JP2011252245A - Water repellent paper - Google Patents
Water repellent paper Download PDFInfo
- Publication number
- JP2011252245A JP2011252245A JP2010125649A JP2010125649A JP2011252245A JP 2011252245 A JP2011252245 A JP 2011252245A JP 2010125649 A JP2010125649 A JP 2010125649A JP 2010125649 A JP2010125649 A JP 2010125649A JP 2011252245 A JP2011252245 A JP 2011252245A
- Authority
- JP
- Japan
- Prior art keywords
- paper
- water
- water repellent
- wax
- repellent
- 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.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000005871 repellent Substances 0.000 title claims abstract description 89
- 230000002940 repellent Effects 0.000 title claims abstract description 58
- 229920000642 polymer Polymers 0.000 claims abstract description 58
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 53
- 238000000576 coating method Methods 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 17
- 239000011247 coating layer Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 abstract description 13
- 239000007864 aqueous solution Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 abstract description 2
- 239000000123 paper Substances 0.000 description 70
- -1 alkyl ketene dimer Chemical compound 0.000 description 54
- 239000001993 wax Substances 0.000 description 41
- 239000000178 monomer Substances 0.000 description 22
- 239000006185 dispersion Substances 0.000 description 21
- 150000003839 salts Chemical class 0.000 description 21
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 13
- 235000014113 dietary fatty acids Nutrition 0.000 description 13
- 239000000194 fatty acid Substances 0.000 description 13
- 229930195729 fatty acid Natural products 0.000 description 13
- 229920001131 Pulp (paper) Polymers 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000000306 component Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000005995 Aluminium silicate Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 235000012211 aluminium silicate Nutrition 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000011111 cardboard Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 239000010893 paper waste Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000005037 alkyl phenyl group Chemical group 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 238000005063 solubilization Methods 0.000 description 3
- 230000007928 solubilization Effects 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 102000011632 Caseins Human genes 0.000 description 2
- 108010076119 Caseins Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000003926 acrylamides Chemical class 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 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
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 229920003118 cationic copolymer Polymers 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000012055 fruits and vegetables Nutrition 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 239000013054 paper strength agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 238000007717 redox polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- BFXKJHOJSIMHSJ-UHFFFAOYSA-N 1-(hexadecoxymethyl)pyridin-1-ium Chemical class CCCCCCCCCCCCCCCCOC[N+]1=CC=CC=C1 BFXKJHOJSIMHSJ-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 1
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- SYENVBKSVVOOPS-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butyl prop-2-enoate Chemical compound CCC(CO)(CO)COC(=O)C=C SYENVBKSVVOOPS-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
- 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
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- BRRJLIHBOSHINH-UHFFFAOYSA-M C[n+]1ccccc1.CCCCCCCCCCCCCCCCCC([NH-])=O Chemical compound C[n+]1ccccc1.CCCCCCCCCCCCCCCCCC([NH-])=O BRRJLIHBOSHINH-UHFFFAOYSA-M 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N DEAEMA Natural products CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-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
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- HZVVJJIYJKGMFL-UHFFFAOYSA-N almasilate Chemical compound O.[Mg+2].[Al+3].[Al+3].O[Si](O)=O.O[Si](O)=O HZVVJJIYJKGMFL-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- WTPRWPLPFYNFMC-UHFFFAOYSA-N dimethyl-[[4-(6-methylheptyl)phenyl]methyl]-[2-(2-phenoxyethoxy)ethyl]azanium Chemical class C1=CC(CCCCCC(C)C)=CC=C1C[N+](C)(C)CCOCCOC1=CC=CC=C1 WTPRWPLPFYNFMC-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical class C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-UHFFFAOYSA-N 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229940094506 lauryl betaine Drugs 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 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
- CDJQLDOSFSALHP-UHFFFAOYSA-N n-[5-(oxiran-2-ylmethoxy)pentyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCOCC1CO1 CDJQLDOSFSALHP-UHFFFAOYSA-N 0.000 description 1
- MMMCIGSNLXGQIZ-UHFFFAOYSA-N n-[6-(oxiran-2-ylmethoxy)hexyl]prop-2-enamide Chemical compound C=CC(=O)NCCCCCCOCC1CO1 MMMCIGSNLXGQIZ-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- ZQXSMRAEXCEDJD-UHFFFAOYSA-N n-ethenylformamide Chemical compound C=CNC=O ZQXSMRAEXCEDJD-UHFFFAOYSA-N 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention 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
- 230000001681 protective effect Effects 0.000 description 1
- QYPWRPSMKLUGJZ-UHFFFAOYSA-N pyridin-1-ium;sulfate Chemical compound [O-]S([O-])(=O)=O.C1=CC=[NH+]C=C1.C1=CC=[NH+]C=C1 QYPWRPSMKLUGJZ-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 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
- 229920003169 water-soluble polymer Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paper (AREA)
Abstract
Description
本発明は、熱による撥水性の低下が少ない撥水紙に関する。 The present invention relates to a water-repellent paper that is less likely to cause a decrease in water repellency due to heat.
従来から、各種包装用紙材、例えば段ボール、重袋、包装紙などは、輸送中における内容物の品質保全、安全輸送、強度劣化防止のため種々の処理、加工が行われている。特に青果物、水産物などの包装に用いる包装紙材においては、水分による強度劣化防止のため、撥水性を付与したものが広く使用されている。紙材料に撥水性を付与する手段としては、一般にワックス系エマルジョンからなる撥水剤をオンマシンコーターやオフマシンコーターで塗工したり、スプレーを用いて噴霧したりすることが広く行われてきた。 Conventionally, various wrapping paper materials, such as cardboard, heavy bags, wrapping paper, and the like, have been subjected to various processing and processing for quality maintenance of contents during transportation, safe transportation, and prevention of strength deterioration. In particular, wrapping paper materials used for packaging fruits and vegetables, marine products, and the like are widely used to impart water repellency to prevent strength deterioration due to moisture. As a means for imparting water repellency to paper materials, it has been widely practiced to apply a water-repellent agent composed of a wax-based emulsion with an on-machine coater or an off-machine coater, or to spray it with a spray. .
近年、特にライナーにおいて古紙パルプの配合率が高まっており、こうしたライナーではワックス系撥水剤を塗工しても、古紙パルプ由来の填料や微細繊維の影響で撥水性が発現し難く、段ボールシートに加工する際の熱処理で、撥水性がさらに低下し易くなっている。その対策としてワックス系撥水剤の塗工量を増やすといった方法が挙げられるが、塗工量の増加によりコストアップとなるばかりでなく、塗工時のコーター汚れが顕著になり生産に支障をきたす場合もある。このため、古紙パルプの配合率が高い紙材料においても、少ない撥水剤塗工量で十分な撥水性を得る方法が求められている。 In recent years, the percentage of recycled paper pulp has increased especially in liners, and even when a wax-based water repellent is applied to such liners, water repellency is hardly exhibited due to the effects of fillers and fine fibers derived from waste paper pulp. The water repellency is more likely to be lowered by the heat treatment during processing. As a countermeasure, there is a method of increasing the coating amount of the wax-based water repellent, but not only will the cost increase due to the increase in the coating amount, but also the coater stains at the time of coating will become noticeable and hinder production. In some cases. For this reason, there is a demand for a method for obtaining sufficient water repellency with a small amount of water repellent coating even in paper materials having a high content ratio of waste paper pulp.
