JPS6240477B2 - - Google Patents
Info
- Publication number
- JPS6240477B2 JPS6240477B2 JP54172487A JP17248779A JPS6240477B2 JP S6240477 B2 JPS6240477 B2 JP S6240477B2 JP 54172487 A JP54172487 A JP 54172487A JP 17248779 A JP17248779 A JP 17248779A JP S6240477 B2 JPS6240477 B2 JP S6240477B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- component
- paper
- carbon atoms
- ester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 238000004513 sizing Methods 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 13
- 239000000194 fatty acid Substances 0.000 claims description 13
- 229930195729 fatty acid Natural products 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- 229920001567 vinyl ester resin Polymers 0.000 claims description 13
- 238000007127 saponification reaction Methods 0.000 claims description 11
- 150000004665 fatty acids Chemical class 0.000 claims description 10
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 8
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 8
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 125000005907 alkyl ester group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- VUTSITSGGYCKFP-UHFFFAOYSA-J [C+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [C+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VUTSITSGGYCKFP-UHFFFAOYSA-J 0.000 claims 1
- 239000000123 paper Substances 0.000 description 47
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- 230000002209 hydrophobic effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- -1 alkyl vinyl ether Chemical compound 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000005187 foaming Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 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
- 239000000835 fiber Substances 0.000 description 3
- 125000003010 ionic group Chemical group 0.000 description 3
- 239000002655 kraft paper Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 3
- LAYAKLSFVAPMEL-UHFFFAOYSA-N 1-ethenoxydodecane Chemical compound CCCCCCCCCCCCOC=C LAYAKLSFVAPMEL-UHFFFAOYSA-N 0.000 description 2
- XXCVIFJHBFNFBO-UHFFFAOYSA-N 1-ethenoxyoctane Chemical compound CCCCCCCCOC=C XXCVIFJHBFNFBO-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- DQYSALLXMHVJAV-UHFFFAOYSA-M 3-heptyl-2-[(3-heptyl-4-methyl-1,3-thiazol-3-ium-2-yl)methylidene]-4-methyl-1,3-thiazole;iodide Chemical compound [I-].CCCCCCCN1C(C)=CS\C1=C\C1=[N+](CCCCCCC)C(C)=CS1 DQYSALLXMHVJAV-UHFFFAOYSA-M 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 2
- 229940018557 citraconic acid Drugs 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000007787 solid Substances 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
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- QJJDJWUCRAPCOL-UHFFFAOYSA-N 1-ethenoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOC=C QJJDJWUCRAPCOL-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 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 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は優れたサイズ度を有する中性紙に関す
る。
更に詳しくは、
硫酸バン土を含有せず、かつ、
(A) 炭素数が6以上の脂肪酸のビニルエステル、
炭素数が6以上のアルキル基のビニルエーテ
ル、炭素数が6以上のα−オレフインよりなる
群より選ばれる単量体の少なくとも一種、
(B) エチレン性不飽和カルボン酸もしくはその低
級アルキルエステルまたは酸無水物の少なくと
も一種、および、
(C) 酢酸ビニルエステル
の三成分を必須成分として含む共重合体をアルカ
リケン化して得られる水溶性変性ポリビニルアル
コール(以下ポリビニルアルコールをPVAと略
記する)を0.1〜5重量%含有することを特徴と
する優れたサイズ度を有する中性紙に関する。
紙はパルプを主原料とする親水性の多孔質材料
であるが、単にパルプを抄紙したままでは実用に
耐えない。そこでサイズ剤とか填料とか各種の紙
薬品を用いてはじめて実用に耐える紙をうるので
ある。紙は実用物性として多くの項目があげられ
るが、中でもサイズ度は、印刷インキのにじみ、
浸透性、筆記用インキのにじみさらには加工用原
紙にあつては加工液の浸透性およびそれに伴なう
加工紙物性と密接に関係する重要な性質である。
一般に従来使用されているサイズ性を有する紙
の多くは硫酸バン土の介在によつてロジン系サイ
ズ剤をパルプ繊維上に定着せしめることによつて
製造されるものである。
しかしながら硫酸バン土を定着剤として使用し
た場合には製造工程中に硫酸バン土の硫酸根によ
り紙が酸性になり、カレンダーロール、ドライヤ
