JPH0147598B2 - - Google Patents
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- Publication number
- JPH0147598B2 JPH0147598B2 JP19923982A JP19923982A JPH0147598B2 JP H0147598 B2 JPH0147598 B2 JP H0147598B2 JP 19923982 A JP19923982 A JP 19923982A JP 19923982 A JP19923982 A JP 19923982A JP H0147598 B2 JPH0147598 B2 JP H0147598B2
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- JP
- Japan
- Prior art keywords
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- reaction
- acid
- minutes
- Prior art date
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- 229920000642 polymer Polymers 0.000 claims description 26
- 125000002091 cationic group Chemical group 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 150000001408 amides Chemical class 0.000 claims description 9
- 125000000129 anionic group Chemical group 0.000 claims description 9
- 150000002825 nitriles Chemical class 0.000 claims description 9
- 239000003623 enhancer Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000000123 paper Substances 0.000 description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 8
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- -1 acrylamide Chemical class 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 4
- 150000008041 alkali metal carbonates Chemical class 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229920006318 anionic polymer Polymers 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000012744 reinforcing agent Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KIWBPDUYBMNFTB-UHFFFAOYSA-N Ethyl hydrogen sulfate Chemical compound CCOS(O)(=O)=O KIWBPDUYBMNFTB-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 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
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 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 1
- 238000011282 treatment Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Description
本発明はアクリルアミドなどのα，β−不飽和
アミドとアクリロニトリルなどのα，β−不飽和
ニトリルと必要に応じてこれらと共重合可能なノ
ニオン性単量体を含む共重合体を、水酸化ナトリ
ウムなどのアルカリ金属水酸化物、炭酸ナトリウ
ムなどのアルカリ金属炭酸塩またはジメチルアミ
ンなどのアミン系塩基によりアルカリ性下で反応
させることにより、重合体中にアニオン性基およ
びカチオン性基を同時に導入してなる両性重合体
よりなる紙力増強剤に関するものである。
従来よりアクリルアミド−アクリル酸共重合体
又はポリアクリルアミドの部分加水分解反応によ
りカルボキシル基を導入した重合体に代表される
アクリルアミドを主体とするアニオン性重合体
は、製紙業界で硫酸バンドを定着剤として用いる
紙力増強剤などに使用されている。しかしながら
従来のアクリルアミドを主体とするアニオン性紙
力増強剤は、バルブ繊維への定着率は通常60〜80
％といわれており十分な紙力増強効果を発揮して
いるとは言い難い。
本発明者らはパルプ繊維への定着率を高め、優
れた紙力増強効果を発揮する紙力増強剤を得るこ
とを目的として鋭意研究を重ねた結果、本発明に
到つたものである。
