JP4630396B2 - Water-soluble film - Google Patents
Water-soluble film Download PDFInfo
- Publication number
- JP4630396B2 JP4630396B2 JP2003417980A JP2003417980A JP4630396B2 JP 4630396 B2 JP4630396 B2 JP 4630396B2 JP 2003417980 A JP2003417980 A JP 2003417980A JP 2003417980 A JP2003417980 A JP 2003417980A JP 4630396 B2 JP4630396 B2 JP 4630396B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- film
- soluble film
- polyvinyl alcohol
- weight
- 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 - Fee Related
Links
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 64
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 64
- 229920005989 resin Polymers 0.000 claims description 55
- 239000011347 resin Substances 0.000 claims description 55
- -1 alkali metal sulfite Chemical class 0.000 claims description 41
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 32
- 239000004014 plasticizer Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 20
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 18
- 235000010265 sodium sulphite Nutrition 0.000 claims description 16
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 15
- 239000003599 detergent Substances 0.000 claims description 14
- 238000004806 packaging method and process Methods 0.000 claims description 14
- 238000007127 saponification reaction Methods 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000011976 maleic acid Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 10
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 4
- 229940105990 diglycerin Drugs 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 description 46
- 239000008107 starch Substances 0.000 description 45
- 235000019698 starch Nutrition 0.000 description 44
- 238000000034 method Methods 0.000 description 18
- 239000000178 monomer Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000003814 drug Substances 0.000 description 12
- 229940079593 drug Drugs 0.000 description 12
- 229920001567 vinyl ester resin Polymers 0.000 description 12
- 239000011342 resin composition Substances 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 238000004040 coloring Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000002829 reductive effect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920000881 Modified starch Polymers 0.000 description 6
- 239000004368 Modified starch Substances 0.000 description 6
- 230000000903 blocking effect Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 235000019426 modified starch Nutrition 0.000 description 5
- 229920001451 polypropylene glycol Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 239000012766 organic filler Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-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
- 229920001353 Dextrin Polymers 0.000 description 3
- 239000004375 Dextrin Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 239000003513 alkali Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 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
- 238000001035 drying Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000009512 pharmaceutical packaging Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 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
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 240000003183 Manihot esculenta Species 0.000 description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001408 amides 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
- 239000002585 base Substances 0.000 description 2
- 229920006167 biodegradable resin Polymers 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 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
- 229920006319 cationized starch Polymers 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 150000002596 lactones Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 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
- 229940100486 rice starch Drugs 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- TZYULTYGSBAILI-UHFFFAOYSA-M trimethyl(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC=C TZYULTYGSBAILI-UHFFFAOYSA-M 0.000 description 2
- 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 2
- 229920002554 vinyl polymer Polymers 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
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 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
- 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
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- NTKCAHRZWRIYFH-UHFFFAOYSA-N 2-sulfanyloctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(S)C(O)=O NTKCAHRZWRIYFH-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 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
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- QJSFUOBKBXVTMN-UHFFFAOYSA-N C=C.P(O)(O)=O Chemical compound C=C.P(O)(O)=O QJSFUOBKBXVTMN-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- 229920002261 Corn starch Polymers 0.000 description 1
- 244000168525 Croton tiglium Species 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 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
- 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
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- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-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
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
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- 239000002557 mineral fiber Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NWGNCXZRVUMBAL-UHFFFAOYSA-N o-octadecylhydroxylamine Chemical compound CCCCCCCCCCCCCCCCCCON NWGNCXZRVUMBAL-UHFFFAOYSA-N 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 235000013808 oxidized starch Nutrition 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002304 perfume Substances 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
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- 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
- 239000002685 polymerization catalyst Substances 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
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 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
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 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
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 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
- 230000002123 temporal effect Effects 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- 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
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 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
Landscapes
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、ポリビニルアルコール（以下、「ＰＶＡ」とも称する）系樹脂を主成分とする水溶性フィルムに関し、さらに詳しくは、製膜時の着色が少なく、かつ薬剤と接触しても経時的な着色が少ない水溶性フィルムに関する。 The present invention relates to a water-soluble film comprising a polyvinyl alcohol (hereinafter also referred to as “PVA”) resin as a main component, and more specifically, coloring with the passage of time even when it is in contact with a drug with little coloring during film formation. The present invention relates to a water-soluble film with a small amount.
従来より、ＰＶＡ系フィルムは、その水溶性を生かして、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、使用時に薬剤量を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。
Conventionally, PVA film is used for packaging of chemicals such as agricultural chemicals and detergents (unit packaging), (hydraulic pressure) transfer film, sanitary products such as napkins and paper diapers, and filth treatment for ostomy bags, etc. It is used for supplies, medical supplies such as blood-sucking sheets, temporary substrates such as seedling sheets, seed tapes, and embroidery base fabrics.
Above all, in the unit packaging application of chemicals such as agricultural chemicals and detergents, there is an advantage that the labor of measuring the amount of chemicals at the time of use can be saved and the hands are not soiled.
かかる用途に用いる水溶性ユニット包装袋として、例えば、カルボキシル基を１〜１０モル％含有し、ケン化度が８０モル％以上で、かつ２０℃における４重量％水溶液粘度が４６ｃｐｓ以上の変性ポリビニルアルコールからなる水溶性フィルム（例えば、特許文献１参照）や、アニオン性基による変性率が２．０〜４０．０モル％の変性ＰＶＡと平均粒径１５０μｍ以下の水不溶もしくは難溶性の微粉末とを含有してなる水溶性フィルム（例えば、特許文献２参照）、更には、ＰＶＡ１００重量部に対して、可塑剤５〜３０重量部、澱粉１〜１０重量部及び界面活性剤０．０１〜２重量部を配合してなる水溶性フィルム（例えば、特許文献３参照）、ＰＶＡ系樹脂１００重量部に対して還元剤を０．１〜２０重量部配合した水溶性フィルム（例えば、特許文献４参照）等が知られている。 Examples of water-soluble unit packaging bags used in such applications include modified polyvinyl alcohol containing 1 to 10 mol% of carboxyl groups, having a saponification degree of 80 mol% or more, and a 4 wt% aqueous solution viscosity at 20 ° C of 46 cps or more. A water-soluble film (see, for example, Patent Document 1), a modified PVA having a modification rate of 2.0 to 40.0 mol% by an anionic group, and a water-insoluble or hardly soluble fine powder having an average particle size of 150 μm or less A water-soluble film (see, for example, Patent Document 2), and further 5 to 30 parts by weight of a plasticizer, 1 to 10 parts by weight of starch, and 0.01 to 2 parts of a surfactant with respect to 100 parts by weight of PVA. Water-soluble film in which parts by weight are blended (for example, see Patent Document 3), water-soluble film in which 0.1 to 20 parts by weight of a reducing agent is blended with 100 parts by weight of PVA resin For example, see Patent Document 4), and the like.
しかしながら、かかる公知の水溶性フィルムは、フィルムの製膜時に受ける熱履歴や、充填する薬剤との接触により、フィルムが徐々に淡黄色に変色し、製品の商品価値を著しく損なう等の問題があった。
本発明の目的は、製膜時の着色が少なく、かつ、薬剤と接触しても経時的な着色が少ない、ＰＶＡ系樹脂を主成分とする水溶性フィルムを提供することにある。 An object of the present invention is to provide a water-soluble film containing a PVA resin as a main component, which is less colored during film formation and less colored over time even when contacted with a drug.
本発明者らは、鋭意研究の結果、ＰＶＡ系樹脂（Ａ）に、少なくとも特定の２種類の可塑剤（Ｂ）と亜硫酸塩（Ｃ）を特定量含有させることによって、製膜時の着色が少なく、かつ、薬剤と接触しても経時的な着色の増大が少ない水溶性フィルムが得られることを見出し、本発明を完成するに至った。 The present invention intensively studied, the PVA-based resin (A), the by containing specified amounts of at least two specific types of plasticizer (B) and sulfite (C), the coloring at the time of film The inventors have found that a water-soluble film can be obtained with little and little increase in coloring over time even when contacted with a drug, and the present invention has been completed.