ーロールその他工程中に接触する金属を腐食する
ばかりでなく、紙の強度や耐久性に悪い影響をあ
たえることにもなり、又或る種の印刷に対しても
障害をおこすことがある。又、硫酸バン土を使用
して抄造した紙の実用上の大きな問題点として
は、接触した金属が極めて錆び易いことが広く知
られており、金属製品の包装用紙、缶詰め用ダン
ボール、止め金を用いてとじる印刷用紙等では発
錆をおさえるために種々の対策が必要となつてい
る。このような事情から、硫酸バン土を添加する
ことなく抄紙した、いわゆる中性紙に対するサイ
ズ度の向上が近年クローズアツプされつつある。
一方、PVAは耐油性とか造膜性のすぐれた水
溶性高分子化合物であり従来より広く紙や板紙の
表面サイジング剤として用いられてきた。しかし
ながらここではPVAを塗布することによりステ
キヒトサイズ度のごとき物性に関してはむしろ低
下するという欠点が指摘されている。
また、PVAにCH2=CHOCOCR1R2R3(但し
R1、R2、R3はアルキル基)で示される分岐脂肪
酸ビニルエステルあるいはCH2=CHOR(但し、
Rはアルキル基)で示されるアルキルビニルエー
テルの如き疎水性基を共重合により導入した疎水
基変性PVAは公知であり、これらを紙加工に用
いることも特公昭44−16802や特公昭46−25521で
知られている。しかしながら、疎水基のみによる
変性PVAの場合には、顕著な性能を得るに充分
な量の疎水基を導入しようとすると、水不溶性に
なつたり、きわめて高粘度水溶液を与えるものに
なるため実用上難点があり、さらには発泡性が著
しく大きい点もまた重大な欠点であつた。以上の
如き理由のために、疎水基変性PVAは紙加工用
途に未だ利用されていないのが現状である。
また一方、PVA中にカルボキシル基、スルホ
ン基等のイオン性基を導入したイオン基変性
PVAもまた公知であり、これらを紙加工に用い
ることも知られている。これらイオン基変性
PVAは、紙中に存在する硫酸バン土との相互作
用によりすぐれた性能を発揮するため1部の分野
で実用に供せられているが、近時生産量が増大し
つつある中性紙に対しては、変性の効果がほとん
ど認められない。
本発明者らは、上述の如き状況に鑑み高いサイ
ズ性を有する中性紙を得るべく鋭意研究した結
果、
硫酸バン土を含有せず、かつ、
(A) 炭素数が6以上の脂肪酸のビニルエステル、
炭素数が6以上のアルキル基のビニルエーテ
ル、炭素数が6以上のα−オレフインよりなる
群より選ばれる単量体の少なくとも一種、
(B) エチレン性不飽和カルボン酸もしくはその低
級アルキルエステルまたは酸無水物の少なくと
も一種、および、
(C) 酢酸ビニルエステル
の三成分を必須成分として含む共重合体をアルカ
リケン化して得られる水溶性変性ポリビニルアル
コールを0.1〜5重量%含有することを特徴とす
る中性紙が、JIS−P−8122によるステキヒトサ
イズ度が10秒以上と、極めてサイズ度に優れてお
り、かつ硫酸バン土を含有していない為に強度、
印刷性および耐久性にも著しく優れ、また金属と
接触して使用される形態においても、金属になん
らの発錆をもたらさない等、優れた諸効果を奏す
ることを見出し、本発明を完成したものである。
また本発明の中性紙は、性能面のみならず経済
性からも有利な製紙用填料である炭酸カルシウム
を含有し得るという利点も有するものである。
即ち、すでに述べた様に一般的な製紙用サイズ
剤であるロジン系サイズ剤の多くは硫酸バン土に
よる酸性下で使用されるものであるが、填料とし
て前述の有利な炭酸カルシウムを用いる場合は炭
酸カルシウムが分解して発泡するという不都合を
招来する。
本発明の中性紙はかかる問題をも解決するもの
であり、安価な炭酸カルシウムを填料として用い
ることを可能ならしめることにより、経済性に優
れた中性紙を提供し得る。
本発明の中性紙に含有される変性PVAは前記
の(A)、(B)、(C)の三成分を必須成分として含む共重
合体をアルカリケン化することによつてのみ得ら
れるものであり、(A)と(C)あるいは(B)と(C)の組合わ
せからは予想することのできない顕著な性能が得
られることは驚くべきことである。
本発明で使用される共重合体の(A)成分に用いる
脂肪酸ビニルエステルは、炭素数が6以上のいわ
ゆる高級脂肪酸のビニルエステルであることが必
要であつて、炭素数が5以下の低級脂肪酸のビニ
ルエステルでは効果が十分でない。この理由は十
分明らかではないが、側鎖脂肪酸の炭素数がある
程度以上大きくないと疎水性効果が充分でないこ
とおよびアルカリケン化時にエステル結合が加水
分解され易いことの二つの理由によるものと推定
される。本発明に用いうる炭素数が6以上の脂肪
酸のビニルエステルとしては、カプリン酸陛ビニ
ルエステル、ラウリン酸ビニルエステル、ステア
リン酸ビニルエステル、1・1・3・3−テトラ
メチル酪酸ビニルエステル、2・2・4・4−テ
トラメチルバレリアン酸ビニルエステル、その他
の飽和分岐脂肪酸ビニルエステル等があげられる
が、なかんずくカルボキシル基が3級もしくは4
級の炭素原子に対してα−位に存在する飽和分岐
脂肪酸ビニルエステルが好適である。
本発明で使用される共重合体の(A)成分に用いる
炭素数が6以上のアルキル基のビニルエーテルと
しては、オクチルビニルエーテル、ラウリルビニ
ルエーテル、ステアリルビニルエーテル等があげ
られる。炭素数が5以下のアルキル基のビニルエ
ーテルを用いた場合は、疎水性が弱いためか効果
の発現が不充分である。
本発明で使用される共重合体の(A)成分に用いる
炭素数が6以上のα−オレフインとしては、ヘプ
テン−1、ドデセン−1、オクタデセン−1、そ
の他エチレンのテロメリゼーシヨンによつて得ら
れる炭素数10〜25のα−オレフインおよびこれら
の混合物等があげられる。α−オレフインの場合
は、側鎖の炭素数が4以上、すなわち単量体の総
炭素数が6以上で効果が明瞭に現われはじめる。
本発明で使用される共重合体の(B)成分に用いる
エチレン性不飽和カルボン酸もしくはその低級ア
ルキルエステルまたは酸無水物としては、アクリ
ル酸、メタクリル酸、クロトン酸、マレイン酸、
フマール酸、イタコン酸、シトラコン酸、および
それらのメチル−あるいはエチル−等の低級アル
キルエステル、さらにはそれらの酸無水物等があ
げられるが、中でもマレイン酸、フマール酸、イ
タコン酸、シトラコン酸等のジカルボン酸および
その低級アルキルエステルあるいは酸無水物がよ
り有効であり、とりわけイタコン酸、無水マレイ
ン酸、マレイン酸モノメチルが実用上すぐれてい
る。
本発明において用いる前述の(A)、(B)および(C)成
分を必須成分として含む共重合体中の各成分の割
合は、疎水基の炭素数、親水性成分となるべきエ
チレン性不飽和カルボン酸誘導体の分子構造等に
よつて適宜選択する必要があるが、塗被加工に用
いる場合の水溶解性および性能の点から、共重合
体中における(A)成分の割合、0.2〜10モル%、よ
り好ましくは0.8〜7モル%が適当であり、(B)成
分の割合は(A)成分の含有量によつても異なるが
0.1〜10モル%、好ましくは0.3〜5モル%が適当
である。また(A)成分のモル%に対する(B)成分のモ
ル%の好ましい比は通常0.2〜3.0であるが、この
範囲に限定されるものではない。
本発明に用いる変性PVAの製造には、とくに
困難な点はなく、従来公知の重合方法およびケン
化方法を適用することが出来る。すなわち、重合
方法としては、(A)、(B)および(C)成分をそれぞれの
共重合反応性比に応じて一括もしくは分割的ある
いは連続的に、重合系に投入し、無溶剤下もしく
は水性媒体中あるいはメチルアルコール、エチル
アルコール等の低級アルコールの共存下で、2・
2′−アゾビスイソブチロニトリル、過酸化ベンゾ
イル等のラジカル重合触媒によつて重合する方法
が適用できる。このようにして得られる(A)、(B)お
よび(C)成分を含む共重合体をアルカリケン化する
方法としては、ポリ酢酸ビニル共重合体のケン化
に用いられる多くの公知方法が適用できるが、通
常は、アルコール溶剤あるいは含水アルコール溶
剤中で、ナトリウムアルコラート、苛性ソーダ、
苛性カリ等のアルカリを作用させてケン化する方
法が適当である。アルコールとしては、メチルア
ルコール、エチルアルコール等の低級アルコール
が特に好適である。また、これらのアルコール溶