こうした問題の解決方法として、正電荷のコロイダルシリカ水分散体を塗工した紙表面にアニオン性撥水剤を塗工する方法（特許文献１）や、カチオン性共重合体の４級化合物とポリアミドポリアミン−エピハロヒドリン樹脂からなる混合液を下塗り後、撥水剤を塗工する方法（特許文献２）や、カチオン性共重合体とカルボン酸含有のポリアミドあるいはアルキルケテンダイマーからなる混合液を下塗り後、撥水剤を塗工する方法（特許文献３）や、アニオン性モノマーと疎水性モノマーを重合させたアクリル系ポリマー乳化物を下塗り後、撥水剤を塗工する方法（特許文献４）や、特定のアニオン性高分子分散剤存在下で疎水性ビニルモノマーを乳化重合した乳化物を下塗り後、撥水剤を塗工する方法（特許文献５）などが提案されている。 To solve these problems, a method of applying an anionic water repellent to the paper surface coated with a positively charged colloidal silica aqueous dispersion (Patent Document 1), a quaternary compound of a cationic copolymer and a polyamide After undercoating a mixed solution composed of a polyamine-epihalohydrin resin, after applying a water repellent (Patent Document 2) or undercoating a mixed solution composed of a cationic copolymer and a carboxylic acid-containing polyamide or alkyl ketene dimer, A method of applying a water repellent (Patent Document 3), a method of applying a water repellent after applying an acrylic polymer emulsion obtained by polymerizing an anionic monomer and a hydrophobic monomer (Patent Document 4), A method of applying a water repellent after applying an emulsion obtained by emulsion polymerization of a hydrophobic vinyl monomer in the presence of a specific anionic polymer dispersant (Patent Document 5) has been proposed. .
これらの方法は、古紙パルプの配合率が高い紙材料においても、少ない撥水剤塗工量で十分な撥水性を得ることができるが、いずれも下塗り剤を塗工、乾燥後に撥水剤を塗工、乾燥するもので、撥水性付与のために片面当り２回以上の塗工が必要となり、製造が煩雑となるといった問題がある。特に片面当り１回の塗工しかできない製造設備では、下塗り剤を塗工、乾燥した下塗り紙を一度リールに巻き取った後、改めて塗工機にセットして撥水剤を塗工する必要があり、生産効率の低下が著しくなる。 These methods can obtain sufficient water repellency with a small amount of water repellent coating amount even in paper materials with a high content ratio of waste paper pulp. Since the coating and drying are performed, two or more coatings per side are required for imparting water repellency, and there is a problem that the production becomes complicated. In particular, in a production facility that can only apply once per side, it is necessary to coat the primer, wind up the dried primer paper once on a reel, and set it on the coating machine again to apply the water repellent. There is a significant reduction in production efficiency.
下塗り剤を塗工することなく、少ない撥水剤塗工量でも熱による撥水性の低下が少ない撥水紙を提供することを目的とする。 An object of the present invention is to provide a water-repellent paper that does not cause a decrease in water repellency due to heat even when applied with a small amount of water-repellent agent without applying a primer.
本発明者らは前記課題を解決すべく鋭意検討した結果、紙支持体にワックス系撥水剤とポリアクリルアミド系高分子を特定の配合比率で含む塗工層を設けることで前記課題が解決可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by providing a coating layer containing a wax-based water repellent and a polyacrylamide polymer at a specific blending ratio on a paper support. As a result, the present invention has been completed.
本発明は、以下の各発明を包含する。
（１）紙支持体の少なくとも片面に塗工層を設けてなる撥水紙において、該塗工層のワックス系撥水剤とポリアクリルアミド系高分子の固形質量比が９９．９〜９８．０：０．１〜２．０である撥水紙。
The present invention includes the following inventions.
(1) In a water-repellent paper having a coating layer provided on at least one side of a paper support, the solid mass ratio of the wax-based water repellent and the polyacrylamide polymer in the coating layer is 99.9 to 98.0. : Water repellent paper of 0.1 to 2.0.
（２）前記ポリアクリルアミド系高分子の濃度０．５質量％水性液の２０℃におけるＪＩＳ Ｚ ８８０３−１９９１に規定されるＢ型粘度が５０〜２０００ｍＰａ・ｓである（１）に記載の撥水紙。 (2) The water repellent property according to (1), wherein the B-type viscosity defined in JIS Z 8803-1991 at 20 ° C. of the aqueous liquid having a concentration of 0.5% by mass of the polyacrylamide polymer is 50 to 2000 mPa · s. paper.
（３）前記塗工層中のワックス系撥水剤とポリアクリルアミド系高分子の合計塗工量が０．１〜１．０ｇ／ｍ２である（１）または（２）に記載の撥水紙。 (3) The water repellent according to (1) or (2), wherein the total coating amount of the wax-based water repellent and the polyacrylamide polymer in the coating layer is 0.1 to 1.0 g / m 2. paper.
本発明によれば、下塗りが不要のため生産効率を低下させることなく、熱による撥水性の低下が少ない撥水紙を提供することができる。 According to the present invention, it is possible to provide a water-repellent paper that is less likely to cause a decrease in water repellency due to heat without lowering the production efficiency because an undercoat is unnecessary.
本発明は紙支持体の少なくとも片面にワックス系撥水剤（Ａ）とポリアクリルアミド系高分子（Ｂ）とを含む塗工層を設けた撥水紙であって、（Ａ）と（Ｂ）の配合比が特定比率となるように配合したことを特徴とする。 The present invention is a water-repellent paper provided with a coating layer containing a wax-based water repellent (A) and a polyacrylamide-based polymer (B) on at least one side of a paper support, wherein (A) and (B) The blending ratio is characterized in that the blending ratio is a specific ratio.
本発明では、ワックス系撥水剤とポリアクリルアミド系高分子との混合液を紙支持体に塗工する際に、ポリアクリルアミド系高分子の増粘作用によりワックス系撥水剤の紙支持体内部への浸透を抑制し、ワックス成分を紙支持体表面に定着させるため、熱による撥水性の低下を抑制することができる。このため、ワックス系撥水剤（Ａ）とポリアクリルアミド系高分子（Ｂ）との固形分質量比（配合比率）は（Ａ）：（Ｂ）＝９９．９〜９８．０：０．１〜２．０の範囲とする必要があり、好ましくは（Ａ）：（Ｂ）＝９９．８〜９９．０：０．２〜１．０の範囲である。ポリアクリルアミド系高分子の配合比率が０．１質量％未満、ワックス系撥水剤が９９．９質量％以上であると、熱による撥水性の低下を抑制する効果が不十分となる。逆に、ポリアクリルアミド系高分子の配合比率が２．０質量％以上、ワックス系撥水剤が９８．０質量％未満であると、ポリアクリルアミド系高分子に起因する親水性が強まり、十分な撥水性が発現しない。 In the present invention, when a mixed liquid of a wax-based water repellent and a polyacrylamide polymer is applied to a paper support, the inside of the paper support of the wax-based water repellent is increased by the thickening action of the polyacrylamide polymer. Inhibition of water penetration and fixing of the wax component on the surface of the paper support can suppress a decrease in water repellency due to heat. For this reason, the solid content mass ratio (blending ratio) of the wax-based water repellent (A) and the polyacrylamide-based polymer (B) is (A) :( B) = 99.9 to 98.0: 0.1. It is necessary to make it the range of -2.0, Preferably it is the range of (A) :( B) = 99.8-99.0: 0.2-1.0. When the blending ratio of the polyacrylamide polymer is less than 0.1% by mass and the wax-based water repellent is 99.9% by mass or more, the effect of suppressing the decrease in water repellency due to heat becomes insufficient. On the other hand, when the blending ratio of the polyacrylamide polymer is 2.0% by mass or more and the wax-based water repellent is less than 98.0% by mass, the hydrophilicity due to the polyacrylamide polymer is increased and sufficient. No water repellency.
本発明で使用されるポリアクリルアミド系高分子は主にアクリルアミド、メタアクリルアミドなどのモノマーを重合したポリマーであり、前記モノマー以外に、イオン性モノマー、疎水性モノマー、親水性モノマー、分岐構造を付与できるモノマー、架橋構造を付与できる多官能性モノマーなども共重合することができる。 The polyacrylamide polymer used in the present invention is a polymer obtained by polymerizing monomers such as acrylamide and methacrylamide. In addition to the monomers, an ionic monomer, a hydrophobic monomer, a hydrophilic monomer, and a branched structure can be added. Monomers, polyfunctional monomers capable of imparting a crosslinked structure, and the like can also be copolymerized.