すなわち、本発明は以下のとおりである。
〔１〕 ポリビニルアルコール系樹脂（Ａ）、可塑剤（Ｂ）及び亜硫酸塩（Ｃ）を含有してなり、可塑剤（Ｂ）は、（１）グリセリン（Ｂ１）と、（２）ジグリセリン及び／又はトリメチロールプロパン（Ｂ２）を含み、ポリビニルアルコール系樹脂（Ａ）１００重量部に対する可塑剤（Ｂ）の含有量が５〜５０重量部であり、亜硫酸塩（Ｃ）が、亜硫酸アルカリ金属塩であり、可塑剤（Ｂ）に対する亜硫酸塩（Ｃ）の含有割合（Ｃ／Ｂ：重量比）が０．０２を越えて０．３５以下である、水溶性フィルム。
〔２〕 ポリビニルアルコール系樹脂（Ａ）が、アニオン性基変性量１〜１０モル％のアニオン性基変性ポリビニルアルコール系樹脂である、上記〔１〕記載の水溶性フィルム。
〔３〕 アニオン性基変性ポリビニルアルコール系樹脂が、カルボキシル基変性ポリビニルアルコール系樹脂である、上記〔２〕記載の水溶性フィルム。
〔４〕 カルボキシル基変性ポリビニルアルコール系樹脂が、マレイン酸、マレイン酸塩、マレイン酸モノアルキルエステル及び無水マレイン酸のいずれかで変性されたポリビニルアルコール系樹脂である、上記〔３〕記載の水溶性フィルム。
〔５〕 ポリビニルアルコール系樹脂（Ａ）の平均ケン化度が８０．０〜９９．９モル％である、上記〔１〕〜〔４〕のいずれかに記載の水溶性フィルム。
〔６〕 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１０〜３５ｍＰａ・ｓである、上記〔１〕〜〔５〕のいずれかに記載の水溶性フィルム。
〔７〕 亜硫酸塩（Ｃ）が亜硫酸ソーダである、上記〔１〕〜〔６〕のいずれかに記載の水溶性フィルム。
〔８〕 更に、界面活性剤（Ｄ）を含有してなる、上記〔１〕〜〔７〕のいずれかに記載の水溶性フィルム。
〔９〕 ３ｃｍ×５ｃｍのフィルムを、１リットルの水を含有するビーカーに入れ、回転子長３ｃｍおよび回転数２００〜３００ｒｐｍの条件で、水温２０℃に保ちつつ、攪拌を続けた場合に、１０分以内に溶解する、上記〔１〕〜〔８〕のいずれかに記載の水溶性フィルム。
〔１０〕 ｐＨが６〜１２で、水分量が１０重量％未満の液体洗剤の包装用である、上記〔１〕〜〔９〕のいずれかに記載の水溶性フィルム。
That is, the present invention is as follows.
[1] A polyvinyl alcohol-based resin (A), a plasticizer (B), and a sulfite (C). The plasticizer (B) includes (1) glycerin (B1), (2) diglycerin, and And / or trimethylolpropane (B2), the plasticizer (B) content is 5 to 50 parts by weight with respect to 100 parts by weight of the polyvinyl alcohol resin (A), and the sulfite (C) is an alkali metal sulfite. A water-soluble film in which the content ratio (C / B: weight ratio) of the sulfite (C) to the plasticizer (B) exceeds 0.02 and is 0.35 or less.
[2] The water-soluble film according to [1], wherein the polyvinyl alcohol resin (A) is an anionic group-modified polyvinyl alcohol resin having an anionic group modification amount of 1 to 10 mol%.
[3] The water-soluble film according to [2], wherein the anionic group-modified polyvinyl alcohol resin is a carboxyl group-modified polyvinyl alcohol resin.
[4] The water-soluble property according to the above [3], wherein the carboxyl group-modified polyvinyl alcohol resin is a polyvinyl alcohol resin modified with any of maleic acid, maleate, monoalkyl maleate and maleic anhydride. the film.
[5] The water-soluble film according to any one of [1] to [4], wherein the polyvinyl alcohol resin (A) has an average saponification degree of 80.0 to 99.9 mol%.
[6] The water-soluble film according to any one of [1] to [5], wherein the polyvinyl alcohol-based resin (A) has a 4 wt% aqueous solution viscosity at 20 ° C of 10 to 35 mPa · s.
[ 7 ] The water-soluble film according to any one of [1] to [ 6 ], wherein the sulfite (C) is sodium sulfite.
[ 8 ] The water-soluble film according to any one of [1] to [ 7 ], further comprising a surfactant (D).
[ 9 ] When a 3 cm × 5 cm film is put into a beaker containing 1 liter of water and stirring is continued while maintaining a water temperature of 20 ° C. under conditions of a rotor length of 3 cm and a rotation speed of 200 to 300 rpm, 10 The water-soluble film according to any one of [1] to [ 8 ], which dissolves within minutes.
[ 10 ] The water-soluble film according to any one of [1] to [ 9 ], which is for packaging a liquid detergent having a pH of 6 to 12 and a water content of less than 10% by weight.
本発明の水溶性フィルムは、製膜時の着色がなく、かつ、薬剤と接触しても経時的な着色が少ない非常に優れた水溶性フィルムであるため、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、（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の用途に利用することができ、中でも薬剤（特に液体洗剤）包装用途に非常に有用である。 The water-soluble film of the present invention is a very excellent water-soluble film that is not colored during film formation and has little coloration with time even when contacted with a drug. Pharmaceutical packaging (unit packaging) applications, (hydraulic) transfer film, sanitary products such as napkins and paper diapers, filth disposal products such as ostomy bags, medical supplies such as blood-absorbing sheets, seedling sheets, seed tape, and embroidery base fabrics Can be used for applications such as temporary substrates, and is particularly useful for packaging of drugs (particularly liquid detergents).
本発明で用いられるＰＶＡ系樹脂（Ａ）としては、特に限定されることなく、公知の方法で製造することができるものである。即ち、ビニルエステル系化合物を重合して得られたビニルエステル系重合体をケン化して得られるものである。 The PVA resin (A) used in the present invention is not particularly limited and can be produced by a known method. That is, it is obtained by saponifying a vinyl ester polymer obtained by polymerizing a vinyl ester compound.
かかるビニルエステル系化合物としては、ギ酸ビニル、酢酸ビニル、トリフルオロ酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、カプリン酸ビニル、ラウリル酸ビニル、バーサティック酸ビニル、パルミチン酸ビニル、ステアリン酸ビニル等が単独又は併用で用いられるが、実用上は酢酸ビニルが好適である。 Examples of such vinyl ester compounds include vinyl formate, vinyl acetate, vinyl trifluoroacetate, vinyl propionate, vinyl butyrate, vinyl caprate, vinyl laurate, vinyl versatate, vinyl palmitate, vinyl stearate, etc. Although used in combination, vinyl acetate is preferred for practical use.
本発明で用いるＰＶＡ系樹脂（Ａ）としては、溶解性の点で、アニオン性基変性ＰＶＡ系樹脂が好ましい。又、アニオン性基の種類としては、カルボキシル基、スルホン酸基、リン酸基等が挙げられるが、中でも、上記の点から、カルボキシル基、スルホン酸基が好ましく、特にカルボキシル基が好ましい。 The PVA resin (A) used in the present invention is preferably an anionic group-modified PVA resin from the viewpoint of solubility. Examples of the anionic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, a carboxyl group and a sulfonic acid group are preferable, and a carboxyl group is particularly preferable.
本発明において特に好適なＰＶＡ系樹脂（Ａ）であるカルボキシル基変性ＰＶＡ系樹脂は、任意の方法で製造することができ、例えば、（ｉ）カルボキシル基を有する不飽和単量体とビニルエステル系化合物を共重合した後にケン化する方法、（ii）カルボキシル基を有するアルコールやアルデヒドあるいはチオール等を連鎖移動剤として共存させてビニルエステル系化合物を重合した後にケン化する方法等を挙げることができ、これらについてより具体的に説明するが、本発明ではこれらに限定されるものではない。 The carboxyl group-modified PVA resin which is a particularly preferred PVA resin (A) in the present invention can be produced by any method, for example, (i) an unsaturated monomer having a carboxyl group and a vinyl ester Examples include saponification after copolymerization of the compound, and (ii) saponification after polymerization of the vinyl ester compound in the presence of a carboxyl group-containing alcohol, aldehyde or thiol as a chain transfer agent. These will be described more specifically, but the present invention is not limited to these.