すなわち、アクリルアミドなどのα，β−不飽
和アミドと、アクリロニトリルなどのα，β−不
飽和ニトリルとを主体とする共重合体の水溶液
を、水酸化ナトリウムなどのアルカリ金属水酸化
物又はジメチルアミンなどのアミン系塩基を添加
してアルカリ性下反応することにより、重合体中
にアニオン性基およびカチオン性基が同時に導入
された両性重合体が得られることを発見した。ま
たこの両性重合体はパルプ繊維への定着率が90％
以上で従来のアニオン性重合体より高く、紙力増
強効果も著しく優れることを見出し、ここに本発
明を完成するに至つた。
本発明の両性重合体中のアニオン性基は、アミ
ド基がアルカリ性下で加水分解されてカルボキシ
ル基となることにより導入される。又カチオン性
基の導入機構については現在明らかではないが、
アクリルアミドのようなα，β−不飽和アミドの
ホモポリマーではアルカリ性下同様に反応しても
カチオン性基は導入されず、カチオン性基を導入
するためには本発明のようにニトリル基の存在が
不可欠である。このようなことからアミド基の加
水分解反応によりカルボキシル基とともに副生す
るアンモニアがニトリル基と反応することにより
カチオン性を発現するものと考えられる。
本発明の重合体中のα，β−不飽和アミドとし
て、具体的にはアクリルアミド、メタアクリルア
ミド、ジメチルアクリルアミド等が挙げられる。
又α，β−不飽和ニトリルとして、具体的にはア
クリロニトリル、メタアクリロニトリル等が挙げ
られる。またこれらと共重合可能なノニオン性単
量体は、共重合体中に必要に応じて添加できる成
分であつて、具体的にはスチレン、α−メチルス
チレンなどの芳香族炭化水素類、アクリル酸メチ
ル、アクリル酸エチル、アクリル酸ブチル、アク
リル酸２−ヒドロキシエチル、メタアクリル酸メ
チル、メタアクリル酸エチルなどのアクリル酸又
はメタアクリル酸の炭素数１〜８のアルキルエス
テル類、酢酸ビニルプロピオン酸ビニル等のビニ
ルエステル類が使用可能である。
上記のα，β−不飽和アミド成分、α，β−不
飽和ニトリル成分及びノニオン性単量体成分の使
用割合は、α，β−不飽和アミド成分は50〜90モ
ル％であるが好ましくは60〜80モル％が適当であ
る。このα，β−不飽和アミド成分が50モル％以
下では紙力増強効果が十分に発揮されず好ましく
ない。又、α，β−不飽和ニトリル成分は、10〜
50モル％であるが好ましくは20〜40モル％であ
る。このα，β−不飽和ニトリル成分が10モル％
以下では、この後に行うアルカリ性下での反応で
カチオン性基がほとんど導入されず、本発明の特
徴とする両性重合体は得られない。又α，β−不
飽和ニトリル成分が50モル％以上では水に不溶性
となり好ましくない。ノニオン性単量体成分は、
20モル％以下の範囲で必要に応じて添加される成
分である。
上記α，β−不飽和アミド成分、α，β−不飽
和ニトリル成分及びノニオン性単量体成分の共重
合反応は通常の方法で実施でき、特に水溶液重合
が一般的である。
例えば過硫酸アンモニウム、過硫酸カリウム、
過酸化水素等の水溶性過酸化物、あるいはこれら
とジメチルアミン、亜硫酸ナトリウムなどの還元
剤またはアリルアルコール、イソプロピルアルコ
ールなどの連鎖移動剤を組み合せて前記重合性単
量体混合物に対し0.05〜５重量％使用し、水溶媒
で単量体混合物の濃度10〜50重量％濃度、40〜95
℃の温度で１〜５時間窒素ガス雰囲気中で共重合
反応を行う。このようにして前記３つの成分で構
成された共重合体は、15％濃度の水溶液の粘度が
1000〜100000cps（25℃）のものである。
次にこの共重合体の10〜50重量％濃度の水溶液
にアルカリ金属水酸化物、アルカリ金属炭酸塩ま
たはアミン塩基を共重合体に対して１〜15重量％
加え、PH９以上、温度40〜95℃で５〜120分反応
させる。而してアニオン性基１〜20モル％及びカ
チオン性基１〜10モル％が導入された時点で、鉱
酸、有機カルボン酸又は有機スルホン酸等の酸を
加え、PH３〜９として本反応を停止する。ここで
アルカリ金属水酸化物としては具体的に水酸化ナ
トリウム、水酸化カリウム、水酸化リチウム等が
例示できる。また、アルカリ金属炭酸塩としては
炭酸ナトリウム、炭酸カリウム、炭酸リチウム等
が例示できる。又アミン塩基とは具体的に、アン
モニア、メチルアミン、ジメチルアミン、トリメ
チルアミン、ジエチルアミン等の脂肪族アミンが
例示される。ここでアルカリ金属水酸化物、アル
カリ金属炭酸塩およびアミン塩基は、共重合体に
対し１〜15重量％の範囲で加えてPH９以上、好ま
しくはPH10〜13のアルカリ性とする必要がある。
PH９以下ではアミド基の加水分解反応およびカチ
オン性基導入反応の反応速度が極端に遅くなり、
従つて本発明の特徴とする両性重合体は得られな
い。而して、前記共重合体を上記PH以下で、温度
40〜95℃で５〜120分反応させることにより、目
的の両性重合体を得る。ここで反応時間が５分以
下では、得られる重合体水溶液が１週間程度で２
相分離するなど安定性が悪く、好ましくない。ま
た反応時間120分以上ではアミド基の加水分解反
応が進みすぎてカルボキシル基を過剰に生成する
ため、紙力増強効果の上で好ましくない。上記反
応条件下で共重合体中にアニオン性基１〜20モル
％、カチオン性基１〜10モル％が生成した後、鉱
酸、有機カルボン酸または有機スルホン酸等の酸
を加えて水溶液をPH３〜９に下げて本反応を停止
終了させる。ここで鉱酸とは具体的には塩酸、硫
酸、硝酸、リン酸等が例示される。有機カルボン
酸としては具体的には蟻酸、酢酸、プロピオン酸
等が例示できる。又、有機スルホン酸としては、
具体的にメチル硫酸、エチル硫酸、ベンゼンスル
ホン酸等が例示される。
本発明の両性重合体は15％濃度で1000〜
100000cps（25℃）のものであり特に2000〜
50000cps程度が紙力増強剤として使用する上で好
ましい。
本発明の両性重合体を紙力増強剤として内添で
使用する場合、従来のアニオン性紙力増強剤と同
様に硫酸バンドを定着剤としてPH４〜5.5の範囲
で使用することが好ましい。またサイズプレス、
ロールコータなどによる塗布も行うことができ
る。パルプとしては、クラフトパルプ、サルフア
イトパルプ、グランドパルプ、古紙等その種類に
限定はなく、またサイズ剤、填料等通常の製紙用
添加剤を併用、添加することができる。
以下実施例により本発明を説明する。
実施例 １
アクリルアミド42.6ｇ、アクリロニトリル21.2
ｇ（モル比60：40）および水365ｇを500mlセパラ
ブルフラスコにとり、充分に窒素ガスで重合系内
の酸素を除去した後、過硫酸アンモニウム0.1ｇ
を60℃で添加し、この後80℃まで徐々に昇温して
80℃で２時間窒素ガスを流しながら共重合反応を
行う。その後、15重量％の水酸化ナトリウム水溶
液25ｇを加え、PH12のアルカリ性下で80℃で15分
間、30分間及び90分間の３種の反応時間で反応さ
せた後、15重量％の硫酸水溶液39ｇを加えてPHを
下げ、反応を停止させ、各々重合体Ａ，Ｂ及びＣ
を得た。
実施例 ２
アクリルアミド49.8ｇ、アクリロニトリル15.9
ｇ〔モル比70：30）、水375ｇに過硫酸アンモニウ
ム0.1ｇを加え、実施例１と同様の方法で共重合
反応を行う。この後15重量％の水酸化ナトリウム
水溶液25ｇを加えてPH12のアルカリ性とし、80℃
で15分、30分および90分の３種の反応時間で反応
を行い、この後15重量％の硫酸水溶液39ｇを加
え、各々重合体Ｄ，Ｅ，Ｆを得た。
実施例 ３
アクリルアミド49.8ｇ、アクリロニトリル15.9
ｇ（モル比70：30）、水375ｇに過硫酸アンモニウ
ム0.1ｇを加え、実施例１と同様に共重合反応を
行い、この後15重量％ジメチルアミン水溶液30ｇ
加え、PH11のアルカリ性下80℃で30分反応を行
い、次に15重量％塩酸水溶液30ｇを加えて重合体
Ｇを得た。
実施例 ４
アクリルアミド49.8ｇ、アクリロニトリル15.9
ｇ（モル比70：30）、水375ｇに過硫酸アンモニウ
ム0.1ｇを加え、実施例１と同様に共重合反応を
行いこの後15％の水酸化カリウム20ｇを加えてPH
12のアルカリ性下75℃で30分反応させ、次に15重
量％の塩酸18ｇを加えて重合体Ｈを得た。
実施例 ５
アクリルアミド42.6ｇ、アクリロニトリル15.9
ｇ、酢酸ビニル8.6ｇ（モル比60：30：10）、水
380ｇに過硫酸アンモニウム0.1ｇ、亜硫酸ナトリ
ウム0.02ｇを45℃で加え、この後徐々に昇温しな
がら80℃にする。その後80℃で２時間共重合反応
を続ける。その次に15重量％の水酸化ナトリウム
水溶液16ｇを加え、PH11のアルカリ性下80℃で30
分間反応させた後、15％の酢酸32ｇを加えて重合
体Ｉを得た。
比較例 １
アクリルアミド42.6ｇ、アクリロニトリル15.9
ｇ、アクリル酸ナトリウム9.4ｇ（モル比60：
30：10）、水385ｇに過硫酸アンモニウム0.1ｇを
65℃で加え、徐々に昇温して80℃にする。この後
80℃で２時間共重合反応を続ける。そしてその共
重合体をそのまゝ重合体Ｊとした。
比較例 ２
アクリルアミド71ｇ、水405ｇに過硫酸アンモ
ニウム２ｇ、イソプロピルアルコール１ｇを65℃
で加える。これにより急激に発熱するので、水浴
で冷却しながら80℃まで昇温するように調整し、
この後80℃で２時間重合反応を続けた。次に15重
量％の水酸化ナトリウム水溶液16ｇを80℃で加
え、PH11のアルカリ性とし30分反応後15重量％の
塩酸18ｇを加え、重合体Ｋを得た。
以上の実施例、比較例で得られた重合体の固形
分、粘度、PH、アニオン量およびカチオン量を表
１に示した。
The present invention uses a copolymer containing an α,β-unsaturated amide such as acrylamide, an α,β-unsaturated nitrile such as acrylonitrile, and optionally a nonionic monomer copolymerizable with these, using sodium hydroxide. An anionic group and a cationic group are simultaneously introduced into the polymer by reacting with an alkali metal hydroxide such as, an alkali metal carbonate such as sodium carbonate, or an amine base such as dimethylamine under alkaline conditions. This invention relates to a paper strength enhancer made of an amphoteric polymer. Conventionally, anionic polymers mainly composed of acrylamide, such as acrylamide-acrylic acid copolymers or polymers into which carboxyl groups have been introduced through a partial hydrolysis reaction of polyacrylamide, have been used in the paper manufacturing industry using sulfuric acid as a fixing agent. It is used as a paper strength enhancer. However, conventional anionic paper strength agents mainly based on acrylamide usually have a fixation rate of 60 to 80% on valve fibers.
%, and it is difficult to say that it has a sufficient effect of increasing paper strength. The present inventors have conducted extensive research with the aim of obtaining a paper strength enhancer that increases the fixation rate to pulp fibers and exhibits an excellent paper strength enhancing effect, and as a result, the present invention was achieved. That is, an aqueous solution of a copolymer mainly composed of an α,β-unsaturated amide such as acrylamide and an α,β-unsaturated nitrile such as acrylonitrile is mixed with an alkali metal hydroxide such as sodium hydroxide or dimethylamine, etc. It has been discovered that an amphoteric polymer in which an anionic group and a cationic group are simultaneously introduced into the polymer can be obtained by adding an amine base and reacting under alkaline conditions. In addition, this amphoteric polymer has a fixation rate of 90% on pulp fibers.
As described above, it has been found that the paper strength enhancing effect is higher than that of conventional anionic polymers and is significantly superior, and the present invention has now been completed. The anionic group in the amphoteric polymer of the present invention is introduced by hydrolyzing the amide group under alkaline conditions to become a carboxyl group. Furthermore, although the mechanism of introduction of the cationic group is currently unclear,
In a homopolymer of α,β-unsaturated amide such as acrylamide, a cationic group is not introduced even if the same reaction is performed under alkaline conditions, and in order to introduce a cationic group, the presence of a nitrile group is required as in the present invention. It is essential. For this reason, it is thought that ammonia, which is produced as a by-product along with carboxyl groups due to the hydrolysis reaction of amide groups, reacts with nitrile groups to develop cationic properties. Specific examples of the α,β-unsaturated amide in the polymer of the present invention include acrylamide, methacrylamide, dimethylacrylamide, and the like.
Specific examples of the α,β-unsaturated nitrile include acrylonitrile and methacrylonitrile. In addition, nonionic monomers that can be copolymerized with these are components that can be added to the copolymer as necessary. Specifically, aromatic hydrocarbons such as styrene and α-methylstyrene, acrylic acid C1-8 alkyl esters of acrylic acid or methacrylic acid such as methyl, ethyl acrylate, butyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, and ethyl methacrylate, vinyl acetate vinyl propionate Vinyl esters such as The ratio of the above α,β-unsaturated amide component, α,β-unsaturated nitrile component and nonionic monomer component is such that the α,β-unsaturated amide component is 50 to 90 mol%, but preferably 60-80 mol% is suitable. If the α,β-unsaturated amide component is less than 50 mol %, the paper strength enhancing effect will not be sufficiently exhibited, which is not preferable. In addition, the α,β-unsaturated nitrile component is 10 to
The content is 50 mol%, preferably 20 to 40 mol%. This α,β-unsaturated nitrile component is 10 mol%
In the following, hardly any cationic groups are introduced in the subsequent reaction under alkaline conditions, and the amphoteric polymer, which is a feature of the present invention, cannot be obtained. Moreover, if the α,β-unsaturated nitrile component is more than 50 mol%, it becomes insoluble in water, which is not preferable. The nonionic monomer component is
It is a component that is added as necessary in a range of 20 mol% or less. The copolymerization reaction of the α,β-unsaturated amide component, the α,β-unsaturated nitrile component, and the nonionic monomer component can be carried out by a conventional method, and aqueous solution polymerization is particularly common. For example, ammonium persulfate, potassium persulfate,
A water-soluble peroxide such as hydrogen peroxide, or a combination of these with a reducing agent such as dimethylamine or sodium sulfite, or a chain transfer agent such as allyl alcohol or isopropyl alcohol, is added to the polymerizable monomer mixture in an amount of 0.05 to 5% by weight. % used, concentration of monomer mixture in water solvent 10-50% concentration by weight, 40-95
The copolymerization reaction is carried out in a nitrogen gas atmosphere at a temperature of .degree. C. for 1 to 5 hours. In this way, the copolymer composed of the above three components has a viscosity of 15% aqueous solution.
1000~100000cps (25℃). Next, an alkali metal hydroxide, an alkali metal carbonate, or an amine base is added to an aqueous solution of this copolymer at a concentration of 1 to 15% by weight based on the copolymer.
Add and react for 5 to 120 minutes at a pH of 9 or higher and a temperature of 40 to 95°C. When 1 to 20 mol% of anionic groups and 1 to 10 mol% of cationic groups have been introduced, an acid such as a mineral acid, an organic carboxylic acid, or an organic sulfonic acid is added to adjust the pH to 3 to 9 to carry out the reaction. Stop. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, and the like. Examples of alkali metal carbonates include sodium carbonate, potassium carbonate, and lithium carbonate. Specific examples of the amine base include ammonia, aliphatic amines such as methylamine, dimethylamine, trimethylamine, and diethylamine. Here, the alkali metal hydroxide, alkali metal carbonate, and amine base must be added in an amount of 1 to 15% by weight based on the copolymer to make the copolymer alkaline with a pH of 9 or more, preferably 10 to 13.
At pH 9 or lower, the reaction rate of amide group hydrolysis reaction and cationic group introduction reaction becomes extremely slow.
Therefore, the amphoteric polymer characteristic of the present invention cannot be obtained. Then, the copolymer was heated at a temperature below the above pH.
The desired amphoteric polymer is obtained by reacting at 40 to 95°C for 5 to 120 minutes. Here, if the reaction time is 5 minutes or less, the obtained polymer aqueous solution will be
It is not preferable because it has poor stability such as phase separation. Further, if the reaction time is 120 minutes or more, the hydrolysis reaction of the amide groups will proceed too much and excessive carboxyl groups will be produced, which is not preferable in terms of the paper strength enhancement effect. After 1 to 20 mol% of anionic groups and 1 to 10 mol% of cationic groups are formed in the copolymer under the above reaction conditions, an acid such as a mineral acid, an organic carboxylic acid, or an organic sulfonic acid is added to form an aqueous solution. The reaction is stopped and completed by lowering the pH to 3-9. Here, specific examples of mineral acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Specific examples of organic carboxylic acids include formic acid, acetic acid, and propionic acid. In addition, as organic sulfonic acids,
Specific examples include methyl sulfate, ethyl sulfate, and benzenesulfonic acid. The amphoteric polymer of the present invention has a concentration of 1000 to 15%.
100000cps (25℃), especially 2000~
Approximately 50,000 cps is preferable for use as a paper strength enhancer. When the amphoteric polymer of the present invention is internally added as a paper strength enhancer, it is preferable to use sulfuric acid as a fixing agent within a pH range of 4 to 5.5, similar to conventional anionic paper strength enhancers. Also size press,
Coating can also be performed using a roll coater or the like. The type of pulp is not limited to kraft pulp, sulfite pulp, ground pulp, waste paper, etc., and ordinary papermaking additives such as sizing agents and fillers can be used or added. The present invention will be explained below with reference to Examples. Example 1 Acrylamide 42.6g, acrylonitrile 21.2g
(mole ratio 60:40) and 365 g of water in a 500 ml separable flask, and after thoroughly removing oxygen in the polymerization system with nitrogen gas, add 0.1 g of ammonium persulfate.
was added at 60°C, and then the temperature was gradually raised to 80°C.