イオン性モノマーのうちアニオン性モノマーとしては、例えばアクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸などの不飽和カルボン酸およびそれらの塩、またはビニルスルホン酸、スチレンスルホン酸、アクリルアミドメチルプロパンスルホン酸などのスルホン酸類およびそれらの塩等が挙げられる。 Among the ionic monomers, anionic monomers include, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and their salts, or vinyl sulfonic acid, styrene sulfonic acid, acrylamidomethylpropane sulfone. Examples thereof include sulfonic acids such as acids and salts thereof.
また、カチオン性モノマーとしては、例えばＮ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリレート、Ｎ，Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチルアミノプロピル（メタ）アクリルアミド等のアミンおよびそれらの塩、およびそれらの４級化物等が挙げられる。 Examples of the cationic monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-dimethylamino. Examples thereof include amines such as propyl (meth) acrylamide and N, N-diethylaminopropyl (meth) acrylamide and salts thereof, and quaternized products thereof.
疎水性モノマーとしては、例えばアクリロニトリル、Ｎ，Ｎ−ジ−ｎ−プロピル（メタ）アクリルアミド、Ｎ−ｎ−ブチル（メタ）アクリルアミド、Ｎ−ｎ−ヘキシル（メタ）アクリルアミド、Ｎ−ｎ−オクチル（メタ）アクリルアミド、Ｎ−ｔｅｒｔ−オクチル（メタ）アクリルアミド、Ｎ−ｎ−ドデシル（メタ）アクリルアミド等のＮ−アルキル（メタ）アクリルアミド誘導体、Ｎ，Ｎ−ジグリシジル（メタ）アクリルアミド、Ｎ−（４−グリシドキシブチル）（メタ）アクリルアミド、Ｎ−（５−グリシドキシペンチル）アクリルアミド、Ｎ−（６−グリシドキシヘキシル）アクリルアミド等のＮ−（ω−グリシドキシアルキル）（メタ）アクリルアミド誘導体、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ブチル（メタ）アクリレート、ラウリル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、グリシジル（メタ）アクリレート等の（メタ）アクリレート誘導体、メタクリロニトリル、酢酸ビニル、塩化ビニル、塩化ビニリデン、エチレン、プロピレン、ブテン等のオレフィン類、スチレン、α−メチルスチレン、ブタジエン、イソプレン等を挙げることができる。 Examples of the hydrophobic monomer include acrylonitrile, N, N-di-n-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide, Nn-octyl (meth) ) N-alkyl (meth) acrylamide derivatives such as acrylamide, N-tert-octyl (meth) acrylamide, Nn-dodecyl (meth) acrylamide, N, N-diglycidyl (meth) acrylamide, N- (4-glycid N- (ω-glycidoxyalkyl) (meth) acrylamide derivatives such as xylbutyl) (meth) acrylamide, N- (5-glycidoxypentyl) acrylamide, N- (6-glycidoxyhexyl) acrylamide, methyl (Meth) acrylate, ethyl (meth) acrylate, butyl ( ) Acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate derivatives such as glycidyl (meth) acrylate, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene, etc. Olefins, styrene, α-methylstyrene, butadiene, isoprene and the like.
親水性モノマーとしては、例えばジアセトンアクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ，Ｎ−ジエチル（メタ）アクリルアミド、Ｎ−プロピルアクリルアミド、Ｎ−アクリロイルピロリジン、Ｎ−アクリロイルピペリジン、Ｎ−アクリロイルモルホリン、ヒドロキシエチル（メタ）アクリレート、ヒドロキシプロピル（メタ）アクリレート、各種のメトキシポリエチレングリコール（メタ）アクリレート、Ｎ−ビニルホルムアミド、Ｎ−ビニルアセトアミド、Ｎ−ビニル−２−ピロリドン等を挙げることができる。 Examples of the hydrophilic monomer include diacetone acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-propyl acrylamide, N-acryloylpyrrolidine, N -Acryloylpiperidine, N-acryloylmorpholine, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, various methoxypolyethylene glycol (meth) acrylates, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone Etc.
分岐構造を付与できるモノマーとしては、Ｎ，Ｎ−ジメチルアクリルアミドのような特定のＮ−置換アクリルアミド誘導体、あるいは（メタ）アリルスルホン酸およびその塩類等を挙げることができる。 Examples of the monomer capable of imparting a branched structure include specific N-substituted acrylamide derivatives such as N, N-dimethylacrylamide, (meth) allylsulfonic acid and salts thereof, and the like.
架橋構造を付与できるモノマーとしては、例えばメチレンビス（メタ）アクリルアミド、エチレンビス（メタ）アクリルアミド、ヘキサメチレンビス（メタ）アクリルアミド、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ジビニルベンゼン、ジアリルアクリルアミドなどの２官能型架橋性モノマー、あるいは１，３，５−トリアクリロイルヘキサヒドロ−Ｓ−トリアジン、トリアリルイソシアヌレート、トリアクリル酸ペンタエリスリトール、トリメチロールプロパンアクリレート、トリアクリルモルマール、ジアクリロイルイミド等の多官能型架橋性モノマー等が挙げられる。 Examples of monomers capable of imparting a crosslinked structure include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, hexamethylene bis (meth) acrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di Bifunctional crosslinkable monomers such as (meth) acrylate, divinylbenzene, diallylacrylamide, or 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate, pentaerythritol triacrylate, trimethylolpropane acrylate , Polyfunctional type crosslinkable monomers such as triacryl mormar and diacryloyl imide.
これらモノマーの重合については、特に制限はなく、溶液重合法、乳化重合法などの従来公知の各種方法により行うことができる。例えば、所定の反応容器に各種モノマー、分散剤および水を仕込み、ラジカル重合開始剤を加え、撹拌下、加温することにより得られる。モノマーの仕込み方法は同時重合、連続滴下重合等の従来公知の各種方法により行うことができる。ラジカル重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、またはこれらと亜硫酸水素ナトリウムといった還元剤とを組み合わせた形のレドックス系重合開始剤等を使用することができる。また、前記ラジカル重合開始剤には、アゾ系開始剤を用いてもよい。反応温度は単一重合開始剤の場合では一般に３０〜１００℃であり、レドックス系重合開始剤の場合ではより低く、一般に５〜９０℃である。分散剤としては、アルキルベンゼンスルホン酸塩、アルキルスルホン酸塩、アルキル硫酸エステル塩、脂肪酸金属塩、ポリオキシアルキルエーテル硫酸エステル塩、ポリオキシエチレンカルボン酸エステル硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩、コハク酸ジアルキルエステルスルホン酸塩等のイオン性界面活性剤や、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテルグリセリンホウ酸エステル、ポリオキシエチレンアルキルエーテルリン酸エステル、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ペンタエリスリトール脂肪酸エステル等のノニオン性界面活性剤が挙げられる。また、重合反応によって生成される高分子の分子量は、反応温度、反応時間で適宜調節することができ、ラジカル重合の場合、公知の連鎖移動剤の使用でも調節することができる。こうした分子量調節によりポリアクリルアミド系高分子水分散液の粘度を調節することができる。 There is no restriction | limiting in particular about superposition | polymerization of these monomers, It can carry out by various conventionally well-known methods, such as a solution polymerization method and an emulsion polymerization method. For example, it can be obtained by charging various monomers, a dispersant and water in a predetermined reaction vessel, adding a radical polymerization initiator, and heating with stirring. The monomer can be charged by various conventionally known methods such as simultaneous polymerization and continuous dropping polymerization. As the radical polymerization initiator, a persulfate such as potassium persulfate or ammonium persulfate, or a redox polymerization initiator in the form of a combination of these with a reducing agent such as sodium bisulfite can be used. An azo initiator may be used as the radical polymerization initiator. In the case of a single polymerization initiator, the reaction temperature is generally 30 to 100 ° C., and in the case of a redox polymerization initiator, it is lower, and generally 5 to 90 ° C. Dispersing agents include alkylbenzene sulfonate, alkyl sulfonate, alkyl sulfate ester, fatty acid metal salt, polyoxyalkyl ether sulfate, polyoxyethylene carboxylic ester sulfate, polyoxyethylene alkyl phenyl ether sulfate Ionic surfactants such as salts and dialkyl ester sulfonates of succinic acid, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether glycerin Borate ester, polyoxyethylene alkyl ether phosphate ester, sorbitan fatty acid ester, glycerin fatty acid ester, pentaerythritol fat Nonionic surfactants such as esters. In addition, the molecular weight of the polymer produced by the polymerization reaction can be appropriately adjusted depending on the reaction temperature and reaction time. In the case of radical polymerization, it can also be adjusted by using a known chain transfer agent. By adjusting the molecular weight, the viscosity of the polyacrylamide polymer aqueous dispersion can be adjusted.