（ｉ）カルボキシル基を有する不飽和単量体とビニルエステル系化合物を共重合した後にケン化する方法。
このときのカルボキシル基を有する単量体として、エチレン性不飽和ジカルボン酸（マレイン酸、フマル酸、イタコン酸等）、又はエチレン性不飽和ジカルボン酸モノエステル（マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、イタコン酸モノアルキルエステル等）、又はエチレン性不飽和ジカルボン酸ジエステル（マレイン酸ジアルキルエステル、フマル酸ジアルキルエステル、イタコン酸ジアルキルエステル等）〔但し、これらのジエステルは共重合体のケン化時に加水分解によりカルボキシル基に変化することが必要である〕、又はエチレン性不飽和カルボン酸無水物（無水マレイン酸、無水イタコン酸等）、あるいはエチレン性不飽和モノカルボン酸（(メタ)アクリル酸、クロトン酸等）等の単量体、及びそれらの塩が挙げられ、その中でも特にマレイン酸、マレイン酸モノアルキルエステル、マレイン酸塩、無水マレイン酸が好適に使用され、更には、マレイン酸モノアルキルエステルが最も好適に使用される。
(I) A method of saponifying an unsaturated monomer having a carboxyl group and a vinyl ester compound after copolymerization.
As the monomer having a carboxyl group at this time, ethylenically unsaturated dicarboxylic acid (maleic acid, fumaric acid, itaconic acid, etc.), or ethylenically unsaturated dicarboxylic acid monoester (maleic acid monoalkyl ester, fumaric acid monoalkyl) Ester, itaconic acid monoalkyl ester, etc.), or ethylenically unsaturated dicarboxylic acid diester (maleic acid dialkyl ester, fumaric acid dialkyl ester, itaconic acid dialkyl ester, etc.) (however, these diesters are added during the saponification of the copolymer). It is necessary to change to a carboxyl group by decomposition], or ethylenically unsaturated carboxylic acid anhydride (maleic anhydride, itaconic anhydride, etc.), or ethylenically unsaturated monocarboxylic acid ((meth) acrylic acid, croton Monomers such as acids) and the like Salts can be mentioned, in particular maleic acid among them, maleic acid monoalkyl esters, maleate, maleic anhydride is preferably used, further, maleic acid monoalkyl esters are most preferably used.
（ii）カルボキシル基を有するアルコールやアルデヒドあるいはチオール等を連鎖移動剤として共存させてビニルエステル系化合物を重合した後にケン化する方法。
このときは、特に連鎖移動効果の大きいチオールに由来する化合物が有効で以下の化合物が挙げられる。
(Ii) A method in which a vinyl ester compound is polymerized in the presence of a carboxyl group-containing alcohol, aldehyde or thiol as a chain transfer agent and then saponified.
In this case, a compound derived from a thiol having a particularly large chain transfer effect is effective, and examples thereof include the following compounds.
［但し、上記一般式（１）、（２）において、ｎは０〜５の整数で、Ｒ１、Ｒ２及びＲ３はそれぞれ水素原子又は置換基を有していてもよい低級アルキル基（好ましくはメチル、エチル、プロピル、ブチル、ペンチル、ヘキシル等の炭素数１〜６のアルキル基）を示す。］ [However, in the above general formulas (1) and (2), n is an integer of 0 to 5, and R 1 , R 2 and R 3 are each a hydrogen atom or a lower alkyl group which may have a substituent ( Preferably, it is an alkyl group having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl). ]
［但し、上記一般式（３）において、ｎは０〜２０の整数である。］ [However, in the said General formula (3), n is an integer of 0-20. ]
又、上記一般式（１）〜（３）で表される化合物の塩も挙げられる。
具体的にはメルカプト酢酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、２−メルカプトステアリン酸等が挙げられる。
Moreover, the salt of the compound represented by the said general formula (1)-(3) is also mentioned.
Specific examples include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 2-mercaptostearic acid and the like.
又、スルホン酸基変性ＰＶＡやリン酸基変性ＰＶＡを製造するに当たっては、スルホン酸基変性ＰＶＡの場合、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、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸等のオレフィンスルホン酸あるいはその塩、リン酸基変性ＰＶＡの場合、エチレンホスホン酸等、と共重合してケン化する方法が挙げられる。 In producing sulfonic acid group-modified PVA and phosphoric acid group-modified PVA, in the case of sulfonic acid group-modified PVA, ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2- In the case of an olefin sulfonic acid such as methylpropane sulfonic acid or a salt thereof, or phosphoric acid group-modified PVA, a method of copolymerization with ethylene phosphonic acid or the like to saponify may be mentioned.
又、本発明で用いられるＰＶＡ系樹脂（Ａ）においては、かかる重合の際に前述した如きカルボキシル基を有する不飽和単量体、スルホン酸基を有する不飽和単量体、リン酸基を有する不飽和単量体、ビニルエステル系化合物以外に、その他の一般の単量体を水溶性を損なわない範囲で少量存在せしめて重合を行なっても良く、これらの単量体としては以下のものが挙げられる。 In addition, the PVA resin (A) used in the present invention has an unsaturated monomer having a carboxyl group, an unsaturated monomer having a sulfonic acid group, or a phosphoric acid group as described above during the polymerization. In addition to unsaturated monomers and vinyl ester compounds, the polymerization may be carried out in the presence of a small amount of other general monomers within the range not impairing the water solubility. Can be mentioned.
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の完全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、アクリルアミド、メタクリルアミド等のアミド類、アルキルビニルエーテル類、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、アリル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、ジアクリルアセトンアミド等が挙げられる。 For example, fully alkyl esters of olefins such as ethylene, propylene, isobutylene, α-octene, α-dodecene, α-octadecene, and unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid Nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylamide, alkyl vinyl ethers, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethyldiallylammonium chloride, dimethylallylvinylketone, N-vinyl Polyoxyalkylenes such as pyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) allyl ether, polyoxypropylene (meth) allyl ether Polyoxyalkylenes such as (meth) allyl ether, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, and other polyoxyalkylene (meth) acrylates, polyoxyethylene (meth) acrylamide, and polyoxypropylene (meth) acrylamide (Meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine , Polyoxypropylene vinylamine, diacrylacetone amide and the like.
更に、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等も挙げられる。
又、アセトアセチル基を含有させたポリビニルアルコール系樹脂等も使用することができる。
Further, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidopropyltrimethylammonium chloride, 2-acryloxyethyltrimethylammonium chloride, 2-methacryloxyethyltrimethylammonium chloride, 2-hydroxy-3- Examples also include cation group-containing monomers such as methacryloyloxypropyltrimethylammonium chloride, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, 3-butenetrimethylammonium chloride, dimethyldiallylammonium chloride, and diethyldiallylammonium chloride.
Also, polyvinyl alcohol resins containing acetoacetyl groups can be used.
本発明においては、これらの単量体を本発明の目的を阻害しない範囲、例えば０．５〜１０モル％、更には１〜７モル％共重合させることができる。 In the present invention, these monomers can be copolymerized in a range that does not impair the object of the present invention, for example, 0.5 to 10 mol%, and further 1 to 7 mol%.
本発明においては、上記ＰＶＡ系樹脂（Ａ）を１種のみならず、２種以上併用して用いることも可能である。 In the present invention, the PVA resin (A) can be used in combination of not only one type but also two or more types.
上記ＰＶＡ系樹脂（Ａ）は、上記ビニルエステル系化合物等の単量体を重合（又は共重合）することにより得られる。
単量体を重合（又は共重合）するにあたっては、特に制限はなく公知の重合方法が任意に用いられるが、普通メタノール、エタノールあるいはイソプロピルアルコール等のアルコール又はこれらの混合物を溶媒とする溶液重合が実施される。勿論、乳化重合、懸濁重合も可能である。
The PVA resin (A) can be obtained by polymerizing (or copolymerizing) monomers such as the vinyl ester compound.
In the polymerization (or copolymerization) of the monomer, there is no particular limitation and a known polymerization method is arbitrarily used, but solution polymerization using an alcohol such as methanol, ethanol or isopropyl alcohol or a mixture thereof as a solvent is usually used. To be implemented. Of course, emulsion polymerization and suspension polymerization are also possible.
又、上記カルボキシル基変性ＰＶＡ系樹脂を製造する場合、かかる溶液重合において単量体の仕込み方法としては、まずビニルエステル系化合物の全量と前記のカルボキシル基を有する不飽和単量体の一部を仕込み、重合を開始し、残りの不飽和単量体を重合期間中に連続的に又は分割的に添加する方法、前者を一括仕込みする方法等任意の手段を用いて良い。
この場合、ラクトン環の形成等により変性ＰＶＡの不溶化が心配される時は、その対策として、水溶性が良いＰＶＡの製法で既に公知であるマレイン酸又は無水マレイン酸に対して０．５〜２．０モル当量のアルカリ存在下でビニルエステルを有機溶媒中で共重合させることもできる。
Moreover, when manufacturing the said carboxyl group modified PVA-type resin, as a preparation method of a monomer in this solution polymerization, first, the whole quantity of a vinyl ester type compound and a part of unsaturated monomer which has the said carboxyl group are included. Arbitrary means such as a method of starting charging and starting polymerization and adding the remaining unsaturated monomer continuously or in a divided manner during the polymerization period, a method of charging the former in a lump may be used.