The copolymerization reaction is carried out at 80°C for 2 hours while flowing nitrogen gas. Thereafter, 25 g of a 15% by weight aqueous sodium hydroxide solution was added, and the reaction was carried out at 80°C for 3 reaction times: 15 minutes, 30 minutes, and 90 minutes under alkaline pH 12, and then 39 g of a 15% by weight sulfuric acid aqueous solution was added. In addition, the pH was lowered, the reaction was stopped, and polymers A, B, and C were formed, respectively.
I got it. Example 2 Acrylamide 49.8g, acrylonitrile 15.9g
g [molar ratio 70:30], 0.1 g of ammonium persulfate was added to 375 g of water, and a copolymerization reaction was carried out in the same manner as in Example 1. After that, add 25g of 15% by weight sodium hydroxide aqueous solution to make it alkaline to PH12 and raise the temperature to 80℃.
The reaction was carried out for three reaction times: 15 minutes, 30 minutes, and 90 minutes, and then 39 g of a 15% by weight aqueous sulfuric acid solution was added to obtain polymers D, E, and F, respectively. Example 3 Acrylamide 49.8g, acrylonitrile 15.9g
g (molar ratio 70:30), 0.1 g of ammonium persulfate was added to 375 g of water, a copolymerization reaction was carried out in the same manner as in Example 1, and then 30 g of a 15% by weight dimethylamine aqueous solution was added.
In addition, a reaction was carried out at 80° C. for 30 minutes under alkaline pH 11, and then 30 g of a 15% by weight aqueous hydrochloric acid solution was added to obtain Polymer G. Example 4 Acrylamide 49.8g, acrylonitrile 15.9g
(molar ratio 70:30), 0.1 g of ammonium persulfate was added to 375 g of water, a copolymerization reaction was carried out in the same manner as in Example 1, and then 20 g of 15% potassium hydroxide was added to adjust the pH.
The reaction was carried out for 30 minutes at 75° C. under alkalinity of 12°C, and then 18 g of 15% by weight hydrochloric acid was added to obtain Polymer H. Example 5 Acrylamide 42.6g, acrylonitrile 15.9g
g, vinyl acetate 8.6 g (molar ratio 60:30:10), water
Add 0.1 g of ammonium persulfate and 0.02 g of sodium sulfite to 380 g at 45°C, and then gradually raise the temperature to 80°C. Thereafter, the copolymerization reaction was continued at 80°C for 2 hours. Next, add 16 g of a 15% by weight aqueous sodium hydroxide solution and heat for 30 minutes at 80℃ under alkaline pH 11.
After reacting for a minute, 32 g of 15% acetic acid was added to obtain Polymer I. Comparative example 1 Acrylamide 42.6g, acrylonitrile 15.9g
g, sodium acrylate 9.4 g (molar ratio 60:
30:10), add 0.1 g of ammonium persulfate to 385 g of water.
Add at 65°C and gradually increase the temperature to 80°C. After this
Continue the copolymerization reaction at 80°C for 2 hours. The copolymer was designated as Polymer J. Comparative Example 2 71g of acrylamide, 405g of water, 2g of ammonium persulfate, and 1g of isopropyl alcohol at 65℃
Add with . This causes rapid heat generation, so adjust the temperature to 80℃ while cooling it in a water bath.
Thereafter, the polymerization reaction was continued at 80°C for 2 hours. Next, 16 g of a 15% by weight aqueous sodium hydroxide solution was added at 80° C. to make the mixture alkaline to pH 11, and after reaction for 30 minutes, 18 g of 15% by weight hydrochloric acid was added to obtain Polymer K. Table 1 shows the solid content, viscosity, PH, anion content, and cation content of the polymers obtained in the above Examples and Comparative Examples.
【表】
以上の実施例及び比較例で得られた重合体の内
Ｂ，Ｅ，Ｇ，Ｈ，Ｉ，Ｊ，Ｋについて、紙力増強
剤としての効果を確認するため、次の実験例に基
づいて行なつた。
実験例 １
Ｌ／Ｎ（70／30）BKP，GP／LBKP／NBKP
（60／20／20）およびNUKPの３種のパルプを使
用し、各パルプの３％スラリーに、硫酸バンドを
パルプに対して３％加え、さらに各々の重合体を
パルプに対して0.5％加え、５分間撹拌した後タ
ツピースタンダードシートマシンで坪量60ｇ／m2
となるように抄紙した。ついでその紙を４Kg／cm2
で１分間脱水したのち、105℃で３分間乾燥した。
この後シートを20℃、65％PHで24時間調湿した
後、比破裂強度を測定した。
結果を表２に示す。[Table] Among the polymers B, E, G, H, I, J, and K obtained in the above examples and comparative examples, in order to confirm their effectiveness as paper strength enhancers, the following experimental examples were used. Based on this. Experimental example 1 L/N (70/30) BKP, GP/LBKP/NBKP
Three types of pulp (60/20/20) and NUKP were used, and to a 3% slurry of each pulp, sulfate was added at 3% based on the pulp, and each polymer was added at 0.5% based on the pulp. After stirring for 5 minutes, the basis weight is 60g/ m2 using a Tatsupi standard sheet machine.
The paper was made to look like this. Then weigh the paper at 4Kg/cm 2
After dehydrating for 1 minute, the sample was dried at 105°C for 3 minutes.
Thereafter, the sheet was conditioned at 20° C. and 65% PH for 24 hours, and the specific bursting strength was measured. The results are shown in Table 2.
【表】【table】
【表】
実験例 ２
さきほどのGP／LBKP／NBKPにタルクを対
パルプで20％加え、実験例１と同様に硫酸バンド
３％、重合体0.5％及びロジンサイズ剤0.5％を加
え、坪量60ｇ／m2となるように抄紙した。この後
の処理も実験例１と同様に行い、IGT強度（ドラ
イ、ウエツト）および裂断長に換算した引張強度
を測定した。結果を表３に示す。[Table] Experimental Example 2 Add 20% talc to the pulp to the previous GP/LBKP/NBKP, add 3% sulfuric acid, 0.5% polymer, and 0.5% rosin sizing agent as in Experimental Example 1, and make a 60g basis weight. / m2 . The subsequent treatments were carried out in the same manner as in Experimental Example 1, and the IGT strength (dry, wet) and tensile strength converted to breaking length were measured. The results are shown in Table 3.
【表】
本発明によれば、表１から明らかな如く紙力補
強剤として適した性状を有すると共に、アニオン
性とカチオン性とを併せ持つた両性を有してい
る。而してこれを用いて抄造した紙は、表２及び
表３に示されるように大きな強度を有しており、
紙力補強剤としてすぐれている。[Table] As is clear from Table 1, the present invention has properties suitable as a paper strength reinforcing agent, and also has amphoteric properties, having both anionic and cationic properties. The paper made using this material has great strength as shown in Tables 2 and 3.
Excellent as a paper strength reinforcing agent.
Claims (1)
−不飽和ニトリル10〜50モル％およびこれらと共
重合可能なノニオン性単量体０〜20モル％からな
る共重合体を、水溶液中アルカリ性下で反応させ
てアニオン基１〜20モル％およびカチオン基１〜
10モル％を同時に導入してなることを特徴とする
両性重合体よりなる紙力増強剤。1 α,β-unsaturated amide 50-90 mol%, α,β
- A copolymer consisting of 10 to 50 mol% of unsaturated nitrile and 0 to 20 mol% of a nonionic monomer copolymerizable with these is reacted in an aqueous solution under alkalinity to form an anionic group of 1 to 20 mol% and a cationic group. Base 1~
A paper strength enhancer comprising an amphoteric polymer, characterized in that 10 mol% of the amphoteric polymer is simultaneously incorporated therein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19923982A JPS5994699A (en) | 1982-11-12 | 1982-11-12 | Paper strength enhancer comprising |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19923982A JPS5994699A (en) | 1982-11-12 | 1982-11-12 | Paper strength enhancer comprising |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5994699A JPS5994699A (en) | 1984-05-31 |
| JPH0147598B2 true JPH0147598B2 (en) | 1989-10-16 |
Family
ID=16404472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19923982A Granted JPS5994699A (en) | 1982-11-12 | 1982-11-12 | Paper strength enhancer comprising |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5994699A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3358377B2 (en) * | 1995-03-17 | 2002-12-16 | 日本ピー・エム・シー株式会社 | Surface paper quality improver |
-
1982
- 1982-11-12 JP JP19923982A patent/JPS5994699A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5994699A (en) | 1984-05-31 |
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