前記ポリアクリルアミド系高分子の水性液のＢ型粘度は、固形分質量濃度０．５％、温度２０℃において５０〜２０００ｍＰａ・ｓの範囲が好ましく、より好ましくは１００〜１５００ｍＰａ・ｓの範囲である。ポリアクリルアミド系高分子水分散液のＢ型粘度が５０ｍＰａ・ｓ未満になると、塗工時にワックス系撥水剤が紙支持体内部へ浸透して撥水性の低下を抑制する効果が不十分となるおそれがある。逆に、粘度が２０００ｍＰａ・ｓを超えると、ポリアクリルアミド系高分子とワックス系撥水剤とが均一に混合し難くなるおそれがある。なお、本発明におけるＢ型粘度とは、ＪＩＳ Ｚ ８８０３−１９９１記載の単一円筒形回転粘度計による粘度測定方法によるものである。また、本発明において水性液とはポリアクリルアミド系高分子の水溶液または微粒子水分散液を意味する。 The B-type viscosity of the aqueous solution of the polyacrylamide polymer is preferably in the range of 50 to 2000 mPa · s, more preferably in the range of 100 to 1500 mPa · s at a solid content mass concentration of 0.5% and a temperature of 20 ° C. . When the B-type viscosity of the polyacrylamide-based polymer aqueous dispersion is less than 50 mPa · s, the wax-based water repellent penetrates into the inside of the paper support during coating, and the effect of suppressing the decrease in water repellency becomes insufficient. There is a fear. On the other hand, when the viscosity exceeds 2000 mPa · s, it may be difficult to uniformly mix the polyacrylamide polymer and the wax water repellent. In addition, the B type viscosity in this invention is based on the viscosity measuring method with a single cylindrical rotational viscometer described in JIS Z 8803-1991. In the present invention, the aqueous liquid means an aqueous solution or a fine particle aqueous dispersion of a polyacrylamide polymer.
本発明において使用される撥水剤は、ワックス系成分を分散質とする水性エマルジョンが好ましい。このエマルジョンにおいて、分散質となるワックス系成分は、パラフィンワックス、マイクロクリスタリンワックス、ポリエチレンワックスやマレイン化石油樹脂などの変性ワックス成分などを単独で使用してもよく、２種以上を混合して使用してもよい。また、ワックス系成分はロジン系樹脂あるいは不飽和高級アルコール等を含有しても差し支えない。なお、本発明において例示するポリエチレンワックスは重量平均分子量として１０００〜１００００、単独でフィルム状に成型できないものである。 The water repellent used in the present invention is preferably an aqueous emulsion having a wax component as a dispersoid. In this emulsion, the wax component used as a dispersoid may be a paraffin wax, a microcrystalline wax, a modified wax component such as polyethylene wax or maleated petroleum resin, or a mixture of two or more. May be. The wax component may contain rosin resin or unsaturated higher alcohol. In addition, the polyethylene wax illustrated in this invention is 1000-10000 as a weight average molecular weight, and cannot be shape | molded in a film form independently.
本発明において、ワックス系撥水剤に用いる分散剤には特に制限はなく、ノニオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤や両性界面活性剤が挙げられる。アニオン性界面活性剤としては、例えば高級アルコールの硫酸エステル塩、高級アルキルスルホン酸塩、高級カルボン酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルサルフェート塩、ポリオキシエチレンアルキルフェニルエーテルサルフェート塩、ビニルスルホサクシネート等が挙げられる。ノニオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリエチレングリコール脂肪酸エステル、エチレンオキサイド−プロピレンオキサイドブロック共重合体、ポリオキシエチレン脂肪酸アミド等のポリオキシエチレン構造を有する化合物や、ポリオキシエチレンソルビタン脂肪酸エステルなどのソルビタン誘導体等が挙げられる。カチオン性界面活性剤としては、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩、アシルアミノエチルジエチルアンモニウム塩、アシルアミノエチルジエチルアミン塩、アルキルアミドプロピルジメチルベンジルアンモニウム塩、アルキルピリジニウム塩、アルキルピリジニウム硫酸塩、ステアラミドメチルピリジニウム塩、アルキルキノリニウム塩、アルキルイソキノリニウム塩、脂肪酸ポリエチレンポリアミド、アシルアミノエチルピリジニウム塩、アシルコラミノホルミルメチルピリジニウム塩等の第４級アンモニウム塩、ステアロオキシメチルピリジニウム塩、脂肪酸トリエタノールアミン、脂肪酸トリエタノールアミンギ酸塩、トリオキシエチレン脂肪酸トリエタノールアミン、セチルオキシメチルピリジニウム塩、ｐ−イソオクチルフェノキシエトキシエチルジメチルベンジルアンモニウム塩等のエステル結合アミンやエーテル結合第４級アンモニウム塩、アルキルイミダゾリン、１−ヒドロキシエチル−２−アルキルイミダゾリン、１−アセチルアミノエチル−２−アルキルイミダゾリン、２−アルキル−４−メチル−４−ヒドロキシメチルオキサゾリン等の複素環アミン、ポリオキシエチレンアルキルアミン、Ｎ−アルキルプロピレンジアミン、Ｎ−アルキルポリエチレンポリアミン、Ｎ−アルキルポリエチレンポリアミンジメチル硫酸塩、アルキルビグアニド、長鎖アミンオキシドなどのアミン誘導体等が挙げられる。両性界面活性剤としては、ラウリルベタイン、ラウリルジメチルアミンオキサイド等が挙げられる。 In the present invention, the dispersant used for the wax-based water repellent is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Examples of the anionic surfactant include sulfate esters of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfone salts. Examples include succinate. Nonionic surfactants include compounds having a polyoxyethylene structure such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide-propylene oxide block copolymer, polyoxyethylene fatty acid amide, etc. And sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters. Cationic surfactants include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, acylaminoethyldiethylammonium salt, acylaminoethyldiethylamine salt, alkylamidopropyldimethylbenzylammonium salt, alkylpyridinium salt, alkyl Quaternary ammonium salts such as pyridinium sulfate, stearamide methylpyridinium salt, alkylquinolinium salt, alkylisoquinolinium salt, fatty acid polyethylene polyamide, acylaminoethylpyridinium salt, acylcoraminoformylmethylpyridinium salt, stearo Oxymethylpyridinium salt, fatty acid triethanolamine, fatty acid triethanolamine formate, trioxyethylene fatty acid tri Ester-bonded amines and ether-bonded quaternary ammonium salts such as tanolamine, cetyloxymethylpyridinium salt, p-isooctylphenoxyethoxyethyldimethylbenzylammonium salt, alkylimidazolines, 1-hydroxyethyl-2-alkylimidazolines, 1-acetyl Heterocyclic amines such as aminoethyl-2-alkylimidazoline, 2-alkyl-4-methyl-4-hydroxymethyloxazoline, polyoxyethylene alkylamine, N-alkylpropylenediamine, N-alkylpolyethylenepolyamine, N-alkylpolyethylenepolyamine Examples thereof include amine derivatives such as dimethyl sulfate, alkyl biguanide, and long chain amine oxide. Examples of amphoteric surfactants include lauryl betaine and lauryl dimethylamine oxide.