In this case, when insolubilization of the modified PVA is concerned due to the formation of a lactone ring or the like, as a countermeasure, 0.5 to 2 relative to maleic acid or maleic anhydride that is already known in the production method of PVA having good water solubility. It is also possible to copolymerize the vinyl ester in an organic solvent in the presence of 0.0 molar equivalent of alkali.
重合反応（又は共重合反応）は、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、過酸化ラウロイル等の公知のラジカル重合触媒を用いて行われる。
又、反応温度は３５℃〜沸点（好ましくは４０℃〜８０℃、特に好ましくは５０〜８０℃）程度の範囲から選択される。
The polymerization reaction (or copolymerization reaction) is performed using a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, or lauroyl peroxide.
The reaction temperature is selected from the range of about 35 ° C. to the boiling point (preferably 40 ° C. to 80 ° C., particularly preferably 50 to 80 ° C.).
ケン化にあたっては、得られた重合体（又は共重合体）をアルコールに溶解してアルカリ触媒の存在下に行なわれる。アルコールとしてはメタノール、エタノール、ブタノール等が挙げられる。アルコール中の重合体（又は共重合体）の濃度は、２０〜５０重量％の範囲から選ばれる。 In saponification, the obtained polymer (or copolymer) is dissolved in alcohol and carried out in the presence of an alkali catalyst. Examples of the alcohol include methanol, ethanol, butanol and the like. The concentration of the polymer (or copolymer) in the alcohol is selected from the range of 20 to 50% by weight.
ケン化触媒としては、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、ナトリウムエチラート、カリ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を用いることができ、場合によっては酸触媒を用いることも可能である。ケン化触媒の使用量はビニルエステル系化合物に対して１〜１００ミリモル当量にすることが必要である。 As the saponification catalyst, alkali catalysts such as alkali metal hydroxides and alcoholates such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate and potassium methylate can be used. It is also possible to use. The amount of saponification catalyst used must be 1 to 100 mmol equivalents relative to the vinyl ester compound.
尚、上記カルボキシル基変性ＰＶＡ系樹脂を製造する場合、通常、かかる方法で製造されたカルボキシル基含有ＰＶＡ系樹脂のカルボキシル基はナトリウム塩等のアルカリ金属塩型となっているが、該ＰＶＡ系樹脂の乾燥時等にラクトン環の形成により、水への不溶化が心配される時は、かかるナトリウム塩をカルシウム、マグネシウム、銅等の２価の金属塩に置換することによって回避することもできる。 When producing the carboxyl group-modified PVA resin, the carboxyl group of the carboxyl group-containing PVA resin produced by such a method is usually an alkali metal salt type such as a sodium salt. When there is a concern about the insolubilization in water due to the formation of a lactone ring during drying, it is possible to avoid this by replacing the sodium salt with a divalent metal salt such as calcium, magnesium or copper.
又、上記カルボキシル基変性ＰＶＡ系樹脂を製造する場合、上記方法に限らず、例えばポリビニルアルコール（部分ケン化物又は完全ケン化物）にジカルボン酸、アルデヒドカルボン酸、ヒドロキシカルボン酸等の水酸基と反応性のある官能基をもつカルボキシル基含有化合物を後反応させる方法等も実施可能である。 Moreover, when manufacturing the said carboxyl group modified PVA-type resin, it is not restricted to the said method, For example, it reacts with hydroxyl groups, such as dicarboxylic acid, aldehyde carboxylic acid, and hydroxycarboxylic acid, to polyvinyl alcohol (partially saponified product or complete saponified product). A method of post-reacting a carboxyl group-containing compound having a certain functional group can also be carried out.
更に、スルホン酸基で変性されたスルホン酸変性ＰＶＡ系樹脂の場合、スルホン酸基を有する単量体をＰＶＡにマイケル付加させる方法等により製造することもできる。 Furthermore, in the case of a sulfonic acid-modified PVA resin modified with a sulfonic acid group, it can also be produced by a method in which a monomer having a sulfonic acid group is added to PVA by Michael.
又、上記ＰＶＡ系樹脂（Ａ）の平均ケン化度は、８０．０〜９９．９モル％が好ましく、更には９０．０〜９８．５モル％、特に９２．０〜９７．０モル％が好ましい。かかる平均ケン化度が８０．０モル％未満では、包装対象の薬剤のｐＨによっては経時的にフィルムの水溶性が低下する等の不都合が生じる虞があり、一方、９９．９モル％を越えると製膜時の熱履歴により水溶性が大きく低下する虞があり好ましくない。 The average saponification degree of the PVA-based resin (A) is preferably 80.0 to 99.9 mol%, more preferably 90.0 to 98.5 mol%, particularly 92.0 to 97.0 mol%. Is preferred. If the average saponification degree is less than 80.0 mol%, there is a risk that the water solubility of the film will decrease over time depending on the pH of the drug to be packaged, while it exceeds 99.9 mol%. In addition, the water history may be greatly lowered due to the heat history during film formation.
更に、上記ＰＶＡ系樹脂（Ａ）の２０℃における４重量％水溶液粘度は１０〜３５ｍＰａ・ｓが好ましく、更には１５〜３０ｍＰａ・ｓ、特には１５〜２５ｍＰａ・ｓが好ましい。かかる粘度が１０ｍＰａ・ｓ未満では、包装材料としてのフィルムの機械的強度が低下する虞があり、一方、３５ｍＰａ・ｓを越えると製膜時の水溶液粘度が高く生産性が低下する虞があり好ましくない。 Further, the viscosity of a 4 wt% aqueous solution of the PVA resin (A) at 20 ° C. is preferably 10 to 35 mPa · s, more preferably 15 to 30 mPa · s, and particularly preferably 15 to 25 mPa · s. If the viscosity is less than 10 mPa · s, the mechanical strength of the film as a packaging material may be reduced. On the other hand, if it exceeds 35 mPa · s, the aqueous solution viscosity at the time of film formation may be high and productivity may be reduced. Absent.
尚、上記の平均ケン化度は、ＪＩＳ Ｋ ６７２６ ３．５に準拠して測定され、４重量％水溶液粘度は、ＪＩＳ Ｋ ６７２６ ３．１１．２に準じて測定される。 In addition, said average saponification degree is measured based on JIS K 6726 3.5, and 4 weight% aqueous solution viscosity is measured according to JIS K 6726 3.1.2.
本発明において好適な上記アニオン性基変性ＰＶＡ系樹脂の変性量は、１〜１０モル％が好ましく、更には２〜６モル％、特には３〜５モル％が好ましい。かかる変性量が１モル％未満では、液体洗浄剤等の薬剤の影響を受けて水溶性が著しく低下する虞があり、一方、１０モル％を越えるとＰＶＡ原末の生産性が低下したり生分解性が低下する等の虞があり好ましくない。 The modified amount of the anionic group-modified PVA resin suitable in the present invention is preferably 1 to 10 mol%, more preferably 2 to 6 mol%, and particularly preferably 3 to 5 mol%. If the amount of modification is less than 1 mol%, the water solubility may be significantly reduced due to the influence of chemicals such as liquid detergents. On the other hand, if the amount exceeds 10 mol%, the productivity of PVA bulk powder may be reduced. There is a possibility that the decomposability is deteriorated, which is not preferable.
本発明においては、少なくとも特定の２種類の可塑剤（Ｂ）を併用することが必要である。可塑剤が１種類の場合、フィルムの製膜直後から亜硫酸塩がフィルム表面に析出したり、フィルムの強度が低下するなどの不都合が生じる。 In the present invention, it is necessary to use at least two specific plasticizers (B) in combination. In the case of one kind of plasticizer, problems such as sulfite being deposited on the film surface immediately after film formation and the strength of the film being lowered occur.
