】【table】
【表】
実施例 １
ブロツク共重合体A3部、コーンスターチ７部
に、固形分が10％になるよう所定量の水を加え撹
拌分散させた後、90〜95℃の温浴上で１時間撹拌
溶解せしめる。
この液のコーンスターチは完全に糊化し、ブロ
ツク共重合体Ａとコーンスターチとの相溶性及び
液の安定性は良好で、70℃で一昼夜放置後も相分
離はしない。
この液から作製したフイルムは透明で、コーン
スターチが７部添加しているとは思えない程光沢
と滑らかさをもち、ヤング率も充分であつた。同
様の試験をブロツク共重合体Ｂ〜Ｆについても行
ない、結果を表２にまとめた。[Table] Example 1 A predetermined amount of water was added to 3 parts of block copolymer A and 7 parts of cornstarch so that the solid content was 10%, stirred and dispersed, and then stirred and dissolved in a hot bath at 90 to 95°C for 1 hour. urge The cornstarch in this liquid was completely gelatinized, and the compatibility between block copolymer A and cornstarch and the stability of the liquid were good, and no phase separation occurred even after standing at 70°C overnight. The film produced from this liquid was transparent, had such gloss and smoothness that it was hard to believe that 7 parts of cornstarch was added, and had a sufficient Young's modulus. Similar tests were conducted on block copolymers B to F, and the results are summarized in Table 2.
【表】【table】
【表】
比較例 １
PVA−117、またはPVA−217の３部及びコー
ンスターチ７部に、固形分がそれぞれ10％になる
よう所定量の水を加えて撹拌分散させたのち、オ
ートクレーブ中120℃、30分撹拌溶解せしめる。
これらの液のコーンスターチは完全に糊化はし
ているもののPVA−117、またはPVA−217との
相溶性、液の安定性は不良で、70℃で一昼夜放置
後の液は完全に相分離していた。
またこれらの液から作製したフイルムは、
PVA−117、またはPVA−217とコーンスターチ
が完全に分離し不透明でざらついており強伸度は
非常に低い値となつた。結果を表１に併記する。
実施例 ２
ブロツク共重合体A2部、化工でんぷん８部に、
固形分が10％になるよう所定量の水を加え撹拌分
散させたのち、90〜95℃の温浴上で１時間撹拌溶
解せしめる。
ブロツク共重合体Ａと化工でんぷんとの相溶
性、液の安定性は良好で、70℃で一昼夜放置後も
相分離しない。
この液から作製したフイルムは透明で、柔軟性
を有している。同様の試験をブロツク共重合体Ｂ
〜Ｆについても行ない、結果を表３にまとめた。[Table] Comparative Example 1 A predetermined amount of water was added to 3 parts of PVA-117 or PVA-217 and 7 parts of cornstarch so that the solid content was 10%, and the mixture was stirred and dispersed. Stir for 30 minutes to dissolve. Although the cornstarch in these liquids was completely gelatinized, its compatibility with PVA-117 or PVA-217 and the stability of the liquid were poor, and after being left at 70°C for a day and night, the liquid did not completely phase separate. was. In addition, films made from these liquids are
PVA-117 or PVA-217 and corn starch were completely separated and became opaque and rough, and the strength and elongation were extremely low. The results are also listed in Table 1. Example 2 2 parts of block copolymer A, 8 parts of modified starch,
After adding a predetermined amount of water to make the solid content 10% and stirring and dispersing, the mixture was stirred and dissolved in a hot bath at 90 to 95°C for 1 hour. The compatibility between block copolymer A and modified starch and the stability of the liquid are good, and there is no phase separation even after standing at 70°C for a day and night. Films made from this liquid are transparent and flexible. A similar test was conducted for block copolymer B.
-F were also tested, and the results are summarized in Table 3.
【表】
比較例 ２
PVA−117またはPVA−217の２部及び化工で
んぷん８部に、固形分がそれぞれ10％になるよう
所定量の水を加え、撹拌分散させたのち、90〜95
℃の温浴上で、１時間撹拌溶解せしめる。
これらの液の相溶性はそれほど良くなく、70℃
一昼夜放置後完全に相分離を起こしていた。
またこれらの液から作製したフイルムは不透明
で、滑らかさを失つていた。結果を表３に併記す
る。[Table] Comparative Example 2 A predetermined amount of water was added to 2 parts of PVA-117 or PVA-217 and 8 parts of modified starch so that the solid content was 10%, and after stirring and dispersing, 90 to 95
Stir and dissolve on a warm bath at ℃ for 1 hour. The compatibility of these liquids is not very good, and at 70℃
After standing for a day and night, complete phase separation occurred. Films made from these solutions were also opaque and lacked smoothness. The results are also listed in Table 3.
Claims (1)
中から選ばれた少くとも１種のでんぷん及び(B)ポ
リビニルアルコール系重合体を一成分としてアク
リルアミド系重合体を他成分とするブロツク共重
合体とを含有することを特徴とする高分子組成
物。1. (A) at least one starch selected from naturally occurring starches or various modified starches, and (B) a block copolymer containing a polyvinyl alcohol polymer as one component and an acrylamide polymer as the other component. A polymer composition characterized by containing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16761484A JPS6144935A (en) | 1984-08-09 | 1984-08-09 | Polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16761484A JPS6144935A (en) | 1984-08-09 | 1984-08-09 | Polymer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6144935A JPS6144935A (en) | 1986-03-04 |
| JPH0369375B2 true JPH0369375B2 (en) | 1991-10-31 |
Family
ID=15853046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16761484A Granted JPS6144935A (en) | 1984-08-09 | 1984-08-09 | Polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6144935A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IL94587A (en) * | 1989-06-19 | 1997-04-15 | Novon International | Polymer base blend compositions containing destructurized starch |
| WO2023085441A1 (en) * | 2021-11-10 | 2023-05-19 | 国立大学法人東京大学 | Macroporous structure |
-
1984
- 1984-08-09 JP JP16761484A patent/JPS6144935A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6144935A (en) | 1986-03-04 |
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