また、分散剤として保護コロイド作用を有する化合物、高酸価の酸変性化合物、水溶性高分子も使用可能である。該化合物としては、例えばポリビニルアルコール、カルボキシル基変性ポリビニルアルコール、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、変性デンプン、ポリビニル２−ピロリドン、ポリアクリル酸およびその塩、アクリル酸−無水マレイン酸共重合体およびその塩、スチレン−（メタ）アクリル酸共重合体、エチレン−（メタ）アクリル酸共重合体、イソブチレン−無水マレイン酸交互共重合体、（メタ）アクリル酸−（メタ）アクリル酸アルキルエステル共重合体等の不飽和カルボン酸単位の含有量が２６質量％以上のカルボキシル基含有ポリマーおよびその塩、ポリイタコン酸およびその塩、アミノ基を有する水溶性アクリル系共重合体、ゼラチン、アラビアゴム、カゼイン等、一般に微粒子の分散安定剤として用いられている化合物等が挙げられる。 Further, a compound having a protective colloid action, a high acid value acid-modified compound, and a water-soluble polymer can be used as a dispersant. Examples of the compound include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl 2-pyrrolidone, polyacrylic acid and salts thereof, acrylic acid-maleic anhydride copolymer, and Its salt, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer Carboxyl group-containing polymer having an unsaturated carboxylic acid unit content of 26% by mass or more, such as a polymer, and a salt thereof, polyitaconic acid and a salt thereof, a water-soluble acrylic copolymer having an amino group, gelatin, gum arabic, casein, etc. ,one Compounds are used as a dispersion stabilizer particles and the like in.
次に、本発明において使用するワックス系撥水剤の製造方法について説明する。本発明において使用するワックス系撥水剤を得るための製造方法は特に限定されないが、例えば、可溶化式による乳化分散、機械力式による乳化分散などを挙げることができる。可溶化式による乳化分散では、溶融したワックス系成分と界面活性剤とを混合して加温水を少しずつ注加していく。このとき、油系のＷ／Ｏ乳化状態から可溶化状態を経て水系のＯ／Ｗ乳化状態へと移り、ワックス系成分の微細粒子を析出する。可溶化式による乳化分散は水の注加以外に、非イオン性界面活性剤を用いて温度を上下することによっても行うことができる。機械力式による乳化分散では、ワックス系成分、界面活性剤および水を全量容器に入れて温度８０〜９０℃に加熱しながらホモミキサーで撹拌し、十分均一になった後ホモジナイザーで分散させる。 Next, the manufacturing method of the wax-type water repellent used in this invention is demonstrated. The production method for obtaining the wax-type water repellent used in the present invention is not particularly limited, and examples thereof include a solubilization type emulsification dispersion and a mechanical force type emulsification dispersion. In the emulsification dispersion by the solubilization formula, the melted wax-based component and the surfactant are mixed and warm water is poured little by little. At this time, the oil-based W / O emulsified state passes through the solubilized state to the water-based O / W emulsified state, and fine particles of the wax-based component are precipitated. The emulsification dispersion by the solubilization formula can be performed by raising or lowering the temperature using a nonionic surfactant in addition to the addition of water. In the emulsification dispersion by the mechanical force method, the wax system component, surfactant and water are all put in a container, stirred with a homomixer while heating to a temperature of 80 to 90 ° C., and after being sufficiently uniform, dispersed with a homogenizer.
本発明において、ワックス系撥水剤とポリアクリルアミド系高分子とを含む塗工液には、通常の塗工紙分野で使用される顔料、接着剤等を必要に応じて適宜混合することができる。 In the present invention, the coating liquid containing the wax-based water repellent and the polyacrylamide-based polymer can be appropriately mixed with a pigment, an adhesive, and the like used in a normal coated paper field as necessary. .
該顔料の具体例としては、重質炭酸カルシウム、軽質炭酸カルシウム、カオリン、焼成カオリン、タルク、硫酸カルシウム、硫酸バリウム、水酸化アルミニウム、二酸化チタン、酸化亜鉛、アルミナ、炭酸マグネシウム、酸化マグネシウム、シリカ、アルミノ珪酸マグネシウム、珪酸カルシウム、ベントナイト、ゼオライト、セリサイト、スメクタイト等の無機顔料や、密実型、中空型、貫通孔型などのプラスチックピグメント、バインダーピグメント等の有機顔料を例示できる。 Specific examples of the pigment include heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, talc, calcium sulfate, barium sulfate, aluminum hydroxide, titanium dioxide, zinc oxide, alumina, magnesium carbonate, magnesium oxide, silica, Examples thereof include inorganic pigments such as magnesium aluminosilicate, calcium silicate, bentonite, zeolite, sericite, and smectite, and plastic pigments such as solid, hollow, and through-hole types, and organic pigments such as binder pigments.
前記接着剤の具体例としては、例えば、酸化澱粉、エステル化澱粉、冷水可溶澱粉などの各種澱粉類、カゼイン、大豆蛋白、合成蛋白などの蛋白質類、カルボキシルメチルセルロース、メチルセルロースなどのセルロール誘導体、ポリビニルアルコールやその変性品等の水溶性接着剤、スチレン−ブタジエン共重合体、メチルメタクリレート−ブタジエン共重合体などの共役ジエン系共重合体ラテックス、アクリル酸アルキルエステルおよび／またはメタクリル酸アルキルエステルの重合体または共重合体ラテックス等のアクリル系（共）重合体ラテックスなどを例示できる。 Specific examples of the adhesive include, for example, various starches such as oxidized starch, esterified starch and cold water-soluble starch, proteins such as casein, soy protein and synthetic protein, cellulose derivatives such as carboxyl methylcellulose and methylcellulose, polyvinyl Water-soluble adhesives such as alcohol and modified products thereof, conjugated diene copolymer latex such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, polymer of alkyl acrylate and / or alkyl methacrylate Alternatively, acrylic (co) polymer latex such as copolymer latex can be exemplified.
また、塗工液には通常の製紙分野で使用される表面紙力剤、表面サイズ剤等を必要に応じて適宜混合することができる。表面紙力剤、表面サイズ剤の具体例としては、澱粉、酸化澱粉および澱粉変性物、ポリビニルアルコールおよびその誘導体、スチレン−マレイン酸系共重合体、α−オレフィン−マレイン酸系共重合体、スチレン−（メタ）アクリル酸系共重合体、アルキルケテンダイマー等の水分散物等を例示できる。 Further, a surface paper strength agent, a surface sizing agent, and the like used in the normal papermaking field can be appropriately mixed with the coating liquid as necessary. Specific examples of surface paper strength agents and surface sizing agents include starch, oxidized starch and modified starch, polyvinyl alcohol and derivatives thereof, styrene-maleic acid copolymer, α-olefin-maleic acid copolymer, styrene. Examples thereof include aqueous dispersions such as-(meth) acrylic acid copolymers and alkyl ketene dimers.
さらに、塗工液には染料、有色顔料、蛍光染料、酸化防止剤、老化防止剤、消泡剤、紫外線吸収剤、分散剤、ｐＨ調整剤等の各種助剤を必要に応じて適宜混合して使用することができる。 Furthermore, various auxiliary agents such as dyes, colored pigments, fluorescent dyes, antioxidants, anti-aging agents, antifoaming agents, ultraviolet absorbers, dispersants, pH adjusters, etc. are mixed in the coating liquid as necessary. Can be used.
ワックス系撥水剤とポリアクリルアミド系高分子とを含む塗工液の固形分濃度は通常１〜２５質量％、好ましくは２〜２０質量％の範囲である。 The solid content concentration of the coating liquid containing the wax-based water repellent and the polyacrylamide-based polymer is usually in the range of 1 to 25 mass%, preferably 2 to 20 mass%.