本発明で用いる可塑剤（Ｂ）としては、例えば、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、ペンタエリスリトール、ポリエチレングリコール、ポリプロピレングリコール、ビスフェノールＡ、ビスフェノールＳ、Ｎ−メチルピロリドン、ソルビトール、マンニトール、キシリトール、２，３−ブタンジオール、１，３−ブタンジオール、還元麦芽糖水あめ類、還元乳糖、還元水あめ（還元澱粉糖化物）等も挙げられるが、本発明では特に、少なくとも
（１）グリセリン（Ｂ１）と、
（２）ジグリセリン及び／又はトリメチロールプロパン（Ｂ２）を含んでなることが必要である。
Examples of the plasticizer (B) used in the present invention include diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, pentaerythritol, polyethylene glycol, polypropylene glycol, bisphenol A, bisphenol S, N-methylpyrrolidone, sorbitol, and mannitol. , Xylitol, 2,3-butanediol, 1,3-butanediol, reduced maltose starch syrup, reduced lactose, reduced starch syrup (reduced starch saccharified product) and the like. In the present invention, at least (1) glycerin ( B1)
(2) It is Ru necessary der comprising diglycerol and / or trimethylolpropane (B2).
上記可塑剤（Ｂ１）及び可塑剤（Ｂ２）を含んでなる可塑剤（Ｂ）においては、Ｂ１及びＢ２の含有割合（Ｂ２／Ｂ１；重量比）が１５／８５〜８５／１５であることが好ましく、特には２０／８０〜８０／２０、更には２５／７５〜７５／２５であることが好ましい。該含有割合が１５／８５未満では耐ブロッキング性が低下する傾向にあり、一方、８５／１５を越えると経時的柔軟性が低下する傾向がある。 In the plasticizer (B) comprising the plasticizer (B1) and the plasticizer (B2), the content ratio (B2 / B1; weight ratio) of B1 and B2 is 15/85 to 85/15. It is particularly preferably 20/80 to 80/20, more preferably 25/75 to 75/25. When the content ratio is less than 15/85, the blocking resistance tends to be lowered. On the other hand, when it exceeds 85/15, the temporal flexibility tends to be lowered.
又、可塑剤（Ｂ）のフィルム中の含有量（総量）は、ＰＶＡ系樹脂（Ａ）１００重量部に対して、５〜５０重量部であり、好適には１０〜４０重量部であり、さらに好適には１５〜３５重量部である。５重量部未満では、可塑効果が得られにくく、５０重量部を越える場合にはフィルム強度が低下したり、経時的に可塑剤がフィルム表面にブリードするなどの不都合が生じる。 Moreover, content (total amount) in the film of a plasticizer (B) is 5-50 weight part with respect to 100 weight part of PVA-type resin (A), Preferably it is 10-40 weight part, More preferably, it is 15 to 35 parts by weight. If it is less than 5 parts by weight, it is difficult to obtain a plastic effect, and if it exceeds 50 parts by weight, the film strength is lowered, and the plasticizer bleeds on the film surface over time.
本発明の水溶性フィルムは、亜硫酸塩（Ｃ）を含有することが必要である。亜硫酸塩（Ｃ）を含有しない場合、液体洗浄剤等の薬剤とフィルムが接触することでフィルムの着色が増大するなどの不都合が生じる。 The water-soluble film of the present invention needs to contain sulfite (C). When the sulfite (C) is not contained, inconveniences such as an increase in coloration of the film occur due to the contact between the film and a chemical such as a liquid detergent.
本発明で用いる亜硫酸塩（Ｃ）としては、亜硫酸のアルカリ金属塩（例えば、亜硫酸ソーダ、亜硫酸カリなど）が挙げられ、好適には亜硫酸ソーダが挙げられる。 Examples of the sulfite (C) used in the present invention include alkali metal salts of sulfite (for example, sodium sulfite, potassium sulfite, etc. ) , and preferably sodium sulfite.
本発明におけるフィルム中の亜硫酸塩（Ｃ）の可塑剤（Ｂ）（総量）に対する含有割合（Ｃ／Ｂ；重量比）は、０．０２を越えて０．３５以下であり、好適には０．０２５〜０．３５であり、更に好適には０．０２５〜０．３である。該含有割合が０．０２以下ではフィルムの着色抑制効果が生じない。一方、０．３５を越えると製膜直後から亜硫酸塩がフィルム表面に析出し、フィルム外観不良や、保存安定性の低下、ヒートシールなどの加工性の低下を生じたり、フィルムの強度が低下するなどの不都合が生じる。 The content ratio (C / B; weight ratio) of the sulfite (C) in the film to the plasticizer (B) (total amount) in the film is more than 0.02 and not more than 0.35, preferably 0. 0.025 to 0.35, and more preferably 0.025 to 0.3. When the content ratio is 0.02 or less, the effect of suppressing coloration of the film does not occur. On the other hand, if it exceeds 0.35, sulfite will be deposited on the film surface immediately after film formation, resulting in poor film appearance, poor storage stability, poor workability such as heat sealing, or reduced film strength. Such inconvenience occurs.
かくして本発明では、上記ＰＶＡ系樹脂（Ａ）に、少なくとも特定の２種類の可塑剤（Ｂ１，Ｂ２）及び亜硫酸塩（Ｃ）を特定量含有させて樹脂組成物［Ｉ］を得て製膜するのであるが、該樹脂組成物［Ｉ］には、必要に応じて、更に界面活性剤（Ｄ）、フィラー（Ｅ）、澱粉（Ｆ）等を含有させることができる。 Thus, in the present invention, the PVA resin (A) contains at least two specific plasticizers ( B1, B2 ) and a specific amount of sulfite (C) to obtain a resin composition [I] to form a film. However, the resin composition [I] can further contain a surfactant (D), a filler (E), starch (F), and the like, if necessary.
上記界面活性剤（Ｄ）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ノエーテル、ポリオキシエチレンステアリルアミノエーテル等のポリオキシエチレンアルキルアミノエーテル等が挙げられ、１種又は２種以上併用して用いられる。中でも、剥離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アルキルアミノエーテルが好適である。 The surfactant (D) is not particularly limited, and examples thereof include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl nonyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate, polyoxyalkylene alkyl ether phosphate monoethanolamine salt, polyoxyethylene lauryl amino ether, polyoxyethylene Examples thereof include polyoxyethylene alkylamino ethers such as stearyl amino ether, and these are used alone or in combination of two or more. Of these, polyoxyalkylene alkyl ether phosphate monoethanolamine salts and polyoxyethylene alkylamino ethers are preferable in terms of peelability.
かかる界面活性剤（Ｄ）のフィルム中の含有量については、特に限定されないが、ＰＶＡ系樹脂（Ａ）１００重量部に対して０．０１〜３．０重量部であることが好ましく、特には０．０３〜２．５重量部、更には０．０５〜２．０重量部であることが好ましい。該含有量が０．０１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、３．０重量部を越えるとフィルム表面にブリードしてブロッキングの原因となり取り扱い性が低下することとなり好ましくない。 The content of the surfactant (D) in the film is not particularly limited, but is preferably 0.01 to 3.0 parts by weight with respect to 100 parts by weight of the PVA resin (A). The amount is preferably 0.03 to 2.5 parts by weight, more preferably 0.05 to 2.0 parts by weight. If the content is less than 0.01 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, making it difficult to produce. This is not preferable because it causes bleeding and causes blocking, resulting in a decrease in handleability.
上記フィラー（Ｅ）としては、無機フィラーや有機フィラーが挙げられる。
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 (E) include inorganic fillers and organic fillers.
The inorganic filler preferably has an average particle diameter of 1 to 10 μm. If the average particle diameter is less than 1 μm, the effect of inhibiting blocking of the film is small, and if it exceeds 10 μm, the appearance of the film deteriorates and the commercial value is high. Decreasing and not preferable. 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.
かかる無機フィラーのフィルム中の含有量は特に限定されないが、ＰＶＡ系樹脂１００重量部に対して０．１〜５０重量部であることが好ましく、特に好ましくは０．５〜１０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少なく、５０重量部を越えるとフィルムの引張伸度が低下し好ましくない。 Although content in the film of this inorganic filler is not specifically limited, It is preferable that it is 0.1-50 weight part with respect to 100 weight part of PVA-type resin, Most preferably, it is 0.5-10 weight part. If the content is less than 0.1 parts by weight, the blocking inhibiting effect is small, and if it exceeds 50 parts by weight, the tensile elongation of the film is undesirably lowered.
又、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。 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.
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。 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.