剤は、40重量%以下のアセトン、酢酸メチルエス
テル、酢酸エチルエステル、ベンゼン等の低誘電
率の溶剤を含んでいてもよい。従来公知の酸性化
合物によるケン化(いわゆる酸ケン化)は、本発
明の共重合体に適用した場合、変性PVAが水不
溶性となり易いため、本発明では採用しえない。
本発明に用いる変性PVAの重合度はその使用
目的によつて適宜選択すべきであるが、通常200
〜3000の範囲が適当である。また酢酸ビニルエス
テル成分のケン化度は、水溶性が損なわれない範
囲であれば任意の値を選択しうるが、通常97モル
%以上の高度ケン化物にすることが耐水性および
強度の点から望ましいが、使用目的によつては部
分ケン化物も使用することが可能である。
本発明において上記変性PVAは紙の要求性能
等によつてもことなるが、例えば塗布等の方法に
より、紙に対して0.1〜5重量%含有させること
が必要である。0.1重量%より少ないと顕著な性
能を発揮しない。又5重量%を越えて用いること
は原料薬品費の増大をまねくので通常の目的には
望ましくない。塗布に際しては通常は本発明の変
性PVAの単独を水溶液として使用するが、本発
明の目的をそこなわない範囲でカルボキシル基含
有PVA、他の変性PVAさらには未変性PVAの小
割合と混合して用いることもできる。又、塗布後
の乾燥ロールへの付着を防止する目的で、デンプ
ン、ワツクスエマルジヨン、各種活性剤の群より
選ばれる剥離剤を併用してもよい。その他グリセ
リン、ジエチレングリコール、エチレングリコー
ルなどの多価アルコール類、可塑剤、カルボキシ
メチルセルロース、デンプン、およびその誘導
体、スチレン−無水マレイン酸共重合体、スチレ
ン−アクリル酸共重合体などの合成系水溶性高分
子、さらには炭酸カルシウム、カオリナイト系ク
レー、ロー石クレー、サチンホワイト、などの鉱
物性顔料等を併用することもできる。塗工方法と
してはサイズプレス、カレンダーサイズ、タブサ
イズ、ゲートロールコーター、ナイフコーター、
ブレードコーター等従来公知の任意の方法が採用
できる。
本発明の中性紙を得るに用いる原紙は針葉樹パ
ルプ、広葉樹パルプ又はその混合物から得られた
ものでもよく、さらに合成繊維、人造繊維、合成
パルプ等の他の繊維を含んでいてもよい。又バー
ジンパルプのみでなく損紙、故紙等を混合してい
てもよい。更には紙力増強剤、濾水促進剤、消泡
剤、クレー、炭酸カルシウムのごとき填料など中
性紙の抄紙にあたつて通常使用される紙薬品類を
含有しても何らさしつかえない。
次に本発明を実施例をあげてさらに詳しく説明
するが本発明はこれらの例のみに限定されるもの
ではない。尚、例中部とあるのは特にことわらな
いかぎり重量基準である。
実施例 1
(1) 試料No.1の作成
重合缶に酢酸ビニルエステル2100部、平均炭
素数10の飽和分岐脂肪酸ビニルエステル(シエ
ル化学社製、商品名VeoVa−10)110部、イタ
コン酸1.1部およびメチルアルコール1750部を
投入する。次いで重合缶内にチツ素気流を通じ
ながら系内を撹拌し、昇温して60℃に達した
ら、α・α′−アゾビスイソブチロニトリル6.0
部を投入し重合を開始する。重合開始時点より
重合系の重合率に応じてイタコン酸26.0部を溶
解したメチルアルコール溶液170部を4時間に
わたつて連続的に滴下しながら重合を行ない、
酢酸ビニルエステルの重合率が75%になつた時
点で重合を終了する。続いてメチルアルコール
蒸気を吹き込む方法によつて未反応の酢酸ビニ
ルエステルモノマーを系外に除去し共重合体の
メチルアルコール溶液を得た。次いで該溶液に
38部の水酸化ナトリウムを含むメチルアルコー
ル溶液を加えて十分に撹拌したのち静置してケ
ン化反応を行ない、折出したゲル状物を粉砕、
洗浄、乾燥して白色のPVA系共重合体を得
た。核磁気共鳴吸収スペクトル法および電導度
滴定法を用いて分析した結果、VeoVa−10成分
を2.2モル%、イタコン酸成分を1.1モル%含有
し、かつ酢酸ビニルエステル成分の98.5%がケ
ン化された変性PVAであつた。また、硝酸カ
リウムを含むジメチルスルホキシド中における
極限粘度数から、重合度を求めたところ、620
であつた。
(2) 試料No.2〜No.5の作成
(A)成分としてVaoVa−10(シエル化学製)も
しくはラウリルビニルエーテルを用い、(B)成分
としては、イタコン酸に代えて無水マレイン酸
もしくはクロトン酸を用いて、試料No.1の作成
方法と同様な方法でポリビニルアルコール系共
重合体を得た。分析値その他の結果は表1に示
す通りである。
(3) 比較試料No.6〜No.12の作成
(A)成分としてVeoVa−10(シエル化学製)も
しくはオクチルビニルエーテルを用い、(B)成分
として無水マレイン酸もしくはクロトン酸を用
い、また(A)成分か(B)成分のいずれか一方の成分
のみを用いて、又は両方とも用いることなく他
は試料No.1の作成方法と同様な方法で比較試料
No.7〜No.12を得た。また比較試料No.6は(A)成分
としてブチルビニルエーテル、(B)成分として無
水マレイン酸を用いて試料No.1と同様な方法で
作成した。分析値、その他の結果を表1にまと
めて示す。なお、比較試料No.7及びNo.8は、熱
水にも冷水にも溶解しないものであつたので、
その後の性能評価は実施できなかつた。
The present invention relates to acid-free paper with excellent sizing properties. More specifically, it does not contain aluminum sulfate and (A) a vinyl ester of a fatty acid having 6 or more carbon atoms;
At least one monomer selected from the group consisting of vinyl ethers of alkyl groups having 6 or more carbon atoms and α-olefins having 6 or more carbon atoms; (B) ethylenically unsaturated carboxylic acid or its lower alkyl ester or acid anhydride; and (C) a water-soluble modified polyvinyl alcohol (hereinafter abbreviated as PVA) obtained by alkali saponification of a copolymer containing the three components of vinyl acetate as essential components. % by weight, and has excellent sizing properties. Paper is a hydrophilic porous material whose main raw material is pulp, but it is not practical if it is simply made from pulp. Therefore, it is necessary to use various paper chemicals such as sizing agents and fillers to produce paper that can be used for practical purposes. There are many practical physical properties of paper, among which sizing is important, such as bleeding of printing ink,
