JP2006257225A - Polyvinyl alcohol film and use thereof - Google Patents
Polyvinyl alcohol film and use thereof Download PDFInfo
- Publication number
- JP2006257225A JP2006257225A JP2005075343A JP2005075343A JP2006257225A JP 2006257225 A JP2006257225 A JP 2006257225A JP 2005075343 A JP2005075343 A JP 2005075343A JP 2005075343 A JP2005075343 A JP 2005075343A JP 2006257225 A JP2006257225 A JP 2006257225A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- film
- resin
- starch
- mol
- 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.)
- Pending
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 91
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 91
- 229920005989 resin Polymers 0.000 claims abstract description 53
- 239000011347 resin Substances 0.000 claims abstract description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000007127 saponification reaction Methods 0.000 claims abstract description 27
- 239000011342 resin composition Substances 0.000 claims abstract description 26
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 229920002554 vinyl polymer Polymers 0.000 claims description 21
- 239000004094 surface-active agent Substances 0.000 claims description 16
- 239000003814 drug Substances 0.000 claims description 12
- 229940079593 drug Drugs 0.000 claims description 11
- 239000000725 suspension Substances 0.000 claims description 4
- 238000009512 pharmaceutical packaging Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 18
- 238000003860 storage Methods 0.000 abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 7
- 229920002472 Starch Polymers 0.000 description 42
- -1 ethylene, propylene, isobutylene Chemical group 0.000 description 42
- 239000008107 starch Substances 0.000 description 41
- 235000019698 starch Nutrition 0.000 description 40
- 238000000034 method Methods 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 18
- 238000004806 packaging method and process Methods 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229940105990 diglycerin Drugs 0.000 description 13
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 229920001567 vinyl ester resin Polymers 0.000 description 11
- 229920001577 copolymer Polymers 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- MWWXARALRVYLAE-UHFFFAOYSA-N 2-acetyloxybut-3-enyl acetate Chemical compound CC(=O)OCC(C=C)OC(C)=O MWWXARALRVYLAE-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 235000011187 glycerol Nutrition 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229920000881 Modified starch Polymers 0.000 description 6
- 239000004368 Modified starch Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 235000019426 modified starch Nutrition 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003905 agrochemical Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- 229920001353 Dextrin Polymers 0.000 description 3
- 239000004375 Dextrin Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 235000019425 dextrin Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000012766 organic filler Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 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 2
- IXAZNYYEGLSHOS-UHFFFAOYSA-N 2-aminoethanol;phosphoric acid Chemical compound NCCO.OP(O)(O)=O IXAZNYYEGLSHOS-UHFFFAOYSA-N 0.000 description 2
- IGDCJKDZZUALAO-UHFFFAOYSA-N 2-prop-2-enoxypropane-1,3-diol Chemical compound OCC(CO)OCC=C IGDCJKDZZUALAO-UHFFFAOYSA-N 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229920000856 Amylose Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229920006167 biodegradable resin Polymers 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920006319 cationized starch Polymers 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920005990 polystyrene resin Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229920001592 potato starch Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229940100486 rice starch Drugs 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- SQTUYFKNCCBFRR-UHFFFAOYSA-N (2,4-dimethoxyphenyl)boronic acid Chemical compound COC1=CC=C(B(O)O)C(OC)=C1 SQTUYFKNCCBFRR-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-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
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- YMDNODNLFSHHCV-UHFFFAOYSA-N 2-chloro-n,n-diethylethanamine Chemical compound CCN(CC)CCCl YMDNODNLFSHHCV-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 241000195955 Equisetum hyemale Species 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 240000005893 Pteridium aquilinum Species 0.000 description 1
- 235000009936 Pteridium aquilinum Nutrition 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- OMNKZBIFPJNNIO-UHFFFAOYSA-N n-(2-methyl-4-oxopentan-2-yl)prop-2-enamide Chemical compound CC(=O)CC(C)(C)NC(=O)C=C OMNKZBIFPJNNIO-UHFFFAOYSA-N 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 238000012858 packaging process Methods 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 description 1
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 description 1
- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- PUVAFTRIIUSGLK-UHFFFAOYSA-M trimethyl(oxiran-2-ylmethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1CO1 PUVAFTRIIUSGLK-UHFFFAOYSA-M 0.000 description 1
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 1
- ZQYKGADTDCTWSZ-UHFFFAOYSA-N trimethyl-[(prop-2-enoylamino)methyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CNC(=O)C=C ZQYKGADTDCTWSZ-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- CCVMLEHYQVSFOM-UHFFFAOYSA-N trimethyl-[2-(prop-2-enoylamino)ethyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCNC(=O)C=C CCVMLEHYQVSFOM-UHFFFAOYSA-N 0.000 description 1
- NFUDTVOYLQNLPF-UHFFFAOYSA-M trimethyl-[3-(2-methylprop-2-enoyloxy)propyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCCC[N+](C)(C)C NFUDTVOYLQNLPF-UHFFFAOYSA-M 0.000 description 1
- OEIXGLMQZVLOQX-UHFFFAOYSA-N trimethyl-[3-(prop-2-enoylamino)propyl]azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCCNC(=O)C=C OEIXGLMQZVLOQX-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Wrappers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
【課題】 冷水溶解性に優れ、更にヒートシール性（ヒートシール強度、ヒートシール部分の溶解性）、耐薬品性、長期保存後の柔軟性に優れたポリビニルアルコール系フィルムを提供すること。
【解決手段】 ２０℃の水に３分以内に溶解するポリビニルアルコール系フィルムであって、かつ、側鎖に１，２−グリコール結合を含有し、ケン化度が８５〜９７モル％であるポリビニルアルコール系樹脂（Ａ）及び多価アルコール（Ｂ）を含有してなる樹脂組成物からなるポリビニルアルコール系フィルム。
PROBLEM TO BE SOLVED: To provide a polyvinyl alcohol film which is excellent in cold water solubility, and further excellent in heat sealability (heat seal strength, heat seal portion solubility), chemical resistance and flexibility after long-term storage.
A polyvinyl alcohol film that dissolves in water at 20 ° C. within 3 minutes, contains a 1,2-glycol bond in the side chain, and has a saponification degree of 85 to 97 mol%. A polyvinyl alcohol film comprising a resin composition containing an alcohol resin (A) and a polyhydric alcohol (B).
Description
本発明は、ポリビニルアルコール系樹脂を主成分とするポリビニルアルコール系フィルムに関し、更に詳しくは、冷水溶解性に優れ、更にヒートシール性（ヒートシール強度、ヒートシール部分の溶解性）、耐薬品性、長期保存後の柔軟性に優れたポリビニルアルコール系フィルムに関するものである。 The present invention relates to a polyvinyl alcohol-based film containing a polyvinyl alcohol-based resin as a main component, more specifically, excellent in cold water solubility, heat sealability (heat seal strength, heat seal portion solubility), chemical resistance, The present invention relates to a polyvinyl alcohol film excellent in flexibility after long-term storage.
従来より、ポリビニルアルコール系フィルムは、その水溶性を活かして、農薬や洗剤等の薬剤の包装（ユニット包装）用途、（水圧）転写用フィルム、ナプキン・紙おむつ等の生理用品、オストミーバッグ等の汚物処理用品、吸血シート等の医療用品、育苗シート・シードテープ・刺繍用基布等の一時的基材等に用いられている。
中でも、農薬や洗剤等の薬剤のユニット包装用途では、使用時に一々計量する手間が省けるうえ、手を汚したりすることもないという利点がある。
これらに用いられる水溶性のポリビニルアルコール系樹脂としては、水溶解性、特に低温水溶解性を有するケン化度８０〜９０モル％程度の未変性部分鹸化ポリビニルアルコール系樹脂やスルホン酸基やカルボキシル基等で変性したポリビニルアルコール系樹脂が一般的である。
しかしながら、これらの従来のポリビニルアルコール系フィルムは、水溶性には優れるものの、農薬や洗剤等を分包（ユニット包装）し、長期間保存する場合には、薬品の影響により、フィルム中の可塑剤が薬剤に移行し、フィルムの可撓性や柔軟性が低下し、運搬中の衝撃等によりフィルムが破袋するなどの不都合が生じている。冬場や寒冷地等では、特に大きな問題となっている。
また、ユニット包装加工の工程において、一般的に行なわれているヒートシール処理により、処理部分におけるポリビニルアルコール系フィルムの結晶性が高くなり、フィルムの一部が溶け残るなどの不都合も生じている。
Conventionally, polyvinyl alcohol films have been used for packaging of chemicals such as agricultural chemicals and detergents (unit packaging), (hydraulic pressure) transfer films, sanitary products such as napkins and disposable diapers, and filth such as ostomy bags. It is used for treatment supplies, medical supplies such as blood-absorbing sheets, temporary substrates such as seedling sheets, seed tapes, and embroidery base fabrics.
Above all, in the unit packaging use of chemicals such as agricultural chemicals and detergents, there is an advantage that it is possible to save the trouble of weighing each time during use and not to get the hands dirty.
Examples of water-soluble polyvinyl alcohol resins used for these include water-soluble, particularly low-temperature water-soluble, unmodified partially saponified polyvinyl alcohol resins having a saponification degree of about 80 to 90 mol%, sulfonic acid groups, and carboxyl groups. A polyvinyl alcohol-based resin modified with the above is generally used.
However, these conventional polyvinyl alcohol-based films are excellent in water solubility, however, when packaging agricultural chemicals and detergents (unit packaging) and storing them for a long time, the plasticizer in the film is affected by the influence of chemicals. However, there is a problem that the flexibility and softness of the film are lowered and the film is broken by an impact during transportation. This is a particularly serious problem in winter and cold regions.
Further, in the unit packaging process, due to the heat sealing process that is generally performed, the crystallinity of the polyvinyl alcohol-based film in the processed part is increased, and there is a problem that part of the film remains undissolved.