かかる有機フィラーの含有量は、特に限定されないが、ＰＶＡ系樹脂（Ａ）１００重量部に対して５〜２５重量部であることが好ましく、特には５〜１５重量部であることが好ましい。かかる含有量が５重量部未満では包材としての機械強度が不足し、２５重量部を越えるとフィルムの可とう性が得られなくなり好ましくない。 Although content of this organic filler is not specifically limited, It is preferable that it is 5-25 weight part with respect to 100 weight part of PVA-type resin (A), and it is especially preferable that it is 5-15 weight part. If the content is less than 5 parts by weight, the mechanical strength as a packaging material is insufficient, and if it exceeds 25 parts by weight, the flexibility of the film cannot be obtained.
又、上記澱粉（Ｆ）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、キャッサバ澱粉、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 (F) 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. Specific examples include raw starch (corn starch, potato Starch, sweet potato starch, wheat starch, cassava 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, enzyme-degraded dextrin, amylose, etc.); Chemically modified starch (acid-treated starch, hypochlorite oxidized starch, dialdehyde starch, etc.); Chemically modified starch derivative (Esterified starch, etherified starch, cationized starch, cross-linked starch, etc.). 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（Ｆ）のフィルム中の含有量は特に限定されないが、ＰＶＡ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、又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。 The content of the starch (F) in the film is not particularly limited, but is preferably 0.1 to 40 parts by weight, particularly preferably 1 to 30 parts by weight with respect to 100 parts by weight of the PVA resin (A). It is. When the content is less than 0.1 parts by weight, the blocking inhibiting effect is low and the mechanical strength improving effect is small, and when the content exceeds 40 parts by weight, the appearance and tensile elongation of the film are significantly lowered.
かくして本発明では、ＰＶＡ系樹脂（Ａ）に、可塑剤（Ｂ）及び亜硫酸塩（Ｃ）を含有してなる樹脂組成物［Ｉ］（該樹脂組成物［Ｉ］は必要に応じて界面活性剤（Ｄ）、フィラー（Ｅ）及び／又は澱粉（Ｆ）を更に含んでいてもよい）を製膜（フィルム化）してＰＶＡ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等の方法を採用することができる。 Thus, in the present invention, the resin composition [I] comprising the PVA-based resin (A) and the plasticizer (B) and the sulfite (C) (the resin composition [I] is surface active as necessary). The agent (D), filler (E) and / or starch (F) may be further formed into a film (film) to form a PVA-based film, and the film formation is particularly limited. A method such as a casting method can be employed without any problem.
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［Ｉ］（粉末）に水を加えて固形分濃度が１０〜４０重量％（好ましくは１１〜３９重量部、更に好ましくは１２〜３８重量％）の樹脂組成物［Ｉ］の水分散液又は水溶性を得る、或いは、ＰＶＡ系樹脂（Ａ）（粉末）に水を加えて固形分濃度を１０〜４０重量％（好ましくは１１〜３８重量部、更に好ましくは１３〜３５重量％）に調整したＰＶＡ系樹脂水溶液に可塑剤（Ｂ）及び亜硫酸塩（Ｃ）を加えて固形分濃度が１０〜４０重量％（好ましくは１１〜３９重量部、更に好ましくは１２〜３８重量％）の樹脂組成物［Ｉ］の水分散液又は水溶液を得る。 For example, the casting method will be described more specifically. Water is added to the resin composition [I] (powder) so that the solid concentration is 10 to 40% by weight (preferably 11 to 39 parts by weight, more preferably Is 12 to 38% by weight) of an aqueous dispersion of the resin composition [I] or water-soluble, or water is added to the PVA resin (A) (powder) to adjust the solid content concentration to 10 to 40% by weight ( Preferably, a plasticizer (B) and a sulfite (C) are added to a PVA resin aqueous solution adjusted to 11 to 38 parts by weight, more preferably 13 to 35% by weight, and the solid content concentration is 10 to 40% by weight (preferably 11 to 39 parts by weight, more preferably 12 to 38% by weight) of an aqueous dispersion or aqueous solution of the resin composition [I].
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５５〜９５℃のエンドレスベルトやドラムロール（好ましくは生産性の点でエンドレスベルトである。）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本発明のＰＶＡ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 an endless belt or drum roll having a surface temperature of 50 to 100 ° C., preferably 55 to 95 ° C. (preferably an endless belt in terms of productivity). ) On the metal surface, dried, and further heat-treated as necessary to obtain the PVA-based film of the present invention.
上記樹脂組成物［Ｉ］の固形分濃度が１０重量％未満あるいは４０重量％を越えると製膜性が悪くなり好ましくない。金属表面の温度が５０℃未満では乾燥効率が低下し、１００℃を越えると発泡する恐れがあり好ましくない。 If the solid content concentration of the resin composition [I] is less than 10% by weight or exceeds 40% by weight, the film-forming property is deteriorated, which is not preferable. If the temperature of the metal surface is less than 50 ° C, the drying efficiency is lowered, and if it exceeds 100 ° C, foaming may occur, which is not preferable.
又、アプリケーターを用いて、樹脂組成物［Ｉ］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ＰＶＡ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。
Also, using an applicator, an aqueous dispersion or aqueous solution of the resin composition [I] is cast on a plastic substrate or a metal substrate such as a polyethylene terephthalate film or a polyethylene film, and dried to obtain a PVA film. You can also.
Although the casting method has been described here, the present invention is not limited to this.
又、本発明の水溶性フィルム（ＰＶＡ系フィルム）は、好適には２０℃の水に１０分以内に溶解するものである。より好適には５分以内、更に好適には３分以内に溶解するものである。１０分を越えても溶解しない場合、例えばフィルムに包装した洗剤を使用して洗濯を行ったときに、洗剤が水槽中にうまく分散しなかったり、あるいはフィルムの一部が衣類に付着するなどの不都合が発生したり、長期間フィルムを保存すると水に溶解しなくなるなどの不都合が生じる虞がある。
ここでいう「２０℃の水に１０分以内に溶解する」とは、フィルムサンプルを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（回転子長３ｃｍ、回転数２００〜３００ｒｐｍ）しながら水温を２０℃に保ちつつ、治具に固定したフィルムをかかる水中に浸漬し、撹拌を続けた場合に、１０分以内に溶解することをいう。又、ここでいう「溶解」とはフィルムを水中に浸漬したときにフィルムの残渣が視認できなくなることをいうものであるが、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本発明では溶解の意味に含めるものである。
Moreover, the water-soluble film (PVA film) of the present invention is preferably dissolved in water at 20 ° C. within 10 minutes. More preferably, it dissolves within 5 minutes, more preferably within 3 minutes. If it does not dissolve after 10 minutes, for example, when washing is performed using a detergent packaged in a film, the detergent does not disperse well in the water tank, or a part of the film adheres to clothing, etc. There is a possibility that inconvenience may occur or inconvenience such as inability to dissolve in water if the film is stored for a long time.
Here, “dissolve in water at 20 ° C. within 10 minutes” means that the film sample 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. Put the film fixed on the jig in the water while keeping the water temperature at 20 ° C. while stirring with a stirrer (rotor length 3 cm, rotation speed 200 to 300 rpm), and within 10 minutes when stirring is continued. It means to dissolve. The term “dissolving” as used herein means that the residue of the film becomes invisible when the film is immersed in water. In this case, insoluble particles having a diameter of 1 mm or less are also dispersed. Then, it is included in the meaning of dissolution.
かかる溶解性の調整は、ＰＶＡ系樹脂のケン化度や、重合度、変性ＰＶＡであれば変性種や変性量、又、製膜時の乾燥温度及び時間、フィルムの厚み等を適宜調整することにより達成される。 Such solubility adjustment is performed by appropriately adjusting the degree of saponification of the PVA-based resin, the degree of polymerization, the modified species and the amount of modified PVA, the drying temperature and time during film formation, the thickness of the film, and the like. Is achieved.
かくして得られたＰＶＡ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機械的強度が低下し、逆に１００μｍを越えると冷水での溶解速度が大幅に遅くなり、又製膜時の効率も低下し好ましくない。
又、該ＰＶＡ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 PVA film thus obtained, the thickness cannot be generally specified depending on the use, but is preferably 5 to 100 μm, particularly preferably 10 to 80 μm. If the thickness is less than 5 μm, the mechanical strength of the film is lowered. On the other hand, if it exceeds 100 μm, the dissolution rate in cold water is significantly slowed, and the efficiency during film formation is also unfavorable.
The surface of the PVA 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.