ワックス系撥水剤とポリアクリルアミド系高分子とを含む塗工液を紙支持体に塗工する設備としては、２本ロールサイズプレコーター、ゲートロールサイズプレスコーター、フィルムメタリングサイズプレスコーター、ブレードコーター、キャレンダー、チャンプレックスコーター、バーコーター、ロールコーター、リバースロールコーター、グラビアコーター、エアーナイフコーター、ダイスロットコーター、カーテンコーター、スプレーコーター等から適宜選択することができる。 Equipment for applying a coating liquid containing a wax-based water repellent and a polyacrylamide polymer to a paper support includes a two-roll size precoater, a gate roll size press coater, a film metering size press coater, and a blade. It can be appropriately selected from a coater, a calendar, a champlex coater, a bar coater, a roll coater, a reverse roll coater, a gravure coater, an air knife coater, a die slot coater, a curtain coater, a spray coater and the like.
本発明において、ワックス系撥水剤とポリアクリルアミド系高分子の合計塗工量は、片面当り０．１〜１ｇ／ｍ２の範囲が好ましい。塗工量が０．１ｇ／ｍ２未満であると、撥水性が不十分となるおそれがある。塗工量が１ｇ／ｍ２を超えると、撥水性が飽和し、経済的にも好ましくない。 In the present invention, the total coating amount of the wax water repellent and the polyacrylamide polymer is preferably in the range of 0.1 to 1 g / m 2 per side. If the coating amount is less than 0.1 g / m 2 , the water repellency may be insufficient. When the coating amount exceeds 1 g / m 2 , the water repellency is saturated, which is not preferable economically.
本発明において使用できる紙支持体としては、ライナー、ボール紙などの板紙や、上質紙、中質紙、クラフト紙等が挙げられる。 Examples of the paper support that can be used in the present invention include paperboard such as liner and cardboard, high quality paper, medium quality paper, and craft paper.
前記紙支持体に使用されるパルプとしては、例えば、一般に使用されている広葉樹晒クラフトパルプ（ＬＢＫＰ）、針葉樹晒クラフトパルプ（ＮＢＫＰ）等の漂白化学パルプや、砕木パルプ（ＧＰ）、加圧式砕木パルプ（ＰＧＷ）、リファイナー砕木パルプ（ＲＰＭ）、サーモメカニカルパルプ（ＴＭＰ）等の機械パルプや、亜硫酸パルプ、古紙パルプなどが適宜混合使用される。古紙パルプとしては、段ボール古紙、雑誌古紙などが挙げられる。また、本発明の効果を損なわない範囲で必要に応じてケナフ等の非木材繊維原料から得られるパルプ繊維、合成パルプ、無機繊維等を混合することができる。 Examples of the pulp used for the paper support include bleached chemical pulp such as commonly used hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP), ground pulp (GP), and pressurized ground wood. Mechanical pulp such as pulp (PGW), refiner groundwood pulp (RPM), and thermomechanical pulp (TMP), sulfite pulp, waste paper pulp, and the like are appropriately mixed and used. Examples of the used paper pulp include cardboard used paper and magazine used paper. Moreover, pulp fiber, synthetic pulp, inorganic fiber, etc. which are obtained from non-wood fiber raw materials, such as kenaf, can be mixed as needed in the range which does not impair the effect of this invention.
紙支持体に内添される填料としては、例えば重質炭酸カルシウム、軽質炭酸カルシウム、亜硫酸カルシウム、石膏、タルク、カオリン、焼成カオリン、ホワイトカーボン、非晶質シリカ、珪藻土、炭酸マグネシウム、二酸化チタン、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、水酸化亜鉛等の無機顔料や、尿素−ホルマリン樹脂微粒子、微小中空粒子等の有機顔料等が例示できる。填料は２種類以上の混合使用も可能である。 Examples of the filler internally added to the paper support include heavy calcium carbonate, light calcium carbonate, calcium sulfite, gypsum, talc, kaolin, calcined kaolin, white carbon, amorphous silica, diatomaceous earth, magnesium carbonate, titanium dioxide, Examples thereof include inorganic pigments such as aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and zinc hydroxide, and organic pigments such as urea-formalin resin fine particles and fine hollow particles. Two or more fillers can be used in combination.
紙支持体にはパルプと填料の他に、内添サイズ剤、アニオン性、ノニオン性、カチオン性あるいは両性の歩留り向上剤、濾水性向上剤、紙力増強剤等の抄紙用内添助剤を必要に応じて添加することができる。内添サイズ剤の具体例としては、例えば、アルキルケテンダイマー系、アルケニル無水コハク酸系、スチレン−アクリル系、高級脂肪酸系、石油樹脂系サイズ剤、ロジン系サイズ剤等が挙げられる。また、歩留り向上剤、濾水性向上剤、紙力増強剤の具体例としては、例えば、アルミニウム等の多価金属化合物（具体的には、硫酸バンド、塩化アルミニウム、アルミン酸ソーダ、塩基性アルミニウム化合物等）、各種澱粉類、ポリアクリルアミド、尿素樹脂、ポリアミド−ポリアミン樹脂、ポリエチレンイミン、ポリアミン、ポリビニルアルコール、ポリエチレンオキサイド等が例示できる。さらに、染料、ｐＨ調整剤、スライムコントロール剤、消泡剤、粘剤等の抄紙用添加助剤も用途に応じて適宜使用できる。 In addition to pulp and filler, the paper support contains internal additives for papermaking, such as internal sizing agents, anionic, nonionic, cationic or amphoteric yield improvers, drainage improvers, and paper strength enhancers. It can be added as necessary. Specific examples of the internally added sizing agent include alkyl ketene dimer, alkenyl succinic anhydride, styrene-acrylic, higher fatty acid, petroleum resin sizing agent, rosin sizing agent and the like. Specific examples of yield improvers, drainage improvers, and paper strength enhancers include, for example, polyvalent metal compounds such as aluminum (specifically, sulfate bands, aluminum chloride, sodium aluminate, basic aluminum compounds). Etc.), various starches, polyacrylamide, urea resin, polyamide-polyamine resin, polyethyleneimine, polyamine, polyvinyl alcohol, polyethylene oxide and the like. Furthermore, additive agents for papermaking such as dyes, pH adjusters, slime control agents, antifoaming agents, and stickers can be appropriately used depending on the application.
紙支持体の抄紙条件については特に制限はなく、例えば、長網式抄紙機、ギャップフォーマー型抄紙機、円網式抄紙機、短網式抄紙機、傾斜式抄紙機、各種コンビネーション抄紙機等の商業規模の抄紙機が、目的に応じて適宜選択して使用できる。また、本発明で上記抄紙工程から得られる紙支持体は単層のみならず、２層以上の抄き合せ紙でもよい。 There are no particular restrictions on the paper making conditions of the paper support. For example, a long net paper machine, a gap former type paper machine, a circular net paper machine, a short net paper machine, an inclined paper machine, various combination paper machines, etc. Commercial scale paper machines can be selected and used as appropriate according to the purpose. Further, the paper support obtained from the paper making process in the present invention may be not only a single layer but also two or more layers of paper.
以下に実施例を挙げて本発明を具体的に説明するが、もちろん、本発明はそれらに限定されるものではない。なお、特に断らない限り、例中の部および％はそれぞれ質量部、および質量％を示す。また、使用した薬剤の添加量は固形分換算の質量部を示す。 EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in an example show a mass part and the mass%, respectively. Moreover, the addition amount of the used chemical | medical agent shows the mass part of solid content conversion.
実施例および比較例で得た撥水紙を以下の方法で評価し、その結果を表１に示した。 The water-repellent paper obtained in Examples and Comparative Examples was evaluated by the following method, and the results are shown in Table 1.
（Ｂ型粘度）
ポリアクリルアミド系高分子の濃度０．５質量％水性液について、液温を２０℃に調整した後、ＪＩＳ Ｚ ８８０３−１９９１記載の単一円筒形回転粘度計による粘度測定方法でＢ型粘度を測定した。
(B type viscosity)
After adjusting the liquid temperature to 20 ° C. for an aqueous liquid having a polyacrylamide polymer concentration of 0.5 mass%, the B-type viscosity is measured by a viscosity measuring method using a single cylindrical rotational viscometer described in JIS Z 8803-1991. did.