かかる問題に対する対策の一つとして、スルホン酸基またはカルボキシル基からなる共重合体単位を含有するポリビニルアルコール系樹脂１００重量部に、３〜６価の多価アルコール１モルに対しアルキレンオキサイド１〜４モルを付加反応して得られた化合物３〜１００重量部を配合してなる組成物からなる水溶性フィルムが提案されている（例えば、特許文献１参照。）。
しかしながら、特許文献１の開示技術では、冷水溶解性や長期保存後の柔軟性については改善されているもののまだまだ満足するものではなく、一般的に可塑剤として用いられるグリセリンやジグリセリンに比べても可塑効果に劣るものであり、更に、上記のヒートシール性については改善されておらず、不充分であり、更なる改良が求められている。
そこで、本発明ではこのような背景下において、冷水溶解性に優れ、更にヒートシール性（ヒートシール強度、ヒートシール部分の溶解性）、耐薬品性、長期保存後の柔軟性に優れたポリビニルアルコール系フィルム及びそれを用いた薬剤包装体を提供することを目的とするものである。
However, the disclosed technology of Patent Document 1 is not yet satisfactory although it is improved in terms of cold water solubility and flexibility after long-term storage, and is generally less than glycerin and diglycerin that are generally used as plasticizers. The plastic effect is inferior, and the heat sealability is not improved and insufficient, and further improvement is required.
Therefore, in the present invention, under such a background, polyvinyl alcohol having excellent cold water solubility, heat sealability (heat seal strength, solubility of heat seal portion), chemical resistance, and flexibility after long-term storage. An object of the present invention is to provide a system film and a medicine package using the same.
しかるに、本発明者等は上記の如き現況に鑑み鋭意研究した結果、２０℃の水に３分以内に溶解するポリビニルアルコール系フィルムであって、かつ、側鎖に１，２−グリコール結合を含有し、ケン化度が８５〜９７モル％であるポリビニルアルコール系樹脂（Ａ）及び多価アルコール（Ｂ）を含有してなる樹脂組成物からなるポリビニルアルコール系フィルムが、上記目的に合致することを見出し、本発明を完成した。
本発明では特に、ポリビニルアルコール系樹脂（Ａ）の側鎖に含有する１，２−グリコール結合量が３〜１２モル％であることが好ましく、また、ポリビニルアルコール系樹脂（Ａ）の２０℃における４重量％水溶液粘度が４〜４００ｍＰａ・ｓであることが好ましい。
本発明では、更に界面活性剤（Ｃ）を含有してなることも好ましい。
また本発明では、１重量％の懸濁液または水溶液とした時のｐＨが１〜１２（２０℃）となるような薬剤を上記ポリビニルアルコール系フィルムで包装してなる薬剤包装体も提供するものである。
However, as a result of intensive studies in view of the present situation as described above, the inventors of the present invention are polyvinyl alcohol films that dissolve in water at 20 ° C. within 3 minutes, and contain 1,2-glycol bonds in the side chains. And a polyvinyl alcohol film made of a resin composition containing a polyvinyl alcohol resin (A) and a polyhydric alcohol (B) having a saponification degree of 85 to 97 mol% is suitable for the above purpose. The headline and the present invention were completed.
In the present invention, the amount of 1,2-glycol bonds contained in the side chain of the polyvinyl alcohol resin (A) is preferably 3 to 12 mol%, and the polyvinyl alcohol resin (A) at 20 ° C. The viscosity of a 4% by weight aqueous solution is preferably 4 to 400 mPa · s.
In the present invention, it is also preferable to further contain a surfactant (C).
In the present invention, there is also provided a drug package in which a drug having a pH of 1 to 12 (20 ° C.) with a 1% by weight suspension or aqueous solution is packaged with the polyvinyl alcohol film. It is.
本発明のポリビニルアルコール系フィルムは、２０℃の水に３分以内に溶解するポリビニルアルコール系フィルムであって、かつ、側鎖に１，２−グリコール結合を含有し、ケン化度が８５〜９７モル％であるポリビニルアルコール系樹脂（Ａ）及び多価アルコール（Ｂ）を含有してなる樹脂組成物からなるため、農薬や洗剤などの薬剤を包装しても、冷水溶解性、ヒートシール性（ヒートシール強度、ヒートシール部分の溶解性）、耐薬品性、長期保存後の柔軟性に優れたフィルムであり、各種の包装用途等に有用で、特に薬剤等のユニット包装用途に有用である。中でも本発明では、水に分散または溶解させて１重量％の懸濁液または水溶液とした時のｐＨが１〜１２（２０℃）となるような薬剤を包装するのに有用である。 The polyvinyl alcohol film of the present invention is a polyvinyl alcohol film that dissolves in water at 20 ° C. within 3 minutes, contains a 1,2-glycol bond in the side chain, and has a saponification degree of 85 to 97. Because it is composed of a resin composition containing a polyvinyl alcohol resin (A) and a polyhydric alcohol (B) that are mol%, cold water solubility, heat sealability ( It is a film excellent in heat seal strength, solubility of heat seal portion), chemical resistance, and flexibility after long-term storage, and is useful for various packaging applications, and particularly useful for unit packaging applications such as drugs. In particular, the present invention is useful for packaging a drug having a pH of 1 to 12 (20 ° C.) when dispersed or dissolved in water to form a 1% by weight suspension or aqueous solution.
以下、本発明について具体的に説明する。
本発明のポリビニルアルコール系フィルムは、２０℃の水に３分以内に溶解するポリビニルアルコール系フィルムであって、かつ、側鎖に１，２−グリコール結合を含有し、ケン化度が８５〜９７モル％であるポリビニルアルコール系樹脂（Ａ）及び多価アルコール（Ｂ）を含有してなるものである。
Hereinafter, the present invention will be specifically described.
The polyvinyl alcohol film of the present invention is a polyvinyl alcohol film that dissolves in water at 20 ° C. within 3 minutes, contains a 1,2-glycol bond in the side chain, and has a saponification degree of 85 to 97. It contains a polyvinyl alcohol-based resin (A) and a polyhydric alcohol (B) that are mol%.
本発明で用いるポリビニルアルコール系樹脂（Ａ）としては、側鎖に１，２−グリコール結合を有するポリビニルアルコール系樹脂、即ち、一般式（１）で示される１，２−グリコール構造単位を含有するポリビニルアルコール系樹脂であれば特に限定されない。 The polyvinyl alcohol resin (A) used in the present invention contains a polyvinyl alcohol resin having a 1,2-glycol bond in the side chain, that is, a 1,2-glycol structural unit represented by the general formula (1). If it is a polyvinyl alcohol-type resin, it will not specifically limit.
（ここで、Ｒ1、Ｒ2、Ｒ3はそれぞれ独立して水素又はアルキル基である。）
(Here, R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group.)
このようなポリビニルアルコール系樹脂（Ａ）は、例えば、（ア）ビニルエステル系モノマーと３，４−ジアセトキシ−１−ブテンとの共重合体をケン化することによって製造することができる。
かかるビニルエステル系モノマーとしては、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、バレリン酸ビニル、酪酸ビニル、イソ酪酸ビニル、ピバリン酸ビニル、カプリン酸ビニル、ラウリン酸ビニル、ステアリン酸ビニル、安息香酸ビニル、バーサチック酸ビニル等が挙げられるが、中でも酢酸ビニルが好ましく用いられる。
Such a polyvinyl alcohol resin (A) can be produced, for example, by saponifying a copolymer of (a) a vinyl ester monomer and 3,4-diacetoxy-1-butene.
Such vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, versatic. Although vinyl acid acid etc. are mentioned, Vinyl acetate is used preferably especially.
かかるビニルエステル系モノマーと共重合される３，４−ジアセトキシ−１−ブテンとは、下記の化学式（２）で示されるものである。
（ここで、Ｒはアルキル基で、好ましくはメチル基である。）
なお、上記の（２）式で示される化合物は、イーストマンケミカル社やアクロス社の製品として市場から入手したり、ブタンジオール製造時の中間体を精製して使用することができる。
The 3,4-diacetoxy-1-butene copolymerized with such a vinyl ester monomer is represented by the following chemical formula (2).
(Here, R is an alkyl group, preferably a methyl group.)
In addition, the compound represented by the above formula (2) can be obtained from the market as a product of Eastman Chemical Co. or Acros Co., or can be used by purifying an intermediate during butanediol production.
また、本発明においては、上記の共重合成分以外にも本発明の目的を阻害しない範囲において、他のモノマーを共重合させることも可能で、例えばエチレン、プロピレン、イソブチレン、α−オクテン、α−ドデセン、α−オクタデセン等のオレフィン類、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸等の不飽和酸類あるいはその塩あるいはモノ又はジアルキルエステル等、アクリロニトリル、メタアクリロニトリル等のニトリル類、ジアセトンアクリルアミド、アクリルアミド、メタクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸あるいはその塩、グリセリンモノアリルエーテル、アルキルビニルエーテル類、ジメチルアリルビニルケトン、Ｎ−ビニルピロリドン、塩化ビニル、塩化ビニリデン、ポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテル等のポリオキシアルキレン（メタ）アリルエーテル、ポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート等のポリオキシアルキレン（メタ）アクリレート、ポリオキシエチレン（メタ）アクリルアミド、ポリオキシプロピレン（メタ）アクリルアミド等のポリオキシアルキレン（メタ）アクリルアミド、ポリオキシエチレン（１−（メタ）アクリルアミド−１，１−ジメチルプロピル）エステル、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル、ポリオキシエチレンアリルアミン、ポリオキシプロピレンアリルアミン、ポリオキシエチレンビニルアミン、ポリオキシプロピレンビニルアミン、エチレンカーボネート、アリルアセテート等が挙げられる。 In the present invention, in addition to the above copolymerization component, other monomers can be copolymerized within a range not inhibiting the purpose of the present invention. For example, ethylene, propylene, isobutylene, α-octene, α- Olefins such as dodecene and α-octadecene, unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride and itaconic acid or salts thereof, mono- or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile Amides such as diacetone acrylamide, acrylamide and methacrylamide, olefin sulfonic acids such as ethylene sulfonic acid, allyl sulfonic acid and methallyl sulfonic acid or salts thereof, glycerol monoallyl ether, alkyl vinyl ethers, dimethylallyl vinyl Luketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) allyl ether, polyoxyalkylene (meth) allyl ether such as polyoxypropylene (meth) allyl ether, polyoxyethylene (meth) acrylate, poly Polyoxyalkylene (meth) acrylates such as oxypropylene (meth) acrylate, polyoxyethylene (meth) acrylamide, polyoxyalkylene (meth) acrylamides such as polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) (Acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allyla Emissions, polyoxyethylene vinyl amine, polyoxypropylene vinyl amine, ethylene carbonate, allyl acetate, and the like.
さらに、Ｎ−アクリルアミドメチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドエチルトリメチルアンモニウムクロライド、Ｎ−アクリルアミドプロピルトリメチルアンモニウムクロライド、２−アクリロキシエチルトリメチルアンモニウムクロライド、２−メタクリロキシエチルトリメチルアンモニウムクロライド、２−ヒドロキシ−３−メタクリロイルオキシプロピルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、メタアリルトリメチルアンモニウムクロライド、３−ブテントリメチルアンモニウムクロライド、ジメチルジアリルアンモニウムクロリド、ジエチルジアリルアンモニウムクロライド等のカチオン基含有単量体、アセトアセチル基含有単量体等も挙げられる。 Furthermore, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 2-hydroxy-3- Cationic group-containing monomers such as methacryloyloxypropyltrimethylammonium chloride, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, 3-butenetrimethylammonium chloride, dimethyldiallylammonium chloride, diethyldiallylammonium chloride, acetoacetyl group-containing monomers And so on.
上記のビニルエステル系モノマーと３，４−ジアセトキシ−１−ブテン（さらには他のモノマー）を共重合するに当たっては、特に制限はなく、塊状重合、溶液重合、懸濁重合、分散重合、またはエマルジョン重合等の公知の方法を採用することができるが、通常は溶液重合が行われる。 There are no particular restrictions on the copolymerization of the above vinyl ester monomer and 3,4-diacetoxy-1-butene (and other monomers), and there are no block polymerization, bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, or emulsion. Although known methods such as polymerization can be employed, solution polymerization is usually performed.
共重合時のモノマー成分の仕込み方法としては特に制限されず、一括仕込み、分割仕込み、連続仕込み等任意の方法が採用されるが、３，４−ジアセトキシ−１−ブテンがポリビニルエステル系ポリマーの分子鎖中に均一に分布させられる、ポリビニルアルコール の融点が降下する等の物性面での点から滴下重合が好ましく、特にはＨＡＮＮＡ法に基づく重合方法が好ましい。 The method for charging the monomer component at the time of copolymerization is not particularly limited, and any method such as batch charging, split charging, continuous charging, etc. is adopted, but 3,4-diacetoxy-1-butene is a molecule of a polyvinyl ester polymer. Drop polymerization is preferred from the standpoint of physical properties such as uniform distribution in the chain and a decrease in the melting point of polyvinyl alcohol, and a polymerization method based on the HANNA method is particularly preferred.
かかる共重合で用いられる溶媒としては、通常、メタノール、エタノール、プロパノール、ブタノール等の低級アルコールやアセトン、メチルエチルケトン等のケトン類等が挙げられ、工業的には、メタノールが好適に使用される。
溶媒の使用量は、目的とする共重合体の重合度に合わせて、溶媒の連鎖移動定数を考慮して適宜選択すればよく、例えば、溶媒がメタノールの時は、Ｓ（溶媒）／Ｍ（モノマー）＝０．０１〜１０（重量比）、好ましくは０．０５〜３（重量比）程度の範囲から選択される。
Examples of the solvent used in such copolymerization include usually lower alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, and industrially, methanol is preferably used.
The amount of the solvent used may be appropriately selected in consideration of the chain transfer constant of the solvent in accordance with the degree of polymerization of the target copolymer. For example, when the solvent is methanol, S (solvent) / M ( Monomer) = 0.01 to 10 (weight ratio), preferably 0.05 to 3 (weight ratio).
共重合に当たっては重合触媒が用いられ、かかる重合触媒としては、例えばアゾビスイソブチロニトリル、過酸化アセチル、過酸化ベンゾイル、過酸化ラウリル等の公知のラジカル重合触媒やアゾビスジメチルバレロニトリル、アゾビスメトキシジメチルバレロニトリル等の低温活性ラジカル重合触媒等が挙げられ、重合触媒の使用量は、触媒の種類により異なり一概には決められないが、重合速度に応じて任意に選択される。例えば、アゾイソブチロニトリルや過酸化アセチルを用いる場合、ビニルエステル系モノマーに対して０．０１〜０．２モル％が好ましく、特には０．０２〜０．１５モル％が好ましい。
また、共重合反応の反応温度は、使用する溶媒や圧力により４０℃〜沸点程度とすることが好ましい。
For the copolymerization, a polymerization catalyst is used. Examples of the polymerization catalyst include known radical polymerization catalysts such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, lauryl peroxide, azobisdimethylvaleronitrile, azo Examples include low-temperature active radical polymerization catalysts such as bismethoxydimethylvaleronitrile, and the amount of polymerization catalyst used varies depending on the type of catalyst and cannot be determined unconditionally, but is arbitrarily selected according to the polymerization rate. For example, when azoisobutyronitrile or acetyl peroxide is used, 0.01 to 0.2 mol% is preferable with respect to the vinyl ester monomer, and 0.02 to 0.15 mol% is particularly preferable.
Moreover, it is preferable that the reaction temperature of a copolymerization reaction shall be about 40 degreeC-about a boiling point by the solvent and pressure to be used.
本発明においては、３，４−ジアセトキシ−１−ブテンの共重合割合は特に限定されないが、後述の１，２−グリコール結合の導入量に合わせて共重合割合を決定すればよい。 In the present invention, the copolymerization ratio of 3,4-diacetoxy-1-butene is not particularly limited, but the copolymerization ratio may be determined in accordance with the amount of 1,2-glycol bond introduced below.
得られた共重合体は、次いでケン化されるのであるが、かかるケン化にあたっては、上記で得られた共重合体をアルコールまたは含水アルコールに溶解し、アルカリ触媒又は酸触媒を用いて行われる。アルコールとしては、メタノール、エタノール、プロパノール、ｔｅｒｔ−ブタノール等が挙げられるが、メタノールが特に好ましく用いられる。アルコール中の共重合体の濃度は系の粘度により適宜選択されるが、通常は１０〜６０重量％の範囲から選ばれる。ケン化に使用される触媒としては、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、ナトリウムエチラート、カリウムメチラート、リチウムメチラート等のアルカリ金属の水酸化物やアルコラートの如きアルカリ触媒、硫酸、塩酸、硝酸、メタスルフォン酸、ゼオライト、カチオン交換樹脂等の酸触媒が挙げられる。 The obtained copolymer is then saponified. In such saponification, the above-obtained copolymer is dissolved in an alcohol or a hydrous alcohol, and an alkali catalyst or an acid catalyst is used. . Examples of the alcohol include methanol, ethanol, propanol, tert-butanol and the like, and methanol is particularly preferably used. The concentration of the copolymer in the alcohol is appropriately selected depending on the viscosity of the system, but is usually selected from the range of 10 to 60% by weight. Catalysts used for saponification include alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium methylate, lithium methylate, etc., sulfuric acid, Examples include acid catalysts such as hydrochloric acid, nitric acid, metasulfonic acid, zeolite, and cation exchange resin.
かかるケン化触媒の使用量については、ケン化方法、目標とするケン化度等により適宜選択されるが、アルカリ触媒を使用する場合は通常、ビニルエステル系モノマー及び３，４−ジアセトキシ−１−ブテンの合計量１モルに対して０．１〜３０ミリモル、好ましくは２〜１７ミリモルが適当である。
また、ケン化反応の反応温度は特に限定されないが、１０〜６０℃が好ましく、より好ましくは２０〜５０℃である。
上記ポリビニルアルコール系樹脂（Ａ）は上記の如くケン化時にビニルエステル系モノマーのエステル部分と３，４−ジアセトキシ−１−ブテンのアセトキシ部分を同時に水酸基へ変換することによって製造される。
The amount of the saponification catalyst used is appropriately selected depending on the saponification method, the target degree of saponification, and the like. Usually, when an alkali catalyst is used, a vinyl ester monomer and 3,4-diacetoxy-1- A suitable amount is 0.1 to 30 mmol, preferably 2 to 17 mmol, based on 1 mol of butene.
Moreover, although the reaction temperature of saponification reaction is not specifically limited, 10-60 degreeC is preferable, More preferably, it is 20-50 degreeC.
The polyvinyl alcohol resin (A) is produced by simultaneously converting the ester portion of the vinyl ester monomer and the acetoxy portion of 3,4-diacetoxy-1-butene into hydroxyl groups during saponification as described above.
かくして、側鎖に１，２−グリコール結合を含有するポリビニルアルコール系樹脂（Ａ）が得られるのであるが、本発明では、かかるポリビニルアルコール系樹脂（Ａ）のケン化度は、８５〜９７モル％、特には８８〜９７モル％が好ましく、かかるケン化度が８５モル％未満ではフィルム強度や耐薬品性が低下し、９７モル％を超えるとヒートシール部の溶解性が低下することとなる。 Thus, a polyvinyl alcohol resin (A) containing a 1,2-glycol bond in the side chain is obtained. In the present invention, the saponification degree of the polyvinyl alcohol resin (A) is 85 to 97 mol. %, Particularly 88 to 97 mol% is preferred. When the degree of saponification is less than 85 mol%, the film strength and chemical resistance are lowered, and when it exceeds 97 mol%, the solubility of the heat seal part is lowered. .
なお、本発明におけるケン化度とは、ビニルエステル系モノマーのエステル部分及び３，４−ジアセトキシ−１−ブテンのアセトキシ部分の総量の水酸基への変化率（モル％）で表示される（ケン化反応において、３，４−ジアセトキシ−１−ブテンのアセトキシ部分はほぼ完全にケン化される）。 The saponification degree in the present invention is expressed by the rate of change (mol%) of the total amount of the ester portion of the vinyl ester monomer and the acetoxy portion of 3,4-diacetoxy-1-butene to the hydroxyl group (saponification). In the reaction, the acetoxy part of 3,4-diacetoxy-1-butene is almost completely saponified).
また、ポリビニルアルコール系樹脂（Ａ）の側鎖に導入される１，２−グリコール結合量としては、３〜１２モル％であることが好ましく、更に好ましくは３〜１０モル％、特に好ましくは４〜８モル％である。かかる結合量が３モル％未満では本発明の効果が得難く、逆に１２モル％を超えると生産性が低下するため好ましくない。 The amount of 1,2-glycol bond introduced into the side chain of the polyvinyl alcohol-based resin (A) is preferably 3 to 12 mol%, more preferably 3 to 10 mol%, and particularly preferably 4 ~ 8 mol%. If the amount is less than 3 mol%, it is difficult to obtain the effect of the present invention. On the other hand, if it exceeds 12 mol%, productivity is lowered, which is not preferable.
更に、上記ポリビニルアルコール系樹脂（Ａ）の２０℃における４重量％水溶液粘度は４〜４００ｍＰａ・ｓ、特には４〜３００ｍＰａ・ｓ、更には８〜２７０ｍＰａ・ｓが好ましく、かかる４重量％水溶液粘度が４ｍＰａ・ｓ未満ではフィルム強度が不足することとなり、４００ｍＰａ・ｓを超えるとフィルムの平面平滑性が低下することとなり好ましくない。 Further, the viscosity of a 4% by weight aqueous solution of the polyvinyl alcohol resin (A) at 20 ° C. is preferably 4 to 400 mPa · s, particularly preferably 4 to 300 mPa · s, and more preferably 8 to 270 mPa · s. If it is less than 4 mPa · s, the film strength will be insufficient, and if it exceeds 400 mPa · s, the planar smoothness of the film will decrease, which is not preferred.
また、本発明で用いるポリビニルアルコール系樹脂（Ａ）の製造方法として、上記（ア）ビニルエステル系モノマーと３，４−ジアセトキシ−１−ブテンとの共重合体をケン化する方法について詳述したが、かかる方法に限定されることなく、例えば、（イ）ビニルエステル系モノマーと一般式（３）で示されるビニルエチレンカーボネートとの共重合体をケン化及び脱炭酸する方法、（ウ）ビニルエステル系モノマーと一般式（４）で示される２，２−ジアルキル−４−ビニル−１，３−ジオキソランとの共重合体をケン化及び脱ケタール化する方法、（エ）ビニルエステル系モノマーとグリセリンモノアリルエーテルとの共重合体をケン化する方法、等も挙げられ、特に限定されるものではない。なお、ビニルエチレンカーボネートは、イーストマンケミカル社品として市場から入手することができる。 In addition, as a method for producing the polyvinyl alcohol-based resin (A) used in the present invention, a method for saponifying the copolymer of the above (a) vinyl ester-based monomer and 3,4-diacetoxy-1-butene was described in detail. However, without being limited to such a method, for example, (a) a method of saponifying and decarboxylating a copolymer of a vinyl ester monomer and a vinyl ethylene carbonate represented by the general formula (3), (c) vinyl A method of saponifying and deketalizing a copolymer of an ester monomer and a 2,2-dialkyl-4-vinyl-1,3-dioxolane represented by the general formula (4), and (d) a vinyl ester monomer A method of saponifying a copolymer with glycerin monoallyl ether, and the like are also exemplified and are not particularly limited. Vinyl ethylene carbonate can be obtained from the market as a product of Eastman Chemical Company.
但し、Ｒ1、Ｒ2、Ｒ3はそれぞれ独立して水素又はアルキル基である。
However, R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group.
但し、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ5はそれぞれ独立して水素又はアルキル基である。
However, R 1 , R 2 , R 3 , R 4 and R 5 are each independently hydrogen or an alkyl group.
本発明で用いる多価アルコール（Ｂ）としては、特に限定されず、例えば、エチレングリコール、グリセリン、プロピレングリコール、ジエチレングリコール、ジグリセリン、トリエチレングリコール、トリエチレングリコール、テトラエチレングリコール、トリメチロールプロパンや、重合度が３００以下のポリエチレングリコール等が挙げられ、これらの多価アルコールは単独または二種以上組み合わせて使用することができる。中でも特にグリセリン単独、ジグリセリン単独、もしくはグリセリンとジグリセリンまたはグリセリンとトリメチロールプロパンの組み合わせ等がユニット包装時の成型加工等の点で好適である。 The polyhydric alcohol (B) used in the present invention is not particularly limited. For example, ethylene glycol, glycerin, propylene glycol, diethylene glycol, diglycerin, triethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, Examples thereof include polyethylene glycol having a degree of polymerization of 300 or less, and these polyhydric alcohols can be used alone or in combination of two or more. Among these, glycerin alone, diglycerin alone, or a combination of glycerin and diglycerin or glycerin and trimethylolpropane is particularly preferable in terms of molding processing during unit packaging.
グリセリンと、ジグリセリン及び／又はトリメチロールプロパンとを併用するに当たっては、グリセリンとトリメチロールプロパン及び／又はジグリセリンの含有割合が１５／８５〜８５／１５（重量比）であることが好ましく、特には２０／８０〜８０／２０（重量比）、更には２５／７５〜７５／２５（重量比）であることが好ましい。かかる含有割合が１５／８５（重量比）未満では常温以下での可塑効果が低く、８５／１５（重量比）を越えると経時安定性が低下する傾向となり好ましくない。 When glycerin and diglycerin and / or trimethylolpropane are used in combination, the content ratio of glycerin and trimethylolpropane and / or diglycerin is preferably 15/85 to 85/15 (weight ratio). Is preferably 20/80 to 80/20 (weight ratio), more preferably 25/75 to 75/25 (weight ratio). When the content ratio is less than 15/85 (weight ratio), the plasticizing effect at room temperature or lower is low, and when it exceeds 85/15 (weight ratio), the stability with time tends to decrease.
かかる多価アルコール（Ｂ）の含有量としては、ポリビニルアルコール系樹脂（Ａ）１００重量部に対して２〜４０重量部であることが好ましく、特には３〜３８重量部、更には４〜３５重量部であることが好ましい。多価アルコール（Ｂ）の含有量が２重量部未満では可塑効果が得られず、４０重量部を超えると放置安定性が低下し好ましくない。 As content of this polyhydric alcohol (B), it is preferable that it is 2-40 weight part with respect to 100 weight part of polyvinyl alcohol-type resin (A), Especially 3-38 weight part, Furthermore, 4-35. It is preferable that it is a weight part. If the content of the polyhydric alcohol (B) is less than 2 parts by weight, the plastic effect cannot be obtained, and if it exceeds 40 parts by weight, the storage stability is unfavorably lowered.
本発明では、上記ポリビニルアルコール系樹脂（Ａ）及び多価アルコール（Ｂ）の他に更に、界面活性剤（Ｃ）を含有することが好ましく、かかる界面活性剤（Ｃ）としては、特に限定されず、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンオクチルノニルエーテル、ポリオキシエチレンドデシルフェニルエーテル、ポリオキシエチレンアルキルアリルエーテル、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシアルキレンアルキルエーテルリン酸エステルモノエタノールアミン塩、ポリオキシエチレンラウリルアミン、ポリオキシエチレンステアリルアミン等のポリオキシエチレンアルキルアミン等が挙げられ、１種又は２種以上併用して用いられる。中でも、製造安定性の点でポリオキシアルキレンアルキルエーテルリン酸エステルモノエタノールアミン塩、ポリオキシエチレンラウリルアミンが好適である。 In the present invention, it is preferable to further contain a surfactant (C) in addition to the polyvinyl alcohol resin (A) and the polyhydric alcohol (B), and the surfactant (C) is particularly limited. For example, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl nonyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxy Ethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyalkylene alkyl ether phosphate monoethanolamine salt, polyoxyethylene laurylamine, polyoxyethylene stearate Polyoxyethylene alkyl amines such as amine and the like, used in combination one or more. Of these, polyoxyalkylene alkyl ether phosphate monoethanolamine salt and polyoxyethylene laurylamine are preferable in terms of production stability.
かかる界面活性剤（Ｃ）の含有量については、ポリビニルアルコール系樹脂（Ａ）１００重量部に対して０．１〜５重量部、好ましくは０．２〜４重量部、特に好ましくは０．３〜３重量部である。該含有量が０．１重量部未満では製膜装置のドラムやベルト等の金属表面と製膜したフィルムとの剥離性が低下して製造困難となり、５重量部を超えるとフィルムを包装体とする場合に実施するヒートシール時の接着強度が低下する等の不都合を生じることとなり好ましくない。 About content of this surfactant (C), 0.1-5 weight part with respect to 100 weight part of polyvinyl alcohol-type resin (A), Preferably 0.2-4 weight part, Especially preferably, it is 0.3. ~ 3 parts by weight. When the content is less than 0.1 part by weight, the peelability between the metal surface such as a drum or belt of the film forming apparatus and the formed film is lowered, and the production becomes difficult. In that case, it causes an inconvenience such as a decrease in adhesive strength during heat sealing, which is not preferable.
かくして本発明では、上記側鎖１，２−グリコール結合を含有するポリビニルアルコール系樹脂（Ａ）及び多価アルコール（Ｂ）、好ましくは更に界面活性剤（Ｃ）を含有してなる樹脂組成物を得、製膜するのであるが、必要に応じて、更にフィラーや澱粉を含有させることができる。 Thus, in the present invention, a resin composition comprising the polyvinyl alcohol resin (A) and polyhydric alcohol (B) containing the side chain 1,2-glycol bond, preferably further containing the surfactant (C). Although it is obtained and formed into a film, a filler and starch can be further contained as required.
フィラーとしては、無機フィラーや有機フィラーが挙げられ、無機フィラーとしては、その平均粒子径が１〜１０μｍのものであることが好ましく、かかる平均粒子径が１μｍ未満ではフィルムのブロッキング抑制効果が少なく、１０μｍを越えるとフィルムの外観が悪くなり商品価値が低下し好ましくない。具体例としては、例えば、タルク、クレー、二酸化ケイ素、ケイ藻土、カオリン、雲母、アスベスト、石膏、グラファイト、ガラスバルーン、ガラスビーズ、硫酸カルシウム、硫酸バリウム、硫酸アンモニウム、亜硫酸カルシウム、炭酸カルシウム、ウイスカー状炭酸カルシウム、炭酸マグネシウム、ドーソナイト、ドロマイト、チタン酸カリウム、カーボンブラック、ガラス繊維、アルミナ繊維、ボロン繊維、加工鉱物繊維、炭素繊維、炭素中空球、ベントナイト、モンモリロナイト、銅粉、硫酸ナトリウム、硫酸カリウム、硫酸亜鉛、硫酸銅、硫酸鉄、硫酸マグネシウム、硫酸アルミニウム、硫酸アルミニウムカリウム、硝酸アンモニウム、硝酸ナトリウム、硝酸カリウム、硝酸アルミニウム、塩化アンモニウム、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、リン酸ナトリウム、クロム酸カリウム、クエン酸カルシウム等が挙げられる。 Examples of the filler include inorganic fillers and organic fillers, and the inorganic filler preferably has an average particle size of 1 to 10 μm. When the average particle size is less than 1 μm, the film blocking suppression effect is small. If it exceeds 10 μm, the appearance of the film deteriorates and the commercial value is unfavorable. Specific examples include, for example, talc, clay, silicon dioxide, diatomaceous earth, kaolin, mica, asbestos, gypsum, graphite, glass balloon, glass beads, calcium sulfate, barium sulfate, ammonium sulfate, calcium sulfite, calcium carbonate, whisker-like Calcium carbonate, magnesium carbonate, dosonite, dolomite, potassium titanate, carbon black, glass fiber, alumina fiber, boron fiber, processed mineral fiber, carbon fiber, carbon hollow sphere, bentonite, montmorillonite, copper powder, sodium sulfate, potassium sulfate, Zinc sulfate, copper sulfate, iron sulfate, magnesium sulfate, aluminum sulfate, potassium aluminum sulfate, ammonium nitrate, sodium nitrate, potassium nitrate, aluminum nitrate, ammonium chloride, sodium chloride, chloride Potassium, magnesium chloride, calcium chloride, sodium phosphate, potassium chromate, calcium citrate.
また、有機フィラーとしては、その平均粒子径が０．５〜１０μｍのものであることが好ましく、より好ましくは０．５〜７μｍ、特に好ましくは０．５〜５μｍ、更に好ましくは０．５〜３μｍである。該平均粒子径が０．５μｍ未満ではコスト面で高くなり、１０μｍを越えると分散性が低下することとなり好ましくない。
かかる有機フィラーの具体例としては、例えば、澱粉、メラミン系樹脂、ポリメチル（メタ）アクリレート系樹脂、ポリスチレン系樹脂の他、ポリ乳酸、米澱粉等の生分解性樹脂等も挙げられるが、特にはポリメチル（メタ）アクリレート系樹脂、ポリスチレン系樹脂、生分解性樹脂が好適に用いられる。
Moreover, as an organic filler, it is preferable that the average particle diameter is 0.5-10 micrometers, More preferably, it is 0.5-7 micrometers, Most preferably, it is 0.5-5 micrometers, More preferably, it is 0.5- 3 μm. If the average particle diameter is less than 0.5 μm, the cost is increased, and if it exceeds 10 μm, the dispersibility is lowered.
Specific examples of such organic fillers include, for example, starch, melamine resin, polymethyl (meth) acrylate resin, polystyrene resin, and biodegradable resins such as polylactic acid and rice starch. Polymethyl (meth) acrylate resins, polystyrene resins, and biodegradable resins are preferably used.
上記フィラーの含有量については、ポリビニルアルコール系樹脂（Ａ）１００重量部に対して２〜３０重量部、好ましくは２．５〜２５重量部、特に好ましくは２．５〜２０重量部であり、かかる含有量が２重量部未満ではフィルムの水中への分散性に効果がなく、３０重量部を越えるとフィルムの水中への分散性が低下することとなり好ましくない。 About content of the said filler, it is 2-30 weight part with respect to 100 weight part of polyvinyl alcohol-type resin (A), Preferably it is 2.5-25 weight part, Most preferably, it is 2.5-20 weight part, If the content is less than 2 parts by weight, the dispersibility of the film in water is not effective, and if it exceeds 30 parts by weight, the dispersibility of the film in water is lowered, which is not preferable.
澱粉は、ブロッキング防止や機械強度の調整の目的で含有されるが、その平均粒子径が１０μｍ以上のもの（上記フィラーで記載の澱粉とは平均粒子径が異なる）であることが好ましく、具体例としては、生澱粉（トウモロコシ澱粉、馬鈴薯澱粉、甘藷澱粉、コムギ澱粉、キッサバ澱粉、サゴ澱粉、タピオカ澱粉、モロコシ澱粉、コメ澱粉、マメ澱粉、クズ澱粉、ワラビ澱粉、ハス澱粉、ヒシ澱粉等）；物理的変性澱粉（α−澱粉、分別アミロース、湿熱処理澱粉等）；酵素変性澱粉（加水分解デキストリン、酵素分解デキストリン、アミロース等）；化学分解変性澱粉（酸処理澱粉、次亜塩素酸酸化澱粉、ジアルデヒド澱粉等）；化学変性澱粉誘導体（エステル化澱粉、エーテル化澱粉、カチオン化澱粉、架橋澱粉等）等が挙げられる。尚、化学変性澱粉誘導体のうちエステル化澱粉としては、酢酸エステル化澱粉、コハク酸エステル化澱粉、硝酸エステル化澱粉、リン酸エステル化澱粉、尿素リン酸エステル化澱粉、キサントゲン酸エステル化澱粉、アセト酢酸エステル化澱粉等、エーテル化澱粉としては、アリルエーテル化澱粉、メチルエーテル化澱粉、カルボキシメチルエーテル化澱粉、ヒドロキシエチルエーテル化澱粉、ヒドロキシプロピルエーテル化澱粉等、カチオン化澱粉としては、澱粉と２−ジエチルアミノエチルクロライドの反応物、澱粉と２,３−エポキシプロピルトリメチルアンモニウムクロライドの反応物等、架橋澱粉としては、ホルムアルデヒド架橋澱粉、エピクロルヒドリン架橋澱粉、リン酸架橋澱粉、アクロレイン架橋澱粉等が挙げられ、中でも入手の容易さや経済性点から、生澱粉が好適である。 The starch is contained for the purpose of preventing blocking and adjusting the mechanical strength, and preferably has an average particle size of 10 μm or more (the average particle size is different from the starch described in the above filler). As raw starch (corn starch, potato starch, sweet potato starch, wheat starch, kissava starch, sago starch, tapioca starch, sorghum starch, rice starch, bean starch, kudzu starch, bracken starch, lotus starch, horsetail starch, etc.); Physically modified starch (α-starch, fractionated amylose, wet heat-treated starch, etc.); Enzyme modified starch (hydrolyzed dextrin, enzymatically degraded dextrin, amylose, etc.); Chemically modified modified starch (acid-treated starch, hypochlorite oxidized starch, Dialdehyde starch, etc.); chemically modified starch derivatives (esterified starch, etherified starch, cationized starch, crosslinked starch, etc.) and the like. Among the chemically modified starch derivatives, esterified starch includes acetate esterified starch, succinate esterified starch, nitrate esterified starch, phosphate esterified starch, urea phosphate esterified starch, xanthate esterified starch, As etherified starch, such as acetate esterified starch, allyl etherified starch, methyl etherified starch, carboxymethyl etherified starch, hydroxyethyl etherified starch, hydroxypropyl etherified starch, etc., as cationized starch, starch and 2 -A reaction product of diethylaminoethyl chloride, a reaction product of starch and 2,3-epoxypropyltrimethylammonium chloride, such as a cross-linked starch, formaldehyde cross-linked starch, epichlorohydrin cross-linked starch, phosphate cross-linked starch, acrolein cross-linked starch, etc. Above all Raw starch is preferred from the viewpoint of ease of hand and economy.
かかる澱粉の含有量は特に限定されないが、ポリビニルアルコール系樹脂（Ａ）１００重量部に対して０．１〜４０重量部であることが好ましく、特に好ましくは１〜３０重量部である。かかる含有量が０．１重量部未満ではブロッキング抑制効果が低く、また機械強度の改善効果も少なく、４０重量部を越えるとフィルムの外観や引張伸度が大幅に低下し好ましくない。 Although content of this starch is not specifically limited, It is preferable that it is 0.1-40 weight part with respect to 100 weight part of polyvinyl alcohol-type resin (A), Most preferably, it is 1-30 weight part. When the content is less than 0.1 parts by weight, the blocking inhibition effect is low and the mechanical strength improvement effect is small, and when the content exceeds 40 parts by weight, the appearance and tensile elongation of the film are significantly lowered.
また、本発明の目的を阻害しない範囲で、上記の他に、他の水溶性高分子（ポリアクリル酸ソーダ、ポリエチレンオキサイド、ポリビニルピロリドン、デキストリン、キトサン、キチン、メチルセルロース、ヒドロキシエチルセルロース等）、香料、防錆剤、着色剤、増量剤、消泡剤、紫外線吸収剤、酸化防止剤、還元剤（亜硫酸ソーダ、酒石酸、アスコルビン酸、チオ硫酸ソーダ、ロンガリット）、等を含有させることも可能である。 In addition to the above, other water-soluble polymers (polyacrylic acid soda, polyethylene oxide, polyvinylpyrrolidone, dextrin, chitosan, chitin, methylcellulose, hydroxyethylcellulose, etc.), flavors, Rust preventives, colorants, extenders, antifoaming agents, ultraviolet absorbers, antioxidants, reducing agents (sodium sulfite, tartaric acid, ascorbic acid, sodium thiosulfate, Rongalite), and the like can also be included.
かくして本発明では、ポリビニルアルコール系樹脂（Ａ）及び多価アルコール（Ｂ）を含有してなる樹脂組成物を製膜（フィルム化）して、ポリビニルアルコール系フィルムとすればよく、かかる製膜に当たっては、特に限定されることなく流延法やインフレーション法等の方法を採用することができる。特に流延法を採用する場合は上記界面活性剤（Ｃ）を含有させることが好ましい。 Thus, in the present invention, a resin composition containing the polyvinyl alcohol-based resin (A) and the polyhydric alcohol (B) may be formed into a film (film) to form a polyvinyl alcohol-based film. A method such as a casting method or an inflation method can be adopted without particular limitation. In particular, when the casting method is adopted, it is preferable to contain the surfactant (C).
例えば、流延法について、より具体的に説明すれば、上記樹脂組成物（粉末）に水を加えて固形分濃度が１０〜５０重量％（好ましくは１５〜３５重量部）の樹脂組成物の水分散液又は水溶性を得る、或いは、ポリビニルアルコール系樹脂（Ａ）（粉末）に水を加えて固形分濃度を１０〜５０重量％（好ましくは１５〜３５重量部）に調整したポリビニルアルコール系樹脂水溶液に多価アルコール（Ｂ）、及び界面活性剤（Ｃ）を加えて固形分濃度が１０〜５０重量％（好ましくは１５〜３５重量部）の樹脂組成物の水分散液又は水溶液を得る。 For example, the casting method will be described more specifically. The resin composition (powder) is added with water to have a solid content concentration of 10 to 50% by weight (preferably 15 to 35 parts by weight). Polyvinyl alcohol system which obtains aqueous dispersion or water solubility, or adjusts the solid content concentration to 10 to 50% by weight (preferably 15 to 35 parts by weight) by adding water to the polyvinyl alcohol resin (A) (powder). A polyhydric alcohol (B) and a surfactant (C) are added to the aqueous resin solution to obtain an aqueous dispersion or aqueous solution of the resin composition having a solid content concentration of 10 to 50% by weight (preferably 15 to 35 parts by weight). .
かかる水分散液又は水溶液をＴ−ダイ等のスリットを通過させ、表面温度が５０〜１００℃、好ましくは７０〜９５℃の鏡面仕上（３S以下）されたエンドレスベルトやドラムロール等の金属表面に流延し、乾燥し、必要に応じて更に熱処理してポリビニルアルコール系フィルムを得ることができる。 Such an aqueous dispersion or aqueous solution is passed through a slit such as a T-die, and is applied to a metal surface such as an endless belt or drum roll having a surface finish of 50 to 100 ° C., preferably 70 to 95 ° C. (3S or less). It can be cast, dried, and further heat treated as necessary to obtain a polyvinyl alcohol film.
上記樹脂組成物の固形分濃度が１０重量％未満では生産性が低下し、５０重量％を超えると高粘度となってドープの脱泡に時間を要したり、フィルム製膜時にダイラインが発生し好ましくなく、金属表面の温度が５０℃未満では乾燥に時間を要し実用上好ましくなく、１００℃を越えると製膜時に発泡し好ましくない。 When the solid content concentration of the resin composition is less than 10% by weight, the productivity decreases, and when it exceeds 50% by weight, the viscosity becomes high and it takes time for defoaming of the dope, or a die line is generated during film formation. When the temperature of the metal surface is less than 50 ° C., it takes time for drying, which is not preferable for practical use. When the temperature exceeds 100 ° C., foaming occurs at the time of film formation.
また、アプリケーターを用いて、樹脂組成物の水分散液又は水溶液をポリエチレンテレフタレートフィルムやポリエチレンフィルム等のプラスチック基材あるいは金属基材上にキャストして、乾燥させてポリビニルアルコール系フィルムを得ることもできる。
ここで、流延法について説明したが、本発明ではこれに限定されるものではない。
In addition, using an applicator, an aqueous dispersion or aqueous solution of the resin composition can be cast on a plastic substrate or a metal substrate such as a polyethylene terephthalate film or a polyethylene film, and dried to obtain a polyvinyl alcohol film. .
Although the casting method has been described here, the present invention is not limited to this.
かくして上記方法によりポリビニルアルコール系フィルムが得られるのであるが、本発明では、２０℃の水に３分以内に溶解することが必要であり、好ましくは２分以内、特に好ましくは１分以内であり、かかるフィルムの溶解性は、ポリビニルアルコール系樹脂（Ａ）の変性量やケン化度（但し、８５〜９７モル％）、粘度、熱処理温度等を適宜調整することにより調整される。
なお、水に対する溶解性の測定については、ポリビニルアルコール系フィルムを３ｃｍ×５ｃｍのサイズにカットし、治具に固定し、次に、１リットルビーカーに水（１リットル）を入れ、スターラーにより撹拌しながら水温を２０℃に保ちつつ、フィルムを水面と平行に固定できる治具にフィルムを固定して、かかる水中に浸漬し、３ｃｍの撹拌子を用い４００ｒｐｍで撹拌を続けながらフィルムが溶解するまでの時間（秒）を測定することとした。ここで溶解とは、かかるフィルムが視認できなくなることをいい、このとき直径１ｍｍ以下の不溶微粒子が分散している場合も溶解の意味に含めるものである。
Thus, a polyvinyl alcohol film can be obtained by the above method. In the present invention, it is necessary to dissolve in water at 20 ° C. within 3 minutes, preferably within 2 minutes, particularly preferably within 1 minute. The solubility of the film is adjusted by appropriately adjusting the amount of modification of the polyvinyl alcohol-based resin (A), the degree of saponification (however, 85 to 97 mol%), the viscosity, the heat treatment temperature, and the like.
For measuring the solubility in water, a polyvinyl alcohol film is cut to a size of 3 cm × 5 cm, fixed to a jig, and then water (1 liter) is put into a 1 liter beaker and stirred with a stirrer. While maintaining the water temperature at 20 ° C., fix the film on a jig that can fix the film parallel to the water surface, immerse in the water, and continue to stir at 400 rpm using a 3 cm stir bar until the film dissolves. Time (seconds) was measured. Here, dissolution means that such a film cannot be visually recognized. At this time, the case where insoluble fine particles having a diameter of 1 mm or less are dispersed is also included in the meaning of dissolution.
かくして得られたポリビニルアルコール系フィルムにおいては、その厚みは、用途により一概に言えないが、５〜１００μｍ、特には１０〜８０μｍであることが好ましく、かかる厚みが５μｍ未満ではフィルムの製膜精度や機械的強度が低下し、逆に１００μｍを超えると冷水での溶解速度が大幅に遅くなり、また製膜時の効率も低下し好ましくない。
また、該ポリビニルアルコール系フィルムの表面はプレーンであってもよいが、該フィルムの片面或いは両面にエンボス模様や梨地模様等を施しておいても良い。
In the polyvinyl alcohol film thus obtained, the thickness cannot be generally specified depending on the use, but it is preferably 5 to 100 μm, particularly preferably 10 to 80 μm. If the thickness is less than 5 μm, the film-forming accuracy or On the other hand, when the mechanical strength is lowered and the thickness exceeds 100 μm, the dissolution rate in cold water is significantly slowed, and the efficiency during film formation is also lowered, which is not preferable.
The surface of the polyvinyl alcohol film may be a plane, but an embossed pattern or a satin pattern may be provided on one side or both sides of the film.
かくして得られたポリビニルアルコール系フィルムは、各種の包装用途等に有用であるが、特に薬剤等のユニット包装用途に有用であり、かかる用途について更に説明する。
かかる薬剤としては、特に制限はないが、水に溶解または分散させて用いる薬剤が良く、また、アルカリ性、中性、酸性のいずれであっても良い。更に、薬剤の形状も顆粒、錠剤、粉体、粉末、液状等いずれの形状でも良い。
The polyvinyl alcohol-based film thus obtained is useful for various packaging applications and the like, but is particularly useful for unit packaging applications for drugs and the like, and such applications will be further described.
Although there is no restriction | limiting in particular as this chemical | medical agent, The chemical | medical agent used by making it melt | dissolve or disperse | distributes to water is good, and any of alkaline, neutral, and acidic may be sufficient. Furthermore, the shape of the drug may be any shape such as granules, tablets, powders, powders, and liquids.
中でも本発明では、水に分散または溶解させて１重量％の懸濁液または水溶液とした時のｐＨ値が１〜１２（２０℃）となるような薬剤を包装するのに有用である。
本発明のポリビニルアルコール系フィルムを用いて薬剤を包装するに当たっては、イ）予め該フィルムを袋状にしておいてから、薬剤を包装する方法、ロ）該フィルムで直接薬剤を包装する方法等が挙げられる。
In particular, the present invention is useful for packaging a drug having a pH value of 1 to 12 (20 ° C.) when dispersed or dissolved in water to form a 1% by weight suspension or aqueous solution.
When packaging a drug using the polyvinyl alcohol film of the present invention, a) a method of packaging the drug in advance after the film is formed into a bag, and b) a method of packaging the drug directly with the film. Can be mentioned.
次に実施例を挙げて本発明を更に詳しく説明する。
尚、例中「％」、「部」とあるのは特に断りのない限り重量基準である。
Next, the present invention will be described in more detail with reference to examples.
In the examples, “%” and “parts” are based on weight unless otherwise specified.
各物性について、次のようにして行なった。
（１）側鎖の１，２−グリコール結合量
1Ｈ−ＮＭＲ（内部標準物質：テトラメチルシラン、溶媒：ｄ６−ＤＭＳＯ）で測定して算出した。
（２）ポリビニルアルコール系樹脂のケン化度
残酢酸ビニル単位の加水分解に要するアルカリ消費で分析を行なった。
（３）ポリビニルアルコール系樹脂の４％水溶液粘度
水温を２０℃に調整しヘプラ−粘度計により測定した。
About each physical property, it carried out as follows.
(1) 1,2-glycol bond amount of side chain
It was calculated by measuring with 1 H-NMR (internal standard substance: tetramethylsilane, solvent: d6-DMSO).
(2) Degree of Saponification of Polyvinyl Alcohol Resin The analysis was performed based on alkali consumption required for hydrolysis of residual vinyl acetate units.
(3) The viscosity of a 4% aqueous solution of polyvinyl alcohol resin was adjusted to 20 ° C. and measured with a Heppler viscometer.
実施例１
４％水溶液粘度１３．０ｍＰａ・ｓ（２０℃）、ケン化度９０．０モル％、側鎖の１，２−グリコール結合量６．０モル％のポリビニルアルコール系樹脂（Ａ）１００部に、多価アルコール（Ｂ）としてジグリセリン１０部、界面活性剤（Ｃ）としてポリオキシエチレンドデシルアミン１部、及び水４００部を混合して、９０〜９９℃で３０分間撹拌し、ポリビニルアルコール系樹脂（Ａ）を溶解した後、更に９０℃で３時間脱泡し、固形分濃度２２％の樹脂組成物の水分散液を得た。
表面が鏡面処理されたＳＵＳ板をホットプレート上に設置し、表面を９０℃に調整した後、上記の樹脂組成物の水分散液を、加熱されたＳＵＳ板上に流延し、その後８０〜９０℃で５分間乾燥して、キャスト基材よりフィルムを剥離し、厚さ７０μｍのポリビニルアルコール系フィルムを得た。
得られたポリビニルアルコール系フィルムについて、以下の評価を行った。
Example 1
To 100 parts of a polyvinyl alcohol resin (A) having a 4% aqueous solution viscosity of 13.0 mPa · s (20 ° C.), a saponification degree of 90.0 mol%, and a side chain 1,2-glycol bond amount of 6.0 mol%, 10 parts of diglycerin as the polyhydric alcohol (B), 1 part of polyoxyethylene dodecylamine as the surfactant (C), and 400 parts of water are mixed and stirred at 90 to 99 ° C. for 30 minutes to obtain a polyvinyl alcohol resin. After dissolving (A), it was further degassed at 90 ° C. for 3 hours to obtain an aqueous dispersion of a resin composition having a solid content concentration of 22%.
A SUS plate having a mirror-finished surface was placed on a hot plate, the surface was adjusted to 90 ° C., and then an aqueous dispersion of the above resin composition was cast on the heated SUS plate, and then 80- It dried at 90 degreeC for 5 minute (s), and the film was peeled from the cast base material, and the 70-micrometer-thick polyvinyl alcohol-type film was obtained.
The following evaluation was performed about the obtained polyvinyl alcohol-type film.
（水溶解性）
得られたポリビニルアルコール系フィルムを３ｃｍ×５ｃｍのサイズにカットし、治具に固定し、次に、１リットルビーカーに水（１リットル）を入れ、スターラーにより撹拌しながら水温を（１）２０℃、（２）１５℃に保ちつつ、フィルムを水面と平行に固定できる治具にフィルムを固定して、かかる水中に浸漬し、３ｃｍの撹拌子を用い４００ｒｐｍで撹拌を続けながらフィルムが溶解するまでの時間（秒）を測定した。ここで溶解とは、かかるフィルムが視認できなくなることをいい、このとき直径１ｍｍ以下の不溶微粒子が分散している場合も溶解の意味に含めるものである。
(Water solubility)
The obtained polyvinyl alcohol film is cut into a size of 3 cm × 5 cm, fixed to a jig, and then water (1 liter) is put into a 1 liter beaker, and the water temperature is (1) 20 ° C. while stirring with a stirrer. (2) While maintaining the temperature at 15 ° C., fix the film on a jig that can fix the film parallel to the water surface, immerse in the water, and continue to stir at 400 rpm using a 3 cm stir bar until the film dissolves The time (seconds) was measured. Here, dissolution means that such a film cannot be visually recognized. At this time, the case where insoluble fine particles having a diameter of 1 mm or less are dispersed is also included in the meaning of dissolution.
（ヒートシール性）
（１）ヒートシール強度
２３℃、５０％ＲＨ雰囲気下で、ヒートシーラー（安田精機製作所社製『ＹＳＳ式ヒートシーラー』）を用いて、上部圧着部（２ｍｍ）２００℃、下部圧着部（２０ｍｍ）１００℃、圧着力約２ＭＰａ、０．５秒の条件で、１週間調湿したポリビニルアルコール系フィルム２枚をヒートシールして、得られたヒートシール部分の破断強度を１５ｍｍ幅でＴピール（１８０度剥離試験）により２００ｍｍ／ｍｉｎの試験速度で測定した。
(Heat sealability)
(1) Heat seal strength 23 ° C., 50% RH atmosphere, using heat sealer (“YSS heat sealer” manufactured by Yasuda Seiki Seisakusho Co., Ltd.), upper pressure bonding part (2 mm), 200 ° C., lower pressure bonding part (20 mm) Two polyvinyl alcohol films conditioned for one week under conditions of 100 ° C., pressing force of about 2 MPa, and 0.5 seconds were heat sealed, and the breaking strength of the resulting heat sealed portion was 15 mm wide with T peel (180 Degree peel test) at a test speed of 200 mm / min.
（２）ヒートシール部の水溶解性
２３℃、５０％ＲＨ雰囲気下で、１週間調湿したポリビニルアルコール系フィルム２枚を、ヒートシーラー（安田精機製作所社製『ＹＳＳ式ヒートシーラー』）を用いて、上部圧着部２００℃、下部圧着部１００℃、圧着力約２ＭＰａ、０．５秒の条件で、ヒートシールして、得られたヒートシール部分の一部を試料（３ｃｍ×１ｃｍ）として、水溶解性の評価と同様にして該試料が溶解するまでの時間（秒）を測定した。なお、撹拌については、５００ｒｐｍで行った。
(2) Water-solubility of heat-sealed part Using a heat sealer ("YSS heat sealer" manufactured by Yasuda Seiki Seisakusyo Co., Ltd.) using two polyvinyl alcohol films conditioned for one week in an atmosphere of 23 ° C and 50% RH Then, heat sealing is performed under the conditions of an upper pressure bonding part 200 ° C., a lower pressure bonding part 100 ° C., a pressure bonding force of about 2 MPa, and 0.5 seconds, and a part of the obtained heat sealing part is used as a sample (3 cm × 1 cm), The time (seconds) until the sample was dissolved was measured in the same manner as in the evaluation of water solubility. The stirring was performed at 500 rpm.
（耐薬品性）
２３℃、５０％ＲＨ雰囲気下で、１週間調湿したポリビニルアルコール系フィルムを６ｃｍ×９ｃｍのサイズにカットした後、そのフィルムを２枚用意して、２３℃、５０％ＲＨ雰囲気下で、ヒートシーラー（安田精機製作所社製『ＹＳＳ式ヒートシーラー』）を用いて、上部圧着部２００℃、下部圧着部１００℃、圧着力約２ＭＰａ、０．５秒の条件で、３辺をシールして袋を作製し、かかる袋に、（１）粉末酸性物質（コハク酸：１％水溶液として時のｐＨが２（２０℃））、（２）粉末アルカリ性物質（炭酸水素ナトリウム：１％水溶液とした時のｐＨが１１（２０℃））を、４０ｇを充填して密封し、これを４０℃×７０％ＲＨの環境下に２週間放置した後、かかる袋から３ｃｍ×５ｃｍのサイズにカットし取り出して１枚のフィルムを得、水溶解性の評価と同様にして該フィルムが溶解するまでの時間（秒）を測定した。
(chemical resistance)
After cutting a polyvinyl alcohol film conditioned for one week in an atmosphere of 23 ° C. and 50% RH into a size of 6 cm × 9 cm, prepare two sheets of the film and heat them in an atmosphere of 23 ° C. and 50% RH. Using a sealer (“YSS heat sealer” manufactured by Yasuda Seiki Seisakusho Co., Ltd.), the bag is sealed on three sides under the conditions of an upper pressure bonding part of 200 ° C., a lower pressure bonding part of 100 ° C., a pressure bonding force of about 2 MPa, and 0.5 seconds. In such a bag, (1) powdered acidic substance (succinic acid: 1% aqueous solution when pH is 2 (20 ° C.)), (2) powdered alkaline substance (sodium bicarbonate: 1% aqueous solution) Was sealed by filling 40 g, and left in an environment of 40 ° C. × 70% RH for 2 weeks, and then cut out from this bag to a size of 3 cm × 5 cm and taken out. 1 film Obtained in the same manner as the water solubility assessment was measured the time (seconds) until the film dissolved.
（促進試験後の柔軟性）
得られたポリビニルアルコール系フィルムについて、（１）製造直後のフィルムと、（２）長期保存を想定した保存の促進条件（綿１００％の布で１５ｃｍ×１５ｃｍのフィルムの両面を挟みサンプル全面に１ｋｇの荷重をかけアルミ袋で密封して４０℃の恒温機中で３０日間放置）で保存した後のフィルムに対して、それぞれの弾性率を、ＪＩＳ Ｋ ７１２７に準拠して、１０℃×３０％ＲＨの環境下で１週間保存した後測定した。
(Flexibility after accelerated test)
About the obtained polyvinyl alcohol film, (1) the film immediately after production, and (2) the conditions for promoting storage assuming long-term storage (100 kg of cotton, 15 kg × 15 cm film sandwiched on both sides of the sample on the entire surface) The elastic modulus is 10 ° C. × 30% in accordance with JIS K 7127 for the film after being stored in a thermostat at 40 ° C. and stored for 30 days in a thermostat at 40 ° C. Measurement was performed after storage for 1 week in an RH environment.
実施例２
４％水溶液粘度１６．５ｍＰａ・ｓ（２０℃）、ケン化度９５．０モル％、側鎖の１，２−グリコール結合量８．０モル％のポリビニルアルコール系樹脂（Ａ）１００部に、多価アルコール（Ｂ）としてジグリセリン２０部、界面活性剤（Ｃ）としてポリオキシエチレンドデシルアミン１部、及び水４００部を混合して、９０〜９９℃で３０分間撹拌し、ポリビニルアルコール系樹脂（Ａ）を溶解した後、更に９０℃で３時間脱泡し、固形分濃度２３％の樹脂組成物の水分散液を得た。
かかる樹脂組成物の水分散液を用いた以外は実施例１と同様に行い、厚さ７０μｍのポリビニルアルコール系フィルムを得た。
得られたポリビニルアルコール系フィルムについて、実施例１と同様の評価を行った。
Example 2
To 100 parts of a polyvinyl alcohol resin (A) having a 4% aqueous solution viscosity of 16.5 mPa · s (20 ° C.), a saponification degree of 95.0 mol%, and a side chain 1,2-glycol bond amount of 8.0 mol%, 20 parts of diglycerin as the polyhydric alcohol (B), 1 part of polyoxyethylene dodecylamine as the surfactant (C), and 400 parts of water are mixed and stirred at 90 to 99 ° C. for 30 minutes to obtain a polyvinyl alcohol resin. After dissolving (A), it was further degassed at 90 ° C. for 3 hours to obtain an aqueous dispersion of a resin composition having a solid content concentration of 23%.
A polyvinyl alcohol film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the aqueous dispersion of the resin composition was used.
About the obtained polyvinyl alcohol-type film, evaluation similar to Example 1 was performed.
実施例３
４％水溶液粘度８．０ｍＰａ・ｓ（２０℃）、ケン化度８８．０モル％、側鎖の１，２−グリコール結合量４．０モル％のポリビニルアルコール系樹脂（Ａ）１００部に、多価アルコール（Ｂ）としてグリセリン１０部、界面活性剤（Ｃ）としてポリオキシエチレンドデシルアミン１部、及び水４００部を混合して、９０〜９９℃で３０分間撹拌し、ポリビニルアルコール系樹脂（Ａ）を溶解した後、更に９０℃で３時間脱泡し、固形分濃度２２％の樹脂組成物の水分散液を得た。
かかる樹脂組成物の水分散液を用いた以外は実施例１と同様に行い、厚さ７０μｍのポリビニルアルコール系フィルムを得た。
得られたポリビニルアルコール系フィルムについて、実施例１と同様の評価を行った。
Example 3
To 100 parts of a polyvinyl alcohol resin (A) having a 4% aqueous solution viscosity of 8.0 mPa · s (20 ° C), a saponification degree of 88.0 mol%, and a side chain 1,2-glycol bond amount of 4.0 mol%, Mix 10 parts of glycerin as the polyhydric alcohol (B), 1 part of polyoxyethylene dodecylamine as the surfactant (C), and 400 parts of water, and stir at 90 to 99 ° C. for 30 minutes to obtain a polyvinyl alcohol resin ( After dissolving A), it was further degassed at 90 ° C. for 3 hours to obtain an aqueous dispersion of a resin composition having a solid content concentration of 22%.
A polyvinyl alcohol film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the aqueous dispersion of the resin composition was used.
About the obtained polyvinyl alcohol-type film, evaluation similar to Example 1 was performed.
比較例１
４％水溶液粘度２２．０ｍＰａ・ｓ（２０℃）、ケン化度８８．０モル％の未変性ポリビニルアルコール系樹脂１００部に、多価アルコール（Ｂ）としてジグリセリン１０部、界面活性剤（Ｃ）としてポリオキシエチレンドデシルアミン１部、及び水４００部を混合して、９０〜９９℃で３０分間撹拌し、ポリビニルアルコール系樹脂を溶解した後、更に９０℃で３時間脱泡し、固形分濃度２２％の樹脂組成物の水分散液を得た。
かかる樹脂組成物の水分散液を用いた以外は実施例１と同様に行い、厚さ７０μｍのポリビニルアルコール系フィルムを得た。
得られたポリビニルアルコール系フィルムについて、実施例１と同様の評価を行った。
Comparative Example 1
4 parts aqueous solution viscosity 22.0 mPa · s (20 ° C), saponification degree 88.0 mol% unmodified polyvinyl alcohol-based resin 100 parts, polyglyceride (B) 10 parts diglycerin, surfactant (C ), 1 part of polyoxyethylene dodecylamine and 400 parts of water are mixed and stirred at 90 to 99 ° C. for 30 minutes to dissolve the polyvinyl alcohol resin, and then defoamed at 90 ° C. for 3 hours to obtain a solid content. An aqueous dispersion of a resin composition having a concentration of 22% was obtained.
A polyvinyl alcohol film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the aqueous dispersion of the resin composition was used.
About the obtained polyvinyl alcohol-type film, evaluation similar to Example 1 was performed.
比較例２
４％水溶液粘度９．８ｍＰａ・ｓ（２０℃）、ケン化度８０．０モル％、側鎖の１，２−グリコール結合量６．０モル％のポリビニルアルコール系樹脂１００部に、多価アルコール（Ｂ）としてジグリセリン１０部、界面活性剤（Ｃ）としてポリオキシエチレンドデシルアミン１部、及び水４００部を混合して、９０〜９９℃で３０分間撹拌し、ポリビニルアルコール系樹脂を溶解した後、更に９０℃で３時間脱泡し、固形分濃度２２％の樹脂組成物の水分散液を得た。
かかる樹脂組成物の水分散液を用いた以外は実施例１と同様に行い、厚さ７０μｍのポリビニルアルコール系フィルムを得た。
得られたポリビニルアルコール系フィルムについて、実施例１と同様の評価を行った。
Comparative Example 2
A polyhydric alcohol is added to 100 parts of a polyvinyl alcohol resin having a 4% aqueous solution viscosity of 9.8 mPa · s (20 ° C.), a saponification degree of 80.0 mol%, and a side chain 1,2-glycol bond amount of 6.0 mol%. (B) 10 parts of diglycerin, 1 part of polyoxyethylene dodecylamine as a surfactant (C), and 400 parts of water were mixed and stirred at 90 to 99 ° C. for 30 minutes to dissolve the polyvinyl alcohol resin. Thereafter, defoaming was further performed at 90 ° C. for 3 hours to obtain an aqueous dispersion of a resin composition having a solid content concentration of 22%.
A polyvinyl alcohol film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the aqueous dispersion of the resin composition was used.
About the obtained polyvinyl alcohol-type film, evaluation similar to Example 1 was performed.
比較例３
４％水溶液粘度１５．０ｍＰａ・ｓ（２０℃）、ケン化度９９．０モル％、側鎖の１，２−グリコール結合量６．０モル％のポリビニルアルコール系樹脂１００部に、多価アルコール（Ｂ）としてジグリセリン１０部、界面活性剤（Ｃ）としてポリオキシエチレンドデシルアミン１部、及び水４００部を混合して、９０〜９９℃で３０分間撹拌し、ポリビニルアルコール系樹脂を溶解した後、更に９０℃で３時間脱泡し、固形分濃度２２％の樹脂組成物の水分散液を得た。
かかる樹脂組成物の水分散液を用いた以外は実施例１と同様に行い、厚さ７０μｍのポリビニルアルコール系フィルムを得た。
得られたポリビニルアルコール系フィルムについて、実施例１と同様の評価を行った。
Comparative Example 3
A polyhydric alcohol was added to 100 parts of a polyvinyl alcohol resin having a 4% aqueous solution viscosity of 15.0 mPa · s (20 ° C.), a saponification degree of 99.0 mol%, and a side chain 1,2-glycol bond amount of 6.0 mol%. (B) 10 parts of diglycerin, 1 part of polyoxyethylene dodecylamine as a surfactant (C), and 400 parts of water were mixed and stirred at 90 to 99 ° C. for 30 minutes to dissolve the polyvinyl alcohol resin. Thereafter, defoaming was further performed at 90 ° C. for 3 hours to obtain an aqueous dispersion of a resin composition having a solid content concentration of 22%.
A polyvinyl alcohol film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the aqueous dispersion of the resin composition was used.
About the obtained polyvinyl alcohol-type film, evaluation similar to Example 1 was performed.
比較例４
４％水溶液粘度１５．０ｍＰａ・ｓ（２０℃）、ケン化度９５．０モル％、マレイン酸モノメチルエステルによる変性量２．０モル％のポリビニルアルコール系樹脂１００部に、多価アルコール（Ｂ）としてジグリセリン１０部、界面活性剤（Ｃ）としてポリオキシエチレンドデシルアミン１部、及び水４００部を混合して、９０〜９９℃で３０分間撹拌し、ポリビニルアルコール系樹脂を溶解した後、更に９０℃で３時間脱泡し、固形分濃度２２％の樹脂組成物の水分散液を得た。
かかる樹脂組成物の水分散液を用いた以外は実施例１と同様に行い、厚さ７０μｍのポリビニルアルコール系フィルムを得た。
得られたポリビニルアルコール系フィルムについて、実施例１と同様の評価を行った。
Comparative Example 4
A polyhydric alcohol (B) is added to 100 parts of a polyvinyl alcohol resin having a viscosity of 4% aqueous solution of 15.0 mPa · s (20 ° C.), a saponification degree of 95.0 mol%, and a modification amount of 2.0 mol% with monomethyl maleate. After mixing 10 parts of diglycerin, 1 part of polyoxyethylene dodecylamine as a surfactant (C), and 400 parts of water and stirring at 90 to 99 ° C. for 30 minutes to dissolve the polyvinyl alcohol-based resin, Defoaming was performed at 90 ° C. for 3 hours to obtain an aqueous dispersion of a resin composition having a solid content concentration of 22%.
A polyvinyl alcohol film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the aqueous dispersion of the resin composition was used.
About the obtained polyvinyl alcohol-type film, evaluation similar to Example 1 was performed.
比較例５
４％水溶液粘度１２．０ｍＰａ・ｓ（２０℃）、ケン化度８８．０モル％、主鎖に直接結合した１，２−グリコール結合量１．８モル％のポリビニルアルコール系樹脂１００部に、多価アルコール（Ｂ）としてジグリセリン１０部、界面活性剤（Ｃ）としてポリオキシエチレンドデシルアミン１部、及び水４００部を混合して、９０〜９９℃で３０分間撹拌し、ポリビニルアルコール系樹脂を溶解した後、更に９０℃で３時間脱泡し、固形分濃度２２％の樹脂組成物の水分散液を得た。
かかる樹脂組成物の水分散液を用いた以外は実施例１と同様に行い、厚さ７０μｍのポリビニルアルコール系フィルムを得た。
得られたポリビニルアルコール系フィルムについて、実施例１と同様の評価を行った。
実施例、比較例の評価結果を表１に示す。
Comparative Example 5
To 100 parts of a polyvinyl alcohol resin having a 4% aqueous solution viscosity of 12.0 mPa · s (20 ° C.), a saponification degree of 88.0 mol%, and a 1,2-glycol bond amount of 1.8 mol% directly bonded to the main chain, 10 parts of diglycerin as the polyhydric alcohol (B), 1 part of polyoxyethylene dodecylamine as the surfactant (C), and 400 parts of water are mixed and stirred at 90 to 99 ° C. for 30 minutes to obtain a polyvinyl alcohol resin. Then, the mixture was further degassed at 90 ° C. for 3 hours to obtain an aqueous dispersion of a resin composition having a solid content concentration of 22%.
A polyvinyl alcohol film having a thickness of 70 μm was obtained in the same manner as in Example 1 except that the aqueous dispersion of the resin composition was used.
About the obtained polyvinyl alcohol-type film, evaluation similar to Example 1 was performed.
Table 1 shows the evaluation results of Examples and Comparative Examples.
本発明のポリビニルアルコール系フィルムは、冷水溶解性に優れ、更に、ヒートシール性（ヒートシール強度、ヒートシール部分の溶解性）、耐薬品性、長期保存後の柔軟性に優れた効果を有し、各種用途、例えば農薬や洗剤等の薬剤の包装（ユニット包装）用途をはじめ、（水圧）転写用フィルム、ナプキン・紙おむつ等の生理用品、オストミーバッグ等の汚物処理用品、吸血シート等の医療用品、育苗シート・刺繍用基布等の一時的基材、等の用途にも利用することができ、中でも薬剤包装用途に非常に有用である。
The polyvinyl alcohol film of the present invention is excellent in cold water solubility, and further has excellent effects in heat sealability (heat seal strength, heat seal portion solubility), chemical resistance, and flexibility after long-term storage. , Various applications such as packaging of chemicals such as agricultural chemicals and detergents (unit packaging), (hydraulic) transfer films, sanitary products such as napkins and paper diapers, filth disposal products such as ostomy bags, and medical supplies such as blood-absorbing sheets It can also be used for temporary substrates such as seedling sheets and embroidery base fabrics, and is particularly useful for pharmaceutical packaging applications.
Claims (6)
A drug having a pH of 1 to 12 (20 ° C) when it is made into a 1% by weight suspension or aqueous solution is packaged with the polyvinyl alcohol film according to any one of claims 1 to 5. Drug packaging body.
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