尚、本発明の水溶性フィルムには、本発明の目的を阻害しない範囲で、他の水溶性高分子（未変性ＰＶＡ系樹脂、アニオン性基以外の変性ＰＶＡ系樹脂、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、紫外線吸収剤等を含有させることも可能である。 The water-soluble film of the present invention includes other water-soluble polymers (unmodified PVA-based resins, modified PVA-based resins other than anionic groups, polyacrylic acid soda, polyethylene, as long as the object of the present invention is not impaired. Oxide, polyvinylpyrrolidone, dextrin, chitosan, chitin, methylcellulose, hydroxyethylcellulose, etc.), perfume, rust preventive, colorant, extender, antifoaming agent, ultraviolet absorber and the like.
本発明の水溶性フィルムは、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、水に溶解又は分散させて用いる薬剤が良く、又、アルカリ性、中性、酸性のいずれで有っても良い。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 water-soluble film of the present invention 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 it may be alkaline, neutral, or acidic. Furthermore, the shape of the drug may be any shape such as granules, tablets, powders, powders, and liquids.
中でも本発明の水溶性フィルムは、ｐＨが６〜１２、好ましくは７〜１１で、水分量が１０重量％未満、好ましくは０．１〜７重量％の液体洗浄剤を包装するのに有用である。このような液体洗浄剤を包装した場合、従来公知の水溶性フィルムでは経時的に着色が増大するのに対して、本発明の水溶性フィルムは着色の増大が少ない。
上記液体洗浄剤としては、例えば、高級脂肪酸、ペンタエチレングリコール及びジプロピレングリコールモノメチルエーテルを主成分とする液体洗浄剤等が挙げられる。
Among them, the water-soluble film of the present invention is useful for packaging a liquid detergent having a pH of 6 to 12, preferably 7 to 11, and a water content of less than 10% by weight, preferably 0.1 to 7% by weight. is there. When such a liquid detergent is packaged, the coloring of the water-soluble film of the present invention is small while the coloring of the water-soluble film of the present invention increases with time.
Examples of the liquid detergent include liquid detergents mainly composed of higher fatty acids, pentaethylene glycol and dipropylene glycol monomethyl ether.
本発明の水溶性フィルムを用いて薬剤を包装するに当たっては、１）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、２）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 packaging the drug using the water-soluble film of the present invention, 1) a method of packaging the drug after the film is formed in a bag in advance, and 2) a method of packaging the drug directly with the film, etc. It is done.
以下に、実施例を挙げて本発明をさらに詳しく説明するが、これらは本発明を限定するものではない。
尚、以下の例中、「％」、「部」とあるのは特に断りのない限り重量基準である。
又、得られたフィルムについて、以下の評価を行った。
Hereinafter, the present invention will be described in more detail with reference to examples, but these do not limit the present invention.
In the following examples, “%” and “part” are based on weight unless otherwise specified.
Moreover, the following evaluation was performed about the obtained film.
（フィルムの着色）
フィルムの着色は、島津製作所社製「ＵＶ３１００」を用いてｂ値を測定することにより評価した。
（フィルム表面の亜硫酸塩の析出）
フィルム表面の亜硫酸塩の析出は目視により評価した。
（２０℃の水に対する溶解性）
フィルムサンプルを３ｃｍ×５ｃｍのサイズにカットし、治具に固定した。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（回転子長３ｃｍ、回転数２００〜３００ｒｐｍ）しながら水温を２０℃に保ちつつ、治具に固定したフィルムをかかる水中に浸漬し、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。
(Film coloring)
The coloring of the film was evaluated by measuring the b value using “UV3100” manufactured by Shimadzu Corporation.
(Sulphite deposition on the film surface)
The precipitation of sulfite on the film surface was evaluated visually.
(Solubility in water at 20 ° C)
The film sample was cut into a size of 3 cm × 5 cm and fixed to a jig. Next, water (1 liter) is put into a 1 liter beaker, and the film fixed on the jig is placed in the water while keeping the water temperature at 20 ° C. while stirring with a stirrer (rotor length 3 cm, rotation speed 200 to 300 rpm). It was immersed and the time (second) until the film was dissolved 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.
（実施例１）
４％水溶液粘度２２．０ｍＰａ・ｓ（２０℃）、平均ケン化度９７．２モル％、マレイン酸モノメチルエステルによる変性量４．０モル％のカルボキシル基変性ＰＶＡ（Ａ）１００部に、可塑剤（Ｂ）としてグリセリン２５部及びトリメチロールプロパン１２部、亜硫酸ソーダ（Ｃ）１．０部、界面活性剤（Ｄ）として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２部、及び水を加え、固形分濃度３０％樹脂組成物の水分散液を得た。
得られた樹脂組成物の水分散液（８０℃、脱泡済み）を、８０〜９０℃に加熱したホットプレート上に流延し、その後８０〜９０℃で、１分間乾燥して、厚さ７６μｍのＰＶＡ系フィルムを得た（亜硫酸ソーダ／可塑剤総量＝０．０３）。
得られたＰＶＡ系フィルムの着色を上記のように測定したところ、初期のｂ値は０．１３であった。又、上記のように２０℃の水に対する溶解性を測定したところ、２３秒であった。
Example 1
A plasticizer was added to 100 parts of a carboxyl group-modified PVA (A) having a 4% aqueous solution viscosity of 22.0 mPa · s (20 ° C.), an average degree of saponification of 97.2 mol%, and a modification amount of 4.0 mol% with maleic acid monomethyl ester. (B) 25 parts of glycerin and 12 parts of trimethylolpropane, 1.0 part of sodium sulfite (C), 2 parts of polyoxyalkylene alkyl ether phosphate monoethanolamine salt as a surfactant (D), and water were added. An aqueous dispersion of a resin composition having a solid content concentration of 30% was obtained.
An aqueous dispersion (80 ° C., defoamed) of the obtained resin composition was cast on a hot plate heated to 80 to 90 ° C., and then dried at 80 to 90 ° C. for 1 minute to obtain a thickness. A 76 μm PVA-based film was obtained (sodium sulfite / plasticizer total amount = 0.03).
When the coloring of the obtained PVA film was measured as described above, the initial b value was 0.13. Moreover, when the solubility with respect to 20 degreeC water was measured as mentioned above, it was 23 seconds.
（薬剤実包装テスト）
得られたＰＶＡ系フィルムを、１２ｃｍ×１０ｃｍのサイズにカットした後、ヒートシーラーを用いて二方向をシールして袋（６ｃｍ×１０ｃｍのサイズ）を作製し、かかる袋に、ｐＨ９．０、水分量１．５％の液体洗浄剤（主成分：高級脂肪酸、ペンタエチレングリコール、ジプロピレングリコールモノメチルエーテル）を３０ｇ収納し、更に残りの一辺をヒートシールしてパケット状の薬剤包装体（６ｃｍ×１０ｃｍのサイズ）を作製した。
得られたサンプルを８０℃の乾燥雰囲気下に７２時間放置し、同様に耐久後のｂ値を測定したところ、０．７７であった。
又、このとき、フィルム表面への亜硫酸ソーダの析出は観察されなかった。
(Drug packaging test)
The obtained PVA-based film was cut to a size of 12 cm × 10 cm, and then sealed in two directions using a heat sealer to produce a bag (6 cm × 10 cm size). Contains 30g of 1.5% liquid detergent (main components: higher fatty acid, pentaethylene glycol, dipropylene glycol monomethyl ether), and heat-sealing the other side to form a packet-shaped drug package (6cm x 10cm) Size).
The obtained sample was allowed to stand in a dry atmosphere at 80 ° C. for 72 hours, and the b value after durability was measured in the same manner. As a result, it was 0.77.
At this time, deposition of sodium sulfite on the film surface was not observed.
（実施例２〜８）
可塑剤、亜硫酸ソーダの種類及び添加量をそれぞれ表１の通りにした以外は実施例１と同様の操作を行いＰＶＡ系フィルムを得た。得られたフィルムについて、実施例１と同様に評価を行った。
(Examples 2 to 8)
A PVA-based film was obtained by performing the same operation as in Example 1 except that the types and addition amounts of the plasticizer and sodium sulfite were as shown in Table 1. The obtained film was evaluated in the same manner as in Example 1.
（比較例１）
亜硫酸ソーダを添加していない以外は実施例１と同様の操作を行いＰＶＡ系フィルムを得た。得られたフィルムについて、実施例１と同様に評価した。
(Comparative Example 1)
A PVA film was obtained by performing the same operation as in Example 1 except that sodium sulfite was not added. The obtained film was evaluated in the same manner as in Example 1.
（比較例２）
亜硫酸ソーダの添加量を０．７部とし亜硫酸ソーダ／可塑剤総量＝０．０２とした以外は実施例１と同様の操作を行いＰＶＡ系フィルムを得た。得られたフィルムについて、実施例１と同様に評価した。初期のｂ値は０．１７であったが、耐久後のｂ値が１．１１と高く、目視にて明らかに着色していることが判別できた。
(Comparative Example 2)
A PVA-based film was obtained in the same manner as in Example 1 except that the amount of sodium sulfite added was 0.7 parts and the total amount of sodium sulfite / plasticizer was 0.02. The obtained film was evaluated in the same manner as in Example 1. Although the initial b value was 0.17, the b value after endurance was as high as 1.11, and it was possible to determine that it was clearly colored visually.
（比較例３）
可塑剤としてグリセリンを６部、ジグリセリンを４部、亜硫酸ソーダを４部（亜硫酸ソーダ／可塑剤総量＝０．４）とした以外は実施例１と同様の操作を行いＰＶＡ系フィルムを得た。得られたフィルムを実施例１と同様に評価した。初期のｂ値は０．２０と低かったが、フィルム表面に亜硫酸ソーダが析出していた。
(Comparative Example 3)
The same operation as in Example 1 was performed except that 6 parts of glycerin, 4 parts of diglycerin, and 4 parts of sodium sulfite (sodium sulfite / total amount of plasticizer = 0.4) were obtained as plasticizers to obtain a PVA film. . The obtained film was evaluated in the same manner as in Example 1. Although the initial b value was as low as 0.20, sodium sulfite was deposited on the film surface.
（比較例４）
可塑剤としてグリセリンを２０部とし、亜硫酸ソーダを３．０部とした以外は実施例１と同様の操作を行いＰＶＡ系フィルムを得た。得られたフィルムを実施例１と同様に評価した。初期のｂ値は０．２６と低かったが、フィルム表面に亜硫酸ソーダが析出していた。
(Comparative Example 4)
A PVA-based film was obtained in the same manner as in Example 1 except that 20 parts of glycerin and 3.0 parts of sodium sulfite were used as plasticizers. The obtained film was evaluated in the same manner as in Example 1. The initial b value was as low as 0.26, but sodium sulfite was precipitated on the film surface.
以上の結果を表１に示す。
尚、表中、可塑剤及び亜硫酸塩の含有量は、ＰＶＡ樹脂１００重量部に対する重量部を示す。
又、ｂ値の「初期」とは、製膜直後の値を示し、「耐久」とは、上記「薬剤実包装テスト」後の値を示す。
The results are shown in Table 1.
In the table, the contents of the plasticizer and sulfite indicate parts by weight relative to 100 parts by weight of the PVA resin.
In addition, “initial value” of the b value indicates a value immediately after film formation, and “durability” indicates a value after the above “actual drug packaging test”.
Claims (10)
可塑剤（Ｂ）は、（１）グリセリン（Ｂ１）と、（２）ジグリセリン及び／又はトリメチロールプロパン（Ｂ２）を含み、
ポリビニルアルコール系樹脂（Ａ）１００重量部に対する可塑剤（Ｂ）の含有量が５〜５０重量部であり、
亜硫酸塩（Ｃ）が、亜硫酸アルカリ金属塩であり、
可塑剤（Ｂ）に対する亜硫酸塩（Ｃ）の含有割合（Ｃ／Ｂ：重量比）が０．０２を越えて０．３５以下である、水溶性フィルム。 Containing polyvinyl alcohol resin (A), plasticizer (B) and sulfite (C),
The plasticizer (B) includes (1) glycerin (B1) and (2) diglycerin and / or trimethylolpropane (B2),
The content of the plasticizer (B) with respect to 100 parts by weight of the polyvinyl alcohol-based resin (A) is 5 to 50 parts by weight,
Sulphite (C) is an alkali metal sulfite,
The water-soluble film whose content rate (C / B: weight ratio) of sulfite (C) with respect to a plasticizer (B) exceeds 0.02 and is 0.35 or less.
The water-soluble film according to any one of claims 1 to 9 , wherein the water-soluble film has a pH of 6 to 12 and a moisture content of less than 10% by weight for packaging a liquid detergent.
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| US7754318B2 (en) | 2005-06-16 | 2010-07-13 | The Nippon Synthetic Chemical Industry Co., Ltd. | Water-soluble film |
| KR100967532B1 (en) * | 2005-08-30 | 2010-07-05 | 가부시키가이샤 구라레 | Thermal recording material |
| US20080176985A1 (en) * | 2006-11-13 | 2008-07-24 | Verrall Andrew P | Water-soluble film |
| JPWO2016035671A1 (en) | 2014-09-01 | 2017-04-27 | 積水化学工業株式会社 | Water-soluble packaging film |
| JP5781676B1 (en) | 2014-09-12 | 2015-09-24 | 株式会社アイセロ | Water-soluble film, packaging bag, contents emitter, and method for producing water-soluble film |
| CN105916685A (en) | 2014-09-17 | 2016-08-31 | 积水化学工业株式会社 | Water-soluble packaging film |
| TWI689547B (en) | 2014-10-13 | 2020-04-01 | 美商摩諾索公司 | Water-soluble polyvinyl alcohol film with plasticizer blend, related methods, and related articles |
| JP2016108426A (en) * | 2014-12-05 | 2016-06-20 | 日本合成化学工業株式会社 | Water-soluble film and medicine package |
| JP6787131B2 (en) * | 2015-09-11 | 2020-11-18 | 三菱ケミカル株式会社 | Drug packaging using a water-soluble film, and a method for producing a water-soluble film |
| JP6787132B2 (en) * | 2015-09-11 | 2020-11-18 | 三菱ケミカル株式会社 | Water-soluble film and drug packaging |
| JP7035313B2 (en) * | 2015-09-11 | 2022-03-15 | 三菱ケミカル株式会社 | Water-soluble film and drug packaging |
| JP6992253B2 (en) * | 2015-09-11 | 2022-01-13 | 三菱ケミカル株式会社 | Water-soluble film and drug packaging |
| CN107922646B (en) * | 2015-09-11 | 2021-08-17 | 三菱化学株式会社 | Water-soluble film for packaging liquid detergent and liquid detergent package |
| CN113845675A (en) * | 2015-09-11 | 2021-12-28 | 三菱化学株式会社 | Water-soluble film and drug package |
| JP7161277B2 (en) * | 2015-11-19 | 2022-10-26 | 三菱ケミカル株式会社 | Water-soluble film and drug package |
| JP2017119434A (en) * | 2015-12-25 | 2017-07-06 | 日本合成化学工業株式会社 | Water-soluble film, medicine package, and manufacturing method of water-soluble film |
| TWI756233B (en) | 2016-06-27 | 2022-03-01 | 日商三菱化學股份有限公司 | Polyvinyl alcohol-based film for polarizing film, method for producing the same, and polarizing film using the polyvinyl alcohol-based film for polarizing film |
| JP2019189706A (en) * | 2018-04-20 | 2019-10-31 | 三菱ケミカル株式会社 | Water soluble film and agent package |
| US11840590B2 (en) | 2018-07-25 | 2023-12-12 | Sekisui Chemical Co., Ltd. | Polyvinyl alcohol film |
| JP7240420B2 (en) | 2018-12-28 | 2023-03-15 | 株式会社クラレ | Water-soluble film, method for producing the same, and package |
| WO2020138438A1 (en) | 2018-12-28 | 2020-07-02 | 株式会社クラレ | Water-soluble film, method of manufacturing same, and package |
| EP3904036A4 (en) | 2018-12-28 | 2022-09-14 | Kuraray Co., Ltd. | Water-soluble film and packaging material |
| CN114945522B (en) * | 2020-01-14 | 2024-08-09 | 株式会社爱赛璐 | Water-soluble film and medicine encapsulation capsule material with same function |
| US20230075035A1 (en) * | 2020-02-14 | 2023-03-09 | Aicello Corporation | Water-soluble film for liquid detergent-packaging capsule |
| JPWO2022004341A1 (en) * | 2020-06-29 | 2022-01-06 | ||
| WO2024181297A1 (en) * | 2023-02-28 | 2024-09-06 | 株式会社アイセロ | Water-soluble film for liquid detergent package capsule, and liquid detergent package capsule |
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| JP3602677B2 (en) * | 1996-03-29 | 2004-12-15 | 株式会社クラレ | Saponified ethylene-vinyl ester copolymer composition and method for producing the same |
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