（撥水度）
得られた評価用撥水紙を２３℃、相対湿度５０％の環境下において２４時間調湿後、ＪＡＰＡＮ ＴＡＰＰＩ 紙パルプ試験方法 Ｎｏ.６８：２０００に規定される方法に準じて撥水度を評価した。また、撥水度の熱劣化を試験するため、定温乾燥機を用いて１４０℃の条件下で２０分間熱処理した後、２３℃、相対湿度５０％の環境下において２４時間調湿して、同様に撥水度を評価した。なお、撥水度の評価はＲ０からＲ１０で判定され、Ｒの数字が大きいほど撥水性が良好であることを示している。
(Water repellency)
The obtained water-repellent paper for evaluation was conditioned for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then evaluated for water repellency according to the method defined in JAPAN TAPPI Paper Pulp Test Method No. 68: 2000. did. In addition, in order to test the thermal deterioration of the water repellency, after heat treatment for 20 minutes at 140 ° C. using a constant temperature dryer, the humidity was adjusted for 24 hours in an environment of 23 ° C. and 50% relative humidity. The water repellency was evaluated. The evaluation of the water repellency is determined from R0 to R10, and the larger the R number, the better the water repellency.
＜実施例１＞
（ポリアクリルアミド系高分子水分散液の調製）
水に対してポリアクリルアミド系高分子水分散液（商品名：「ハイホルダーＣ５０３」、栗田工業社製）を撹拌しながら点滴して、最終的に固形分濃度０．５％のポリアクリルアミド系高分子水分散液を調製した。このとき、０．５％水分散液のＢ型粘度は９９０ｍＰａ・ｓであった。
（撥水処理塗工液の調製）
ワックス系撥水剤（商品名：「ＷＲ３９３６」、星光ＰＭＣ社製）および前記０．５％ポリアクリルアミド系高分子水分散液をワックス系撥水剤：ポリアクリルアミド系高分子＝９９．５部：０．５部となるように混合し、最終的に固形分濃度が４％の撥水処理塗工液を調製した。
（撥水紙の作成）
未塗工のジュートライナー（坪量１６０ｇ／ｍ２）の表面に、上記で得た撥水処理塗工液を固形分塗工量（ワックス系撥水剤とポリアクリルアミド系高分子の合計）が０．４ｇ／ｍ２となるようメイヤーバーで塗工後、熱風乾燥機にて１３０℃、１５秒間乾燥して撥水紙を得た。
<Example 1>
(Preparation of polyacrylamide polymer aqueous dispersion)
A polyacrylamide polymer aqueous dispersion (trade name: “HIHHOLDER C503”, manufactured by Kurita Kogyo Co., Ltd.) is instilled into water with stirring, and finally a polyacrylamide polymer with a solid content concentration of 0.5% is added. A molecular water dispersion was prepared. At this time, the B-type viscosity of the 0.5% aqueous dispersion was 990 mPa · s.
(Preparation of water repellent coating liquid)
Wax-based water repellent (trade name: “WR3936”, manufactured by Seiko PMC Co., Ltd.) and the above 0.5% polyacrylamide-based polymer aqueous dispersion were mixed with wax-based water-repellent: polyacrylamide-based polymer = 99.5 parts: It mixed so that it might become 0.5 part, and finally the water-repellent treatment coating liquid whose solid content concentration is 4% was prepared.
(Create water-repellent paper)
On the surface of an uncoated jute liner (basis weight 160 g / m 2 ), the water-repellent treatment coating solution obtained above has a solid coating amount (total of wax-based water repellent and polyacrylamide polymer). After coating with a Mayer bar so as to be 0.4 g / m 2 , it was dried with a hot air dryer at 130 ° C. for 15 seconds to obtain a water-repellent paper.
＜実施例２＞
ワックス系撥水剤とポリアクリルアミド系高分子の配合比率を、ワックス系撥水剤：ポリアクリルアミド系高分子＝９９．９部：０．１部とした以外は実施例１と同様にして撥水紙を得た。
<Example 2>
The water repellency was the same as in Example 1 except that the mixing ratio of the wax-based water repellent and the polyacrylamide-based polymer was changed to wax-based water repellant: polyacrylamide-based polymer = 99.9 parts: 0.1 parts. I got paper.
＜実施例３＞
ワックス系撥水剤とポリアクリルアミド系高分子の配合比率を、ワックス系撥水剤：ポリアクリルアミド系高分子＝９８部：２部とした以外は実施例１と同様にして撥水紙を得た。
<Example 3>
A water-repellent paper was obtained in the same manner as in Example 1 except that the mixing ratio of the wax-based water repellent and the polyacrylamide-based polymer was changed to wax-based water repellent: polyacrylamide-based polymer = 98 parts: 2 parts. .
＜実施例４＞
ポリアクリルアミド系高分子水分散液を「ハイモロックＦＡ２３０（ハイモ社製）」とした以外は、実施例１と同様にして撥水紙を得た。該ポリアクリルアミド系高分子水分散液の濃度０．５％液のＢ型粘度は５０ｍＰａ・ｓであった。
<Example 4>
A water-repellent paper was obtained in the same manner as in Example 1 except that the polyacrylamide-based polymer aqueous dispersion was “Himoloc FA230 (manufactured by Hymo Co.)”. The B type viscosity of the 0.5% concentration polyacrylamide polymer aqueous dispersion was 50 mPa · s.
＜実施例５＞
ポリアクリルアミド系高分子水分散液を「ハイホルダーＡ７７４（栗田工業社製）」とした以外は、実施例１と同様にして撥水紙を得た。該ポリアクリルアミド系高分子水分散液の濃度０．５％液のＢ型粘度が１８００ｍＰａ・ｓであった。
<Example 5>
A water-repellent paper was obtained in the same manner as in Example 1 except that “High Holder A774 (manufactured by Kurita Kogyo)” was used as the polyacrylamide polymer aqueous dispersion. The B-type viscosity of the 0.5% concentration polyacrylamide polymer aqueous dispersion was 1800 mPa · s.
＜実施例６＞
水に対してポリアクリルアミド系高分子粉末（商品名：「アコパール」、ＭＴアクアポリマー社製）を撹拌しながら添加し、ポリアクリルアミド系高分子の固形分濃度が０．５％の水溶液を調製した。このとき、０．５％水溶液の２０℃におけるＢ型粘度は６４０ｍＰａ・ｓであった。ポリアクリルアミド系高分子を上記の０．５％水溶液とした以外は、実施例１と同様にして撥水紙を得た。
<Example 6>
Polyacrylamide polymer powder (trade name: “Acopearl”, manufactured by MT Aqua Polymer Co., Ltd.) was added to water while stirring to prepare an aqueous solution with a polyacrylamide polymer solid content concentration of 0.5%. . At this time, the B-type viscosity at 20 ° C. of the 0.5% aqueous solution was 640 mPa · s. A water repellent paper was obtained in the same manner as in Example 1 except that the polyacrylamide polymer was changed to the above 0.5% aqueous solution.
＜実施例７＞
ポリアクリルアミド系高分子水溶液を「ポリストロン１２０８Ｆ（荒川化学工業社製）」とした以外は、実施例１と同様にして撥水紙を得た。該ポリアクリルアミド系高分子水分散液の０．５％液のＢ型粘度が１５ｍＰａ・ｓであった。
<Example 7>
A water-repellent paper was obtained in the same manner as in Example 1 except that the polyacrylamide polymer aqueous solution was “Polystron 1208F (Arakawa Chemical Industries, Ltd.)”. The B-type viscosity of 0.5% liquid of the polyacrylamide polymer aqueous dispersion was 15 mPa · s.
＜実施例８＞
撥水処理塗工液の最終固形分濃度を０．５％とし、撥水処理塗工液を塗工する紙支持体を晒クラフト紙（坪量７０ｇ／ｍ２）とし、撥水処理塗工液の塗工量を０．０５ｇ／ｍ２とした以外は、実施例１と同様にして撥水紙を得た。
<Example 8>
The final solid concentration of the water-repellent coating liquid is 0.5%, and the paper support on which the water-repellent coating liquid is coated is bleached kraft paper (basis weight 70 g / m 2 ). A water-repellent paper was obtained in the same manner as in Example 1 except that the coating amount of the liquid was 0.05 g / m 2 .