Penetration, bleeding of writing ink, and in the case of base paper for processing, are important properties that are closely related to the permeability of processing liquid and the associated physical properties of processed paper. Most of the conventionally used sized papers are produced by fixing a rosin-based sizing agent onto pulp fibers through the intervention of sulfuric acid. However, when sulfuric acid is used as a fixing agent, the paper becomes acidic due to the sulfate roots of sulfuric acid during the manufacturing process, which not only corrodes calender rolls, dryer rolls, and other metals that come into contact with the paper during the process. This may have a negative effect on the strength and durability of the paper, and may also cause problems with certain types of printing. In addition, it is widely known that a major practical problem with paper made using banal sulfate soil is that metals that come into contact with it are extremely susceptible to rust. Various measures are required to prevent rust from forming on printing paper that is used for binding. Under these circumstances, in recent years, attention has been focused on improving the size of so-called neutral paper, which is made without adding banal sulfate. On the other hand, PVA is a water-soluble polymer compound with excellent oil resistance and film-forming properties, and has been widely used as a surface sizing agent for paper and paperboard. However, it has been pointed out here that the physical properties such as Steckigt sizing are actually reduced by applying PVA. Also, CH 2 = CHOCOCR 1 R 2 R 3 (however,
R 1 , R 2 , R 3 are alkyl groups) or branched fatty acid vinyl ester represented by CH 2 =CHOR (however,
Hydrophobic group-modified PVA in which a hydrophobic group such as alkyl vinyl ether (R is an alkyl group) is introduced by copolymerization is known, and the use of these for paper processing was also reported in Japanese Patent Publications 16802-1973 and 25521-1973. Are known. However, in the case of modified PVA with only hydrophobic groups, if we try to introduce a sufficient amount of hydrophobic groups to obtain remarkable performance, it becomes water insoluble or gives an extremely high viscosity aqueous solution, which is a practical difficulty. Moreover, the fact that the foaming property was extremely high was also a serious drawback. For the reasons mentioned above, hydrophobic group-modified PVA has not yet been used for paper processing purposes. On the other hand, ionic group modification in which ionic groups such as carboxyl groups and sulfone groups are introduced into PVA
PVA is also known and their use in paper processing. Modification of these ionic groups
PVA has been put into practical use in some fields because it exhibits excellent performance through interaction with the aluminum sulfate present in paper. On the other hand, almost no denaturing effect is observed. In view of the above-mentioned circumstances, the present inventors conducted intensive research to obtain neutral paper with high size properties, and as a result, they found that they do not contain silica sulfate, and (A) contain vinyl fatty acids having 6 or more carbon atoms. ester,
At least one monomer selected from the group consisting of vinyl ethers of alkyl groups having 6 or more carbon atoms and α-olefins having 6 or more carbon atoms; (B) ethylenically unsaturated carboxylic acid or its lower alkyl ester or acid anhydride; and (C) 0.1 to 5% by weight of water-soluble modified polyvinyl alcohol obtained by alkali saponification of a copolymer containing as essential components three components: vinyl acetate. The paper has excellent sizing, with a Steckicht sizing degree of 10 seconds or more according to JIS-P-8122, and is strong and strong because it does not contain sulfuric acid.
The present invention was completed based on the discovery that it has excellent printability and durability, and even when used in contact with metal, it does not cause any rusting on the metal. It is. Furthermore, the neutral paper of the present invention has the advantage that it can contain calcium carbonate, which is a filler for paper manufacturing that is advantageous not only in terms of performance but also in terms of economy. That is, as mentioned above, most of the rosin-based sizing agents, which are common paper-making sizing agents, are used under acidic conditions with silica sulfate, but when using the aforementioned advantageous calcium carbonate as a filler, This causes the inconvenience that calcium carbonate decomposes and foams. The neutral paper of the present invention also solves this problem, and by making it possible to use inexpensive calcium carbonate as a filler, it is possible to provide a neutral paper with excellent economic efficiency. The modified PVA contained in the neutral paper of the present invention can only be obtained by alkali saponification of a copolymer containing the above three components (A), (B), and (C) as essential components. It is surprising that a remarkable performance that could not be expected from the combination of (A) and (C) or (B) and (C) can be obtained. The fatty acid vinyl ester used in component (A) of the copolymer used in the present invention must be a vinyl ester of a so-called higher fatty acid having 6 or more carbon atoms, and a lower fatty acid having 5 or less carbon atoms. Vinyl ester is not effective enough. The reason for this is not fully clear, but it is presumed that it is due to two reasons: the hydrophobic effect is not sufficient unless the number of carbon atoms in the side chain fatty acid is larger than a certain level, and the ester bond is easily hydrolyzed during alkali saponification. Ru. Vinyl esters of fatty acids having 6 or more carbon atoms that can be used in the present invention include capric acid vinyl ester, lauric acid vinyl ester, stearic acid vinyl ester, 1,1,3,3-tetramethylbutyric acid vinyl ester, 2. Examples include 2,4,4-tetramethylvaleric acid vinyl ester and other saturated branched fatty acid vinyl esters, but especially those with a tertiary or quaternary carboxyl group.
Preferred are saturated branched fatty acid vinyl esters which are present in the α-position relative to the carbon atoms of the same class. Examples of the vinyl ether of an alkyl group having 6 or more carbon atoms used in component (A) of the copolymer used in the present invention include octyl vinyl ether, lauryl vinyl ether, stearyl vinyl ether, and the like. When a vinyl ether having an alkyl group having 5 or fewer carbon atoms is used, the effect is insufficient, probably because of its weak hydrophobicity. The α-olefins having 6 or more carbon atoms used in component (A) of the copolymer used in the present invention include heptene-1, dodecene-1, octadecene-1, and other ethylene telomerization products. Examples include the resulting α-olefins having 10 to 25 carbon atoms and mixtures thereof. In the case of α-olefin, the effect begins to become apparent when the number of carbon atoms in the side chain is 4 or more, that is, the total number of carbon atoms in the monomer is 6 or more. Examples of the ethylenically unsaturated carboxylic acid or its lower alkyl ester or acid anhydride used in component (B) of the copolymer used in the present invention include acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Examples include fumaric acid, itaconic acid, citraconic acid, their lower alkyl esters such as methyl or ethyl, and their acid anhydrides, among others, maleic acid, fumaric acid, itaconic acid, citraconic acid, etc. Dicarboxylic acids and their lower alkyl esters or acid anhydrides are more effective, and itaconic acid, maleic anhydride, and monomethyl maleate are particularly excellent in practice. The proportion of each component in the copolymer containing the above-mentioned components (A), (B), and (C) as essential components used in the present invention is determined by the number of carbon atoms in the hydrophobic group, the ethylenically unsaturated The proportion of component (A) in the copolymer should be selected appropriately depending on the molecular structure of the carboxylic acid derivative, etc., but from the viewpoint of water solubility and performance when used for coating processing, the proportion of component (A) in the copolymer should be 0.2 to 10 mol. %, more preferably 0.8 to 7 mol%, and the proportion of component (B) varies depending on the content of component (A).
A suitable amount is 0.1 to 10 mol%, preferably 0.3 to 5 mol%. Further, the preferred ratio of the mole percent of component (B) to the mole percent of component (A) is usually 0.2 to 3.0, but is not limited to this range. There are no particular difficulties in producing the modified PVA used in the present invention, and conventionally known polymerization methods and saponification methods can be applied. In other words, as a polymerization method, components (A), (B), and (C) are added to a polymerization system all at once, in parts, or continuously depending on their respective copolymerization reactivity ratios, and the In a medium or in the presence of lower alcohols such as methyl alcohol and ethyl alcohol, 2.
A method of polymerization using a radical polymerization catalyst such as 2'-azobisisobutyronitrile or benzoyl peroxide can be applied. Many known methods used for saponifying polyvinyl acetate copolymers can be used to alkali saponify the copolymer containing components (A), (B), and (C) obtained in this way. However, usually sodium alcoholate, caustic soda,
A suitable method is saponification using an alkali such as caustic potash. As the alcohol, lower alcohols such as methyl alcohol and ethyl alcohol are particularly suitable. Further, these alcohol solvents may contain 40% by weight or less of a low dielectric constant solvent such as acetone, methyl acetate, ethyl acetate, or benzene. Saponification using a conventionally known acidic compound (so-called acid saponification) cannot be employed in the present invention because when applied to the copolymer of the present invention, the modified PVA tends to become water-insoluble. The degree of polymerization of the modified PVA used in the present invention should be appropriately selected depending on the purpose of use, but is usually 200%.
A range of ~3000 is appropriate. Furthermore, the degree of saponification of the vinyl acetate ester component can be selected as long as it does not impair water solubility, but it is usually recommended to use a highly saponified product of 97 mol% or more in terms of water resistance and strength. Although desirable, partially saponified products can also be used depending on the purpose of use. In the present invention, the modified PVA needs to be contained in an amount of 0.1 to 5% by weight based on the paper, for example, by a method such as coating, although this will vary depending on the required performance of the paper. If it is less than 0.1% by weight, no remarkable performance will be exhibited. Moreover, using more than 5% by weight is not desirable for general purposes because it increases the cost of raw materials and chemicals. When applying, the modified PVA of the present invention is usually used alone as an aqueous solution, but it may be mixed with carboxyl group-containing PVA, other modified PVA, or even a small proportion of unmodified PVA to the extent that the purpose of the present invention is not impaired. It can also be used. Further, for the purpose of preventing adhesion to the drying roll after coating, a release agent selected from the group consisting of starch, wax emulsion, and various activators may be used in combination. Other synthetic water-soluble polymers such as polyhydric alcohols such as glycerin, diethylene glycol, and ethylene glycol, plasticizers, carboxymethyl cellulose, starch, and their derivatives, styrene-maleic anhydride copolymers, and styrene-acrylic acid copolymers. Furthermore, mineral pigments such as calcium carbonate, kaolinite clay, loite clay, and satin white can also be used in combination. Coating methods include size press, calendar size, tab size, gate roll coater, knife coater,
Any conventionally known method such as a blade coater can be used. The base paper used to obtain the neutral paper of the present invention may be obtained from softwood pulp, hardwood pulp, or a mixture thereof, and may further contain other fibers such as synthetic fibers, man-made fibers, and synthetic pulp. Moreover, not only virgin pulp but also broken paper, waste paper, etc. may be mixed. Furthermore, there is no problem in containing paper chemicals commonly used in the production of neutral paper, such as paper strength enhancers, drainage accelerators, antifoaming agents, clays, and fillers such as calcium carbonate. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Note that "Example Middle" is based on weight unless otherwise specified. Example 1 (1) Preparation of Sample No. 1 In a polymerization can, 2100 parts of vinyl acetate, 110 parts of saturated branched fatty acid vinyl ester with an average carbon number of 10 (manufactured by Ciel Chemical Co., Ltd., trade name VeoVa-10), and 1.1 parts of itaconic acid were added. and 1750 parts of methyl alcohol. Next, the system was stirred while passing a nitrogen gas flow into the polymerization reactor, and when the temperature was raised to 60°C, α・α′-azobisisobutyronitrile 6.0
to start polymerization. From the start of the polymerization, 170 parts of a methyl alcohol solution containing 26.0 parts of itaconic acid was continuously added dropwise over 4 hours depending on the polymerization rate of the polymerization system, and the polymerization was carried out.
Polymerization is terminated when the polymerization rate of vinyl acetate reaches 75%. Subsequently, unreacted vinyl acetate monomer was removed from the system by blowing methyl alcohol vapor to obtain a methyl alcohol solution of the copolymer. Then add to the solution
A methyl alcohol solution containing 38 parts of sodium hydroxide was added, stirred thoroughly, and left to stand for a saponification reaction, and the precipitated gel was crushed.
After washing and drying, a white PVA copolymer was obtained. As a result of analysis using nuclear magnetic resonance absorption spectroscopy and conductivity titration, it was found that it contained 2.2 mol% of VeoVa-10 component and 1.1 mol% of itaconic acid component, and 98.5% of the vinyl acetate component was saponified. It was denatured PVA. In addition, the degree of polymerization was determined from the intrinsic viscosity number in dimethyl sulfoxide containing potassium nitrate, and it was found to be 620.
It was hot. (2) Preparation of Samples No. 2 to No. 5 (A) Use VaoVa-10 (manufactured by Schiel Chemical) or lauryl vinyl ether as the component, and use maleic anhydride or crotonic acid as the (B) component instead of itaconic acid. A polyvinyl alcohol copolymer was obtained using a method similar to that used for preparing sample No. 1. The analytical values and other results are shown in Table 1. (3) Preparation of comparative samples No. 6 to No. 12 (A) Using VeoVa-10 (manufactured by Ciel Chemical) or octyl vinyl ether as the component, using maleic anhydride or crotonic acid as the (B) component, and (A) Comparative samples were prepared using either component () or component (B), or by using the same method as sample No. 1 without using both.
No. 7 to No. 12 were obtained. Comparative sample No. 6 was prepared in the same manner as sample No. 1 using butyl vinyl ether as the (A) component and maleic anhydride as the (B) component. The analytical values and other results are summarized in Table 1. In addition, comparative samples No. 7 and No. 8 did not dissolve in either hot water or cold water, so
Subsequent performance evaluation was not possible.
【表】
(4) 性能評価
フリーネス590c.c.に叩解した針葉樹晒クラフ
トパルプ(NBKP)を使用し、硫酸バン土を添
加することなく手抄抄紙機で抄紙した坪量65
g/m2の原紙を得た。上記に得た試料の4%水
溶液を調製し、少量の消泡剤(竹本油脂製パイ
オニンK−17)を添加して、先に得た原紙にラ
ボサイズプレスを用いて固型分塗工量1.0g/
m2になるように塗布、乾燥したのち、20℃、65
%RH(相対湿度)の試験室に一夜放置したの
ち物性測定に供した。
なお、サイズプレスコーテイングを実施する
際に、液の循環経路における泡の発生状況を観
察比較した。結果をまとめて表−2に記す。[Table] (4) Performance evaluation Paper made using a hand paper machine using bleached softwood kraft pulp (NBKP) beaten to a freeness of 590 c.c. without adding banal sulfate soil, basis weight 65
A base paper of g/m 2 was obtained. Prepare a 4% aqueous solution of the sample obtained above, add a small amount of antifoaming agent (Pionin K-17 manufactured by Takemoto Yushi Co., Ltd.), and apply the solids coating amount to the base paper obtained earlier using a lab size press. 1.0g/
After coating to a thickness of m 2 and drying, heat at 20°C and 65°C.
After being left in a test room at %RH (relative humidity) overnight, it was subjected to physical property measurements. In addition, when performing size press coating, the generation of bubbles in the liquid circulation path was observed and compared. The results are summarized in Table-2.
【表】【table】
【表】
表−2の結果より本発明の中性紙は、極めてす
ぐれたステキヒトサイズ度を有することはもちろ
んのこと、本発明に用いる変性PVAは疎水性成
分(A)の効果と親水性成分(B)の効果とが相乗的に作
用してコーテイング時の泡立ちが少なく、極めて
作業性のすぐれたサイズ方法を提供するものであ
ることがわかる。
一方、疎水性成分(A)と親水性成分(B)の両者を含
有していても疎水性成分の炭素数が5以下のアル
キルビニルエーテルでは試料No.6にみられるごと
くステキヒトサイズ度はまつたく高くならない。
さらに、疎水性成分(A)のみを含有する比較試料No.
7、No.8、No.9の場合は水不溶性となつたり、発
泡性が大きかつたりして良好な作業性を有しない
等の重大な欠点がある。
親水性成分(B)のみを含有する比較試料No.10、No.
11の場合はまつたくサイズ度の向上が見られな
い。疎水性成分(A)も親水性成分(B)も共に有しない
比較試料No.12はまつたくサイズ度向上効果が認め
られない。
実施例 2
針葉樹晒クラフトパルプ(NBKP)と広葉樹晒
クラフトパルプ(LBKP)の3:1の混合パルプ
を用い炭酸カルシウムを10%含有せしめた坪量64
g/m2の原紙を得た。
実施例1で得た試料の7%水溶液を調製し少量
の消泡剤(竹本油脂製パイオニンK−17)を添加
して先に得た原紙にラボサイズプレスを用いて固
型分塗工量2.8g/m2となる様にサイズプレス塗
工し乾燥し、20℃、65%RHの試験室に一夜放置
したのちJIS p−8122に従いステキヒトサイズ度
を測定した。
尚、サイズプレスコーテイングを実施する際に
液の循環経路における泡の発生状況を観察比較し
た結果をまとめて表−3に記す。
表−3の結果より本発明の中性紙は填料として
炭酸カルシウムを含有する中性紙であつて、かつ
きわめて高いステキヒトサイズ度を有するものを
あたえることはもちろんのこと、本発明に用いる
変性PVAの疎水性成分(A)の効果と親水性成分(B)
の効果が相乗的に作用してコーテイング時の泡立
ちが少なくきわめて作業性のすぐれたサイズ方法
を提供するものである。
一方疎水性成分(A)のみを含有する試料No.7、No.
8、No.9の場合は水不溶性となつたり、発泡性が
大きかつたりして安定な作業ができないという重
大な欠点がある。
親水性成分(B)のみを含有する試料No.10、No.11及
び疎水性成分(A)と親水性成分(B)の両者とも含有し
ない試料No.12では全くサイズ効果を発揮しない。
疎水性成分(A)と親水性成分(B)を両方含むもので
あつても疎水性成分(A)の側鎖の炭素数が5以下の
アルキルビニルエーテルであるブチルビニルエー
テルでは試料No.6にみられるごとくステキヒトサ
イズ度が低い。[Table] From the results shown in Table 2, the neutral paper of the present invention not only has an extremely excellent Steckigt sizing degree, but also that the modified PVA used in the present invention has a hydrophilicity due to the effect of the hydrophobic component (A). It can be seen that the effect of component (B) acts synergistically to provide a sizing method with little foaming during coating and extremely excellent workability. On the other hand, even if it contains both a hydrophobic component (A) and a hydrophilic component (B), the degree of Stekicht sizing is low for alkyl vinyl ethers in which the hydrophobic component has 5 or less carbon atoms, as seen in sample No. 6. It doesn't get too expensive.
Furthermore, comparative sample No. containing only the hydrophobic component (A).
In the case of No. 7, No. 8, and No. 9, they have serious drawbacks such as being water-insoluble and having a large foaming property and not having good workability. Comparative samples No. 10 and No. 1 containing only the hydrophilic component (B).
In the case of 11, there is no noticeable improvement in size. Comparative sample No. 12, which does not have either the hydrophobic component (A) or the hydrophilic component (B), does not show any significant sizing effect. Example 2 Basis weight 64 containing 10% calcium carbonate using a 3:1 mixed pulp of softwood bleached kraft pulp (NBKP) and hardwood bleached kraft pulp (LBKP)
A base paper of g/m 2 was obtained. A 7% aqueous solution of the sample obtained in Example 1 was prepared, a small amount of antifoaming agent (Pionin K-17 manufactured by Takemoto Yushi Co., Ltd.) was added, and the solid content coating amount was measured using a lab size press on the base paper obtained earlier. It was size-press coated to a density of 2.8 g/m 2 , dried, and left in a test room at 20° C. and 65% RH overnight, after which the Steckigt sizing degree was measured according to JIS p-8122. Table 3 summarizes the results of observation and comparison of bubble generation in the liquid circulation path when performing size press coating. From the results shown in Table 3, the neutral paper of the present invention is a neutral paper containing calcium carbonate as a filler and has an extremely high Steckigt sizing degree, as well as the modified paper used in the present invention. Effect of hydrophobic component (A) and hydrophilic component (B) of PVA
The effects of the above work synergistically to provide a sizing method with very little foaming during coating and excellent workability. On the other hand, samples No. 7 and No. 7 containing only the hydrophobic component (A)
In the case of No. 8 and No. 9, there are serious drawbacks in that they are water-insoluble and have a large foaming property, making stable work impossible. Samples No. 10 and No. 11 containing only the hydrophilic component (B) and sample No. 12 containing neither the hydrophobic component (A) nor the hydrophilic component (B) exhibit no size effect at all. Even if it contains both a hydrophobic component (A) and a hydrophilic component (B), only sample No. 6 has butyl vinyl ether, which is an alkyl vinyl ether in which the hydrophobic component (A) has 5 or less carbon atoms in the side chain. As expected, the Steckicht size degree is low.
【表】
実施例 3
実施例2で得た原紙に実施例1で得た変性
PVAとデンプンの5:5の混合物を2.5g/m2と
なる様にサイズプレス塗工し乾燥後20℃、65%
RH(相対湿度)の試験室に一夜放置したのちJIS
p−8122に従いステキヒトサイズ度を測定した。
結果は表−4に示す。原紙のサイズ度が0秒な
のに対し本発明の中性紙では11〜22秒と高いサイ
ズ度が得られた。
また塗布時の発泡性はきわめて少なかつた。[Table] Example 3 Modification obtained in Example 1 to the base paper obtained in Example 2
Size press coated with a 5:5 mixture of PVA and starch at 2.5g/m 2 and dried at 20℃, 65%
After being left in a RH (relative humidity) test room overnight, JIS
Steckcht size was measured according to p-8122. The results are shown in Table-4. While the sizing degree of the base paper was 0 seconds, the neutral paper of the present invention had a high sizing degree of 11 to 22 seconds. Furthermore, foaming properties during application were extremely low.
Claims (1)
炭素数が6以上のアルキル基のビニルエーテ
ル、炭素数が6以上のα−オレフインよりなる
群より選ばれる単量体の少なくとも一種、 (B) エチレン性不飽和カルボン酸もしくはその低
級アルキルエステルまたは酸無水物の少なくと
も一種、および、 (C) 酢酸ビニルエステル の三成分を必須成分として含む共重合体をアルカ
リケン化して得られる水溶性変性ポリビニルアル
コールを0.1〜5重量%含有することを特徴とす
る優れたサイズ度を有する中性紙。 2 (A)成分が、三級もしくは四級の炭素原子を含
有し、かつ該炭素原子に対しα位にカルボキシル
基を有するような分岐脂肪酸ビニルエステルであ
り、(B)成分が、エチレン性不飽和ジカルボン酸も
しくはその低級アルキルエステルまたは酸無水物
である特許請求の範囲第1項に記載の優れたサイ
ズ度を有する中性紙。 3 (B)成分がマレイン酸もしくはマレイン酸エス
テルまたは無水マレイン酸である特許請求の範囲
第2項に記載の優れたサイズ度を有する中性紙。 4 (B)成分がイタコン酸である特許請求の範囲第
2項に記載の優れたサイズ度を有する中性紙。[Scope of Claims] 1. A vinyl ester of a fatty acid containing no carbon sulfate and (A) having 6 or more carbon atoms;
At least one monomer selected from the group consisting of vinyl ethers of alkyl groups having 6 or more carbon atoms and α-olefins having 6 or more carbon atoms; (B) ethylenically unsaturated carboxylic acid or its lower alkyl ester or acid anhydride; and (C) 0.1 to 5% by weight of water-soluble modified polyvinyl alcohol obtained by alkali saponification of a copolymer containing as essential components three components: vinyl acetate. Acid-free paper with a certain size. 2 Component (A) is a branched fatty acid vinyl ester that contains a tertiary or quaternary carbon atom and has a carboxyl group at the α-position with respect to the carbon atom, and component (B) is The neutral paper having excellent sizing according to claim 1, which is a saturated dicarboxylic acid or its lower alkyl ester or acid anhydride. 3. The neutral paper having excellent sizing according to claim 2, wherein component (B) is maleic acid, maleic ester, or maleic anhydride. 4. A neutral paper having excellent sizing according to claim 2, wherein component (B) is itaconic acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17248779A JPS5696993A (en) | 1979-12-28 | 1979-12-28 | Sizing of neutral paper |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17248779A JPS5696993A (en) | 1979-12-28 | 1979-12-28 | Sizing of neutral paper |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5696993A JPS5696993A (en) | 1981-08-05 |
JPS6240477B2 true JPS6240477B2 (en) | 1987-08-28 |
Family
ID=15942889
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17248779A Granted JPS5696993A (en) | 1979-12-28 | 1979-12-28 | Sizing of neutral paper |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5696993A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0623210B2 (en) * | 1985-11-18 | 1994-03-30 | 日本合成化学工業株式会社 | Polyvinyl alcohol-based polymer, method for producing the same, and paper surface sizing agent and dispersion stabilizer comprising the polymer |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5658098A (en) * | 1979-10-09 | 1981-05-20 | Kuraray Co | Paper processing agent |
-
1979
- 1979-12-28 JP JP17248779A patent/JPS5696993A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5658098A (en) * | 1979-10-09 | 1981-05-20 | Kuraray Co | Paper processing agent |
Also Published As
Publication number | Publication date |
---|---|
JPS5696993A (en) | 1981-08-05 |
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