＜実施例９＞
撥水処理塗工液の最終固形分濃度を１％とし、撥水処理塗工液を塗工する紙支持体を晒クラフト紙（坪量７０ｇ／ｍ２）とし、撥水処理塗工液の塗工量を０．１ｇ／ｍ２とした以外は、実施例１と同様にして撥水紙を得た。
<Example 9>
The final solid content concentration of the water-repellent coating liquid is 1%, the paper support on which the water-repellent coating liquid is applied is bleached kraft paper (basis weight 70 g / m 2 ), and the water-repellent coating liquid A water-repellent paper was obtained in the same manner as in Example 1 except that the coating amount was 0.1 g / m 2 .
＜実施例１０＞
撥水処理塗工液の最終固形分濃度を７％とし、撥水処理塗工液の塗工量を１ｇ／ｍ２とした以外は、実施例１と同様にして撥水紙を得た。
<Example 10>
A water repellent paper was obtained in the same manner as in Example 1 except that the final solid content concentration of the water repellent treatment coating liquid was 7% and the coating amount of the water repellent treatment coating liquid was 1 g / m 2 .
＜実施例１１＞
撥水処理塗工液の最終固形分濃度を１０％とし、撥水処理塗工液の塗工量を１．５ｇ／ｍ２とした以外は、実施例１と同様にして撥水紙を得た。
<Example 11>
A water-repellent paper was obtained in the same manner as in Example 1 except that the final solid content concentration of the water-repellent coating liquid was 10% and the coating amount of the water-repellent coating liquid was 1.5 g / m 2. It was.
＜比較例１＞
ワックス系撥水剤とポリアクリルアミド系高分子の配合比率を、ワックス系撥水剤：ポリアクリルアミド系高分子＝９９．９５部：０．０５部とした以外は実施例１と同様にして撥水紙を得た。
<Comparative Example 1>
The water repellency was the same as in Example 1 except that the blending ratio of the wax-based water repellent and the polyacrylamide polymer was changed to wax-based water repellant: polyacrylamide polymer = 99.95 parts: 0.05 parts. I got paper.
＜比較例２＞
ワックス系撥水剤とポリアクリルアミド系高分子の配合比率を、ワックス系撥水剤：ポリアクリルアミド系高分子＝９７部：３部とした以外は実施例１と同様にして撥水紙を得た。
<Comparative example 2>
A water-repellent paper was obtained in the same manner as in Example 1 except that the mixing ratio of the wax-based water repellent and the polyacrylamide-based polymer was changed to wax-based water repellent: polyacrylamide-based polymer = 97 parts: 3 parts. .
表１から明らかなように、実施例１〜１１は下塗り剤を塗工することなく、少ない撥水剤塗工量でも熱による撥水性の低下を効果的に抑制することができた。一方、比較例１〜２はポリアクリルアミド系高分子の配合比率が本発明の特定する範囲外であるため、熱による撥水性の低下が大きかった。 As is apparent from Table 1, Examples 1 to 11 were able to effectively suppress a decrease in water repellency due to heat even without applying a primer, even with a small amount of water repellent coating. On the other hand, in Comparative Examples 1 and 2, since the blending ratio of the polyacrylamide polymer was outside the range specified by the present invention, the decrease in water repellency due to heat was large.
紙支持体にワックス系撥水剤とポリアクリルアミド系高分子の固形分質量比が９９．９〜９８．０：０．１〜２．０である塗工層を設けた本発明の撥水紙は、下塗り剤の塗工が不要で、熱による撥水性の低下が少なく、青果物、水産物等を包装する段ボール、重袋、包装紙等の各種包装用紙材として優れた適性を有していた。 The water-repellent paper of the present invention in which a coating layer having a solid mass ratio of a wax-based water repellent and a polyacrylamide polymer is 99.9 to 98.0: 0.1 to 2.0 is provided on a paper support. No coating of the undercoat was necessary, and the water repellency was hardly lowered by heat, and had excellent suitability as various packaging paper materials such as corrugated cardboard, heavy bags and wrapping paper for packaging fruits and vegetables.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010125649A JP5454362B2 (en) | 2010-06-01 | 2010-06-01 | Water repellent paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010125649A JP5454362B2 (en) | 2010-06-01 | 2010-06-01 | Water repellent paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011252245A true JP2011252245A (en) | 2011-12-15 |
| JP5454362B2 JP5454362B2 (en) | 2014-03-26 |
Family
ID=45416378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010125649A Active JP5454362B2 (en) | 2010-06-01 | 2010-06-01 | Water repellent paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5454362B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013170327A (en) * | 2012-02-21 | 2013-09-02 | Oji Holdings Corp | Sheet for fruit |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0726495A (en) * | 1993-07-12 | 1995-01-27 | Mitsui Toatsu Chem Inc | Method for production paper board and paper board obtained by this method |
| JPH09169946A (en) * | 1995-12-20 | 1997-06-30 | Mitsui Toatsu Chem Inc | Surface coating agent and its utilization |
| JPH09310297A (en) * | 1996-05-17 | 1997-12-02 | Oji Paper Co Ltd | Wax-coated paper and its production |
-
2010
- 2010-06-01 JP JP2010125649A patent/JP5454362B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0726495A (en) * | 1993-07-12 | 1995-01-27 | Mitsui Toatsu Chem Inc | Method for production paper board and paper board obtained by this method |
| JPH09169946A (en) * | 1995-12-20 | 1997-06-30 | Mitsui Toatsu Chem Inc | Surface coating agent and its utilization |
| JPH09310297A (en) * | 1996-05-17 | 1997-12-02 | Oji Paper Co Ltd | Wax-coated paper and its production |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013170327A (en) * | 2012-02-21 | 2013-09-02 | Oji Holdings Corp | Sheet for fruit |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5454362B2 (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5835093B2 (en) | Oil resistant paper and method for producing oil resistant paper | |
| TWI685546B (en) | Resin emulsion sizing agent and paper obtained by using the sizing agent | |
| JP2017040021A (en) | Rosin-based emulsion sizing agent and paper | |
| JPH03227481A (en) | Sizing agent composition for paper-making and sizing method | |
| JP2020163675A (en) | Paper-made barrier material | |
| EP2593604B1 (en) | Surface sizing of paper | |
| JP2000045197A (en) | Surface-coating agent for making paper and surface- coated paper | |
| JP5005938B2 (en) | Permeation inhibiting method, printing base paper and printing paper using the same | |
| JP5454362B2 (en) | Water repellent paper | |
| JP7298409B2 (en) | Barrier laminate | |
| JP6213253B2 (en) | Fruit bag paper | |
| JP2005226200A (en) | Paper making method | |
| JP5821684B2 (en) | Fruit bag paper | |
| JP5760648B2 (en) | Water repellent cardboard | |
| JP5408560B2 (en) | Sizing composition, papermaking method, and board manufacturing method | |
| JP3936966B2 (en) | Co-binder for pigment-coated paper and pigment-coated paper | |
| JP4316976B2 (en) | Surface coating agent for neutral newsprint and method for producing neutral newsprint | |
| JP2017210701A (en) | Additive for paper and manufacturing method of paper | |
| JP2011117107A (en) | Water-repellent paper | |
| JPH10204792A (en) | Surface sizing agent | |
| JP4941010B2 (en) | Undercoat coating liquid for water repellent, water repellent paper and method for producing the same | |
| JP5910329B2 (en) | Manufacturing method of base paper for processing | |
| JP7413904B2 (en) | Paper additives and paper | |
| JP5464309B2 (en) | Water repellent primer and paper manufacturing method | |
| JP2012036510A (en) | Water repellent paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120720 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130524 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130528 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130708 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20130708 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131210 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131223 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5454362 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |