CN114541172A - 纸力增强剂和纸 - Google Patents
纸力增强剂和纸 Download PDFInfo
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- CN114541172A CN114541172A CN202111358626.6A CN202111358626A CN114541172A CN 114541172 A CN114541172 A CN 114541172A CN 202111358626 A CN202111358626 A CN 202111358626A CN 114541172 A CN114541172 A CN 114541172A
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- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical group [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 13
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- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 5
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- 208000034628 Celiac artery compression syndrome Diseases 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- 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
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- AZFNGPAYDKGCRB-XCPIVNJJSA-M [(1s,2s)-2-amino-1,2-diphenylethyl]-(4-methylphenyl)sulfonylazanide;chlororuthenium(1+);1-methyl-4-propan-2-ylbenzene Chemical compound [Ru+]Cl.CC(C)C1=CC=C(C)C=C1.C1=CC(C)=CC=C1S(=O)(=O)[N-][C@@H](C=1C=CC=CC=1)[C@@H](N)C1=CC=CC=C1 AZFNGPAYDKGCRB-XCPIVNJJSA-M 0.000 description 1
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- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
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- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- CAMXVZOXBADHNJ-UHFFFAOYSA-N ammonium nitrite Chemical compound [NH4+].[O-]N=O CAMXVZOXBADHNJ-UHFFFAOYSA-N 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BBWBEZAMXFGUGK-UHFFFAOYSA-N bis(dodecylsulfanyl)-methylarsane Chemical compound CCCCCCCCCCCCS[As](C)SCCCCCCCCCCCC BBWBEZAMXFGUGK-UHFFFAOYSA-N 0.000 description 1
- WYFGBFHRZGNGAU-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;hydrochloride Chemical compound Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 WYFGBFHRZGNGAU-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 230000001143 conditioned effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
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- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- DNUFCIOKWJELSH-UHFFFAOYSA-O diazanium dioxido(oxo)phosphanium Chemical compound [NH4+].[NH4+].[O-][P+]([O-])=O DNUFCIOKWJELSH-UHFFFAOYSA-O 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
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- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 1
- XBMOWLAOINHDLR-UHFFFAOYSA-N dipotassium;hydrogen phosphite Chemical compound [K+].[K+].OP([O-])[O-] XBMOWLAOINHDLR-UHFFFAOYSA-N 0.000 description 1
- IIRVGTWONXBBAW-UHFFFAOYSA-M disodium;dioxido(oxo)phosphanium Chemical compound [Na+].[Na+].[O-][P+]([O-])=O IIRVGTWONXBBAW-UHFFFAOYSA-M 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal 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
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- BZHCGFBZBPVRFE-UHFFFAOYSA-N monopotassium phosphite Chemical compound [K+].OP(O)[O-] BZHCGFBZBPVRFE-UHFFFAOYSA-N 0.000 description 1
- 238000000569 multi-angle light scattering Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BUIMWOLDCCGZKZ-UHFFFAOYSA-N n-hydroxynitramide Chemical compound ON[N+]([O-])=O BUIMWOLDCCGZKZ-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- 235000010289 potassium nitrite Nutrition 0.000 description 1
- 239000004304 potassium nitrite Substances 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- KIMPPGSMONZDMN-UHFFFAOYSA-N sodium;dihydrogen phosphite Chemical compound [Na+].OP(O)[O-] KIMPPGSMONZDMN-UHFFFAOYSA-N 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- GRPURDFRFHUDSP-UHFFFAOYSA-N tris(prop-2-enyl) benzene-1,2,4-tricarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C(C(=O)OCC=C)=C1 GRPURDFRFHUDSP-UHFFFAOYSA-N 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
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Abstract
本发明提供一种纸力增强剂和纸,所述纸力增强剂具有优异的保存稳定性,在制成纸时表现出良好的纸力效果。一种纸力增强剂,其为包含(甲基)丙烯酰胺系聚合物(A)、水溶性铝化合物(B)、无机酸盐(C)((C)成分中,属于(B)成分的除外)以及无机酸(D)的混合液,其中,所述(甲基)丙烯酰胺系聚合物(A)包含(甲基)丙烯酰胺(a1)、具有阳离子性基团的聚合性单体(a2)、具有阴离子性基团的聚合性单体(a3)以及交联性单体(a4)作为反应成分;将刚制备好的混合液的粘度(浓度15重量%、温度:25℃)设为X1mPa·s,并且将在温度60℃保管3天后的混合液的粘度(浓度15重量%、温度:25℃)设为X2mPa·s时,30≤X1≤30,000且0.8≤X2/X1≤2。
Description
技术领域
本发明涉及纸力增强剂以及使用其而得到的纸。
背景技术
纸力增强剂是为了提高纸本身的强度而使用的化学品。特别是造纸业中造纸体系的封闭化(废纸纸浆的回收利用等)进展,作为原料的纸浆纤维的强度降低导致所得的纸的强度也容易进一步降低,在这样的环境中,纸力增强剂的重要性正在提高。
顺便提及,作为纸力增强剂,(甲基)丙烯酰胺系聚合物被广泛使用,根据其离子性,分类为阴离子型、阳离子型和两性型。其中,主流的两性型的(甲基)丙烯酰胺系聚合物是通过将阳离子性单体、阴离子性单体等聚合性单体与丙烯酰胺共聚而得到的(专利文献1)。
将所述聚合物添加到造纸体系的纸浆浆料时,硫酸铝也作为固定剂加入,但硫酸铝伴随着造纸体系的封闭化,其固定效果降低,另外,从环境负荷的观点出发,有在造纸工厂中减少硫酸铝的添加量的动向,纸力增强剂本身的纸力效果难以进一步发挥成为课题。作为其解决方法,已知与之前相比添加将(甲基)丙烯酰胺聚合物与硫酸铝等水溶性铝化合物混合的纸力增强剂的方法(专利文献2)。像这样的混合的纸力增强剂具有例如在减少添加到纸浆浆料中的硫酸铝的量、另外提高纸力效果的方面的优点。
现有技术文献
专利文献
专利文献1:日本特开2012-251252号公报
专利文献2:日本特开2001-011787号公报
然而,同时包含(甲基)丙烯酰胺系聚合物和水溶性铝化合物的纸力增强剂通过该聚合物中的阴离子性基团与铝原子的阳离子性的静电相互作用,主要形成多个聚合物离子键合至铝原子的交联结构(以下称为“金属交联”),其结果,存在随时间的推移容易增稠、所谓保存稳定性方面的课题。
发明内容
发明要解决的课题
本发明的目的在于提供具有优异的保存稳定性,在纸中表现出良好的纸力效果的纸力增强剂。
用于解决课题的手段
本发明人对纸力增强剂中所包含的成分进行了深入研究,结果发现了解决上述课题的方案,从而完成了本发明。即,本发明涉及以下的纸力增强剂、纸。
1.一种纸力增强剂,其为包含(甲基)丙烯酰胺系聚合物(A)、水溶性铝化合物(B)、无机酸盐(C)((C)成分中,属于(B)成分的除外)以及无机酸(D)的混合液,其中,所述(甲基)丙烯酰胺系聚合物(A)包含(甲基)丙烯酰胺(a1)、具有阳离子性基团的聚合性单体(a2)、具有阴离子性基团的聚合性单体(a3)以及交联性单体(a4)作为反应成分;
将刚制备好的混合液的粘度(浓度15重量%、温度:25℃)设为X1mPa.s,并且将在温度60℃保管3天后的混合液的粘度(浓度15重量%、温度:25℃)设为X2mPa·s时,30≤X1≤30,000且0.8≤X2/X1≤2。
2.根据上述1所述的纸力增强剂,其中,所述反应成分的摩尔比率为:(a1)成分55摩尔%~98摩尔%、(a2)成分0.5摩尔%~20摩尔%、(a3)成分0.5摩尔%~20摩尔%以及(a4)成分0.002摩尔%~2摩尔%。
3.根据上述1或2所述的纸力增强剂,其中,(B)成分为硫酸铝和/或其水合物。
4.根据上述1~3中任一项所述的纸力增强剂,其中,(B)成分的含量以固体成分重量计,相对于(A)成分100重量份以铝离子量的形式计为0.3重量份~20重量份。
5.根据上述1~4中任一项所述的纸力增强剂,其中,(C)成分包含选自磷酸钠、磷酸钾、磷酸氢二钠、磷酸氢二钾、磷酸二氢钠、磷酸二氢钾、硫酸钠、硫酸钾、硫酸氢钠和硫酸氢钾组成的组中的1种以上。
6.根据上述1~5中任一项所述的纸力增强剂,其中,(C)成分的含量以固体成分重量计,相对于(A)成分100重量份,为1重量份~70重量份。
7.根据上述1~6中任一项所述的纸力增强剂,其中,(D)成分为硫酸和/或磷酸。
8.根据上述1~7中任一项所述的纸力增强剂,其中,固体成分浓度1重量%的水溶液在温度25℃的pH为2~3.5。
9.一种纸,其使用上述1~8中任一项所述的纸力增强剂而得到。
发明的效果
本发明的纸力增强剂可抑制粘度随时间推移的增加,并且在纸中表现出优异的纸力效果。
具体实施方式
本发明的纸力增强剂为包含以下物质的混合液:(甲基)丙烯酰胺系聚合物(A)(以下,称为(A)成分。)、水溶性铝化合物(B)(以下,称为(B)成分。)、无机酸盐(C)((C)成分中,属于(B)成分的除外)(以下,称为(C)成分。)、以及无机酸(D)(以下,称为(D)成分。)。
(A)成分为发挥优异的纸力效果的成分,在本发明中,是指包含(甲基)丙烯酰胺(a1)(以下,称为(a1)成分。)、具有阳离子性基团的聚合性单体(a2)(以下,称为(a2)成分。)、具有阴离子性基团的聚合性单体(a3)(以下,称为(a3)成分。)以及交联性单体(a4)(以下,称为(a4)成分。)作为反应成分的聚合物。此处,聚合性单体是指在单体1分子中具有1个以上的双键和/或碳-碳三键的单体。
作为(a1)成分,可以列举甲基丙烯酰胺、丙烯酰胺。这些可以单独使用,也可以组合使用2种以上。
作为(a2)成分,只要是具有阳离子性基团的成分则没有特别限定,可以使用各种公知的成分,可以列举例如具有仲氨基的聚合性单体、具有叔氨基的聚合性单体、这些聚合性单体的季盐等。
作为具有仲氨基的聚合性单体,没有特别限定,可以列举例如二烯丙胺等。作为具有叔氨基的聚合性单体,没有特别限定,可以列举例如(甲基)丙烯酸N,N-二甲基氨基乙酯、(甲基)丙烯酸N,N-二乙基氨基乙酯等具有叔氨基的(甲基)丙烯酸酯;N,N-二甲基氨基丙基(甲基)丙烯酰胺、N,N-二乙基氨基丙基(甲基)丙烯酰胺等具有叔氨基的(甲基)丙烯酰胺等。这些单体的季盐是指,使具有上述仲氨基的聚合性单体或具有叔氨基的聚合性单体与季化剂反应而得到的物质等,作为季盐,可以是盐酸盐、硫酸盐等无机酸盐,也可以是乙酸盐等有机酸盐。另外,作为季化剂,可以列举甲基氯化物、苄基氯化物、二甲基硫酸、表氯醇等。这些可以单独使用,也可以组合使用2种以上。其中,优选具有叔氨基的聚合性单体和/或其季盐,更优选包含具有叔氨基的(甲基)丙烯酸酯和/或该(甲基)丙烯酸酯的季盐,进一步优选(甲基)丙烯酸N,N-二甲基氨基乙酯、(甲基)丙烯酸N,N-二甲基氨基乙酯的季盐,特别优选丙烯酸N,N-二甲基氨基乙酯、丙烯酸N,N-二甲基氨基乙酯苄基氯化物、甲基丙烯酸N,N-二甲基氨基乙酯苄基氯化物。需要说明的是,“(甲基)丙烯酸酯”是指甲基丙烯酸酯或丙烯酸酯。
作为(a3)成分,只要是具有阴离子性基团的成分则没有特别限定,可以使用各种公知的成分。可以列举例如,(甲基)丙烯酸、衣康酸、衣康酸酐、富马酸、马来酸等具有羧基的聚合性单体;乙烯基磺酸、甲基烯丙基磺酸等具有磺酸基的聚合性单体等。需要说明的是,这些(a3)成分可以以钠、钾等碱金属盐、铵盐等盐的形式使用。这些可以单独使用,也可以组合使用2种以上。其中优选(甲基)丙烯酸、衣康酸、甲基烯丙基磺酸钠。
(a4)成分是用于向聚合物中导入支链结构的成分。作为(a4)成分,没有特别限定,可以列举例如N-甲基(甲基)丙烯酰胺、N-乙基(甲基)丙烯酰胺、N-异丙基(甲基)丙烯酰胺、N-叔丁基(甲基)丙烯酰胺等N-烷基(甲基)丙烯酰胺;N,N-二甲基(甲基)丙烯酰胺、N,N-二乙基(甲基)丙烯酰胺、N,N-二异丙基(甲基)丙烯酰胺等N,N-二烷基(甲基)丙烯酰胺;N,N′-亚甲基双(甲基)丙烯酰胺、N,N′-亚乙基双(甲基)丙烯酰胺等N,N′-亚烷基双(甲基)丙烯酰胺;三烯丙基异氰脲酸酯、偏苯三酸三烯丙酯、三烯丙基胺、三烯丙基(甲基)丙烯酰胺等具有三烯丙基的交联性单体;1,3,5-三丙烯酰基-1,3,5-三嗪、1,3,5-三丙烯酰基六氢-1,3,5-三嗪等具有(甲基)丙烯酰基的三嗪等。这些可以单独使用,也可以组合使用2种以上。其中,优选选自N,N-二烷基(甲基)丙烯酰胺、N,N′-亚烷基双(甲基)丙烯酰胺和具有(甲基)丙烯酰基的三嗪组成的组中的至少1种,更优选N,N-二甲基丙烯酰胺、N,N′-亚甲基双丙烯酰胺。
作为各反应成分的使用量,没有特别限定,从得到的纸表现出优异的纸力效果的观点出发,以摩尔比率计,如下设定。
·(a1)成分:优选55~98摩尔%、更优选77.8~93.5摩尔%
·(a2)成分:优选0.5~20摩尔%、更优选3~10摩尔%
·(a3)成分:优选0.5~20摩尔%、更优选1~10摩尔%
·(a4)成分:优选0.002~2摩尔%、更优选0.004~0.5摩尔%
作为上述反应成分,还可以包含(a1)~(a4)成分以外的单体(a5)(以下,称为(a5)成分)。作为(a5)成分,没有特别限定,可以列举例如苯乙烯、α-甲基苯乙烯、乙烯基甲苯等具有芳香环的聚合性单体;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸环己酯等(甲基)丙烯酸烷基酯;乙酸乙烯酯、丙酸乙烯酯等羧酸乙烯酯;丙烯腈等腈;2-巯基乙醇、正十二烷基硫醇等硫醇类;乙醇、异丙醇、正戊醇等醇;α-甲基苯乙烯二聚物、乙基苯、异丙基苯、异丙苯等芳香族化合物;四氯化碳等。这些可以单独使用,也可以组合使用2种以上。另外,(a5)成分的含量在全部构成单体中小于5摩尔%。
在聚合物的制造中,以调节上述单体溶液的pH、抑制单体的水解(聚合稳定化)等为目的,可以加入柠檬酸、琥珀酸、草酸等有机酸;盐酸、硫酸、磷酸等无机酸;氢氧化钠、氢氧化钾、氢氧化钙等无机碱;消泡剂、抗氧化剂等添加剂。这些可以单独使用,也可以组合使用2种以上,作为其含量,相对于全部构成单体100重量份,优选15重量份以下,更优选10重量份以下。
关于(A)成分,没有特别限定,可通过使包含(a1)成分、(a2)成分、(a3)成分和(a4)成分的单体成分、根据需要的(a5)成分和上述添加剂在溶剂中聚合而得到。
作为上述的聚合方法,没有特别限定,可以列举例如仅使用滴加聚合法的方法,或将同时聚合法(一并加入单体混合液)和滴加聚合法组合的方法等。
滴加聚合法为将单体混合液滴加在预先加入了水等溶剂的反应体系中的方法,作为仅使用该聚合法的方法,可以列举例如以下(1)~(3)。需要说明的是,滴加可以连续滴加,也可以在滴加中途停止、使其聚合一定时间后继续滴加。
(1)滴加混合了全部单体成分的单体混合液的方法
(2)分别制备2种以上的单体混合液后,同时滴加的方法
(3)分别制备2种以上的单体混合液后,依次滴加的方法
另外,作为组合同时聚合法和滴加聚合法的方法,可以列举例如以下(4)~(7)。
(4)将各单体混合液分别进行同时聚合后,混合各聚合物的方法
(5)将1种以上的单体混合液进行同时聚合完成后,滴加剩余的单体混合液的方法
(6)将1种以上的单体混合液进行同时聚合的中途开始滴加剩余的单体混合液的聚合方法
(7)将1种以上的单体混合液进行滴加聚合,一并加入剩余的单体混合液后,进行同时聚合的方法
此处,在制备2种以上的单体混合液时,更优选进行在任一种单体混合液中,使反应涉及的(a2)成分、(a3)成分的浓度变高的操作:增多一部分混合液中的(a2)成分、(a3)成分的量,使这些混合液依次反应,或者,在聚合反应中某个时间点追加(a2)成分、(a3)成分等。
作为溶剂,可以列举水、有机溶剂等,这些可以单独使用,也可以组合使用2种以上。作为有机溶剂,没有特别限定,可以列举例如甲醇、乙醇、正丙醇、异丙醇、正丁醇、仲丁醇、叔丁醇、异丁醇、正己醇、正辛醇、乙二醇、丙二醇、二乙二醇、三乙二醇、二丙酮醇等醇;乙二醇单丁基醚、丙二醇单甲基醚、丙二醇单乙基醚等醚等。其中,从使(a1)~(a5)成分溶解的观点出发,通常优选使用水。
作为聚合引发剂,没有特别限定,可以列举例如过硫酸铵、过硫酸钾、过硫酸钠等过硫酸盐;2,2′-偶氮双(2-脒基丙烷)盐酸盐、2,2′-偶氮双[2(2-咪唑啉-2-基)丙烷]盐酸盐等偶氮系化合物;过氧化氢等。这些可以单独使用,也可以组合使用2种以上。其中,从使溶液聚合充分进行的观点出发,优选过硫酸铵、过硫酸钾、2,2′-偶氮双(2-脒基丙烷)盐酸盐。另外,关于聚合引发剂的添加方法也没有特别限定,可以适当选择一并添加或分批添加或连续滴加等。另外,聚合引发剂的含量也没有特别限定,相对于(a1)~(a5)成分100重量份,通常为0.001~5重量份左右,优选为0.01~1重量份左右。
作为聚合条件,没有特别限定,例如温度为50~100℃左右,时间为1~8小时左右。
作为得到的(A)成分的物性,例如,重均分子量从对纸浆的固定性、提高纸力效果的观点出发,通常为50万~700万,优选为100万~600万。此处的“重均分子量”是指通过凝胶渗透色谱(GPC)法得到的值。
另外,(A)成分的粘度通常为500~150,000mpa·s,优选为1,500~100,000mPa·s。此处的“粘度”是指用固体成分浓度为15重量%的溶液,将预先调节至温度25℃的该溶液用B型粘度计进行测定的值(下同)。
(B)成分为水溶性铝化合物,是通过与(A)成分的静电相互作用而发生金属交联,促进纸的优异的纸力效果的成分。作为(B)成分,可以列举例如硫酸铝、氯化铝、碱性硫酸铝、碱性氯化铝、硅酸铝、聚合氯化铝、聚氢氧化铝等。需要说明的是,(B)成分可以使用水合物。这些可以单独使用,也可以组合使用2种以上。其中,从获得容易性出发,优选硫酸铝、氯化铝、聚合氯化铝,更优选硫酸铝。
作为(B)成分的含量,没有特别限定,从不使纸力增强剂的粘度过度上升、表现出优异的纸力效果的观点出发,以固体成分重量计,相对于(A)成分100重量份以铝离子量的形式计,优选0.3~20重量份,更优选0.5~10重量份,进一步优选0.75~5重量份。
(C)成分为无机酸盐,具有减弱(A)成分与(B)成分的静电相互作用的功能,是为了表现纸力增强剂的优异的保存稳定性而使用的成分。
作为(C)成分,可以列举例如硝酸铵、硝酸钠、硝酸钾等硝酸盐;亚硝酸铵、亚硝酸钠、亚硝酸钾等亚硝酸盐;
连二次硝酸铵、连二次硝酸钠、连二次硝酸钾等连二次硝酸盐;
硫酸铵、硫酸钠、硫酸钾、硫酸氢铵、硫酸氢钠、硫酸氢钾等硫酸盐;
亚硫酸铵、亚硫酸钠、亚硫酸钾等亚硫酸盐;
连二亚硫酸铵、连二亚硫酸钠、连二亚硫酸钾等连二亚硫酸盐;
磷酸铵、磷酸钠、磷酸钾、磷酸氢二铵、磷酸氢二钠、磷酸氢二钾、磷酸二氢铵、磷酸二氢钠、磷酸二氢钾等磷酸盐;
亚磷酸铵、亚磷酸钠、亚磷酸钾、亚磷酸氢二铵、亚磷酸氢二钠、亚磷酸氢二钾、亚磷酸二氢铵、亚磷酸二氢钠、亚磷酸二氢钾等亚磷酸盐;
次磷酸铵、次磷酸钠、次磷酸钾、次磷酸氢二铵、次磷酸氢二钠、次磷酸氢二钾、次磷酸二氢铵、次磷酸二氢钠、次磷酸二氢钾等次磷酸盐等。这些可以单独使用,也可以组合使用2种以上。需要说明的是,对于无机酸盐,可以使用水合物。
这些(C)成分中,从减弱(A)成分与(B)成分的静电相互作用、纸力增强剂表现出优异的保存稳定性的观点出发,优选硫酸盐和/或磷酸盐,更优选包含选自磷酸钠、磷酸钾、磷酸氢二钠、磷酸氢二钾、磷酸二氢钠、磷酸二氢钾、硫酸钠、硫酸钾、硫酸氢钠和硫酸氢钾组成的组中的1种以上,进一步优选包含选自上述组中的2种以上。
作为(C)成分的含量,没有特别限定,从减弱(A)成分与(B)成分的静电相互作用、纸力增强剂表现出优异的保存稳定性的观点出发,以固体成分重量计,相对于(A)成分100重量份,优选1~70重量份,更优选1~50重量份,进一步优选1~30重量份。
(D)成分为无机酸。若配合(D)成分,则纸力增强剂的pH降低,纸力增强剂中所包含的阴离子成分(例如,源自(A)成分中的(a3)成分的物质)变得难以解离(例如,R-COOH→R-COO-+H+等)。其结果,(A)成分与(B)成分的静电相互作用减弱,纸力增强剂表现出优异的保存稳定性。作为(D)成分,可以列举例如盐酸、硝酸、亚硝酸、连二次硝酸、硫酸、亚硫酸、连二亚硫酸、磷酸、亚磷酸、次磷酸等。这些可以单独使用,也可以组合使用2种以上。其中,从抑制纸力增强剂的pH上升、纸力增强剂表现出优异的保存稳定性的观点出发,优选硫酸、磷酸。
作为(D)成分的含量,没有特别限定,除了调节纸力增强剂的pH之外,从抑制纸力增强剂的pH上升、纸力增强剂表现出优异的保存稳定性的观点出发,以固体成分重量计,相对于(A)成分100重量份,优选0.5~15重量份,更优选1~12重量份,进一步优选1~10重量份。
对于本发明的纸力增强剂,还可以加入柠檬酸、琥珀酸、草酸等有机酸;氢氧化钠、氢氧化钾、氢氧化钙等无机碱;尿素、多糖类(例如,淀粉)、消泡剂、抗氧化剂、聚合抑制剂、防腐剂等添加剂。
本发明的纸力增强剂通过将(A)成分、(B)成分、(C)成分和(D)成分、根据需要的上述添加剂在室温下混合而得到。另外,也可以加入水用于稀释。需要说明的是,关于(A)成分,可以将在上述单体的种类和/或使用量等不同组成、条件下制造的2种以上的聚合物混合,也可以使用预先用水稀释的物质。另外,这些混合方法、混合顺序没有特别限定。
关于上述得到的纸力增强剂,将刚制备好的混合液的粘度(浓度15重量%、温度:25℃)设为X1mpa·s,并且将在温度60℃保管3天后的混合液的粘度(浓度15重量%、温度:25℃)设为X2mPa·s时,30≤X1≤30,000且0.8≤X2/X1≤2。需要说明的是,此处的“刚制备好”是指,为了使得到的纸力增强剂的温度稳定在25℃,从制备完成起的2小时以内。
(关于粘度X1)
若粘度X1小于30mpa·s,则纸力增强剂溶解在造纸体系中的大量水中,脱水时容易脱落,难以发挥纸的纸力效果。另外,若超过30,000mPa·s,则在以下操作方面容易变得劣化:将纸力增强剂在水等溶剂中进行稀释时难以均匀混合,另外,在纸的制作时难以通过泵等将纸力增强剂送出,未将所期望的量的纸力增强剂添加到纸浆浆料中,其结果,纸的纸力效果容易变差。另外,从同样的观点出发,粘度X1优选100≤X1≤25,000,更优选300≤X1≤20,000。
(关于X2/X1)
X2/X1是纸力增强剂的保存稳定性的指标。若X2/X1超过2,则随着时间的推移粘度持续上升,因此无法将长期保存的纸力增强剂添加到纸浆浆料中。另外,从同样的观点出发,粘度X2/X1优选0.8≤X2/Xx≤1.8,更优选0.8≤X2/X1≤1.5。
作为本发明的纸力增强剂的其它物性,从维持优异的保存稳定性的观点出发,固体成分浓度1重量%的水溶液在温度25℃的pH优选为2~3.5,更优选为2~3,进一步优选为2~2.5。
本发明的纸为使用上述纸力增强剂而得到的物质,作为其制造方法,可以列举例如将纸力增强剂添加到原料纸浆浆料中(以下,也称为内添)、或者涂布于原纸表面等。需要说明的是,纸力增强剂优选用水进行稀释,将其固体成分浓度调节为0.1~2.0重量%。
在内添至原料纸浆浆料中的情况下,将纸力增强剂添加于纸浆浆料中进行造纸。纸力增强剂的使用量((A)成分的固体成分换算)没有特别限定,相对于纸浆的干燥重量,为0.01~4重量%左右。另外,纸浆的种类没有特别限定,可以列举例如阔叶树纸浆(LBKP)、针叶树纸浆(NBKP)等化学纸浆;碎木纸浆(GP)、精制磨木浆(RGP)、热磨机械浆(TMP)等机械纸浆;旧瓦楞纸板等废纸纸浆等。需要说明的是,对纸力剂溶液进行内添时,除此之外,作为固定剂,可以添加:硫酸铝,硫酸、氢氧化钠等pH调节剂;施胶剂、湿润纸力剂等造纸用化学品;滑石、粘土、高岭土、二氧化钛、碳酸钙等填料。
在涂布于原纸表面的情况下,通过各种公知的方法将纸力增强剂涂布于原纸表面。此处,将所述涂布于原纸表面的纸力增强剂称为“涂布液”。作为涂布液的粘度,在50℃下通常为1~40mPa·s。作为原纸的种类,可以使用将木材纤维素纤维作为原料的未涂布的纸,作为涂布装置没有特别限定,可以列举例如棒涂机、刮刀涂布机、气刀涂布机、压光机、门辊涂布机、刮板涂布机、双辊施胶压制机、棒式计量机等。另外,涂布液的涂布量(固体成分换算)没有特别限定,通常为0.001~2g/m2左右,优选为0.005~1g/m2左右。
本发明的纸能够供于各种产品,可以列举例如涂布原纸、报纸用纸、内胆(日文:ライナー)、中芯、纸管、印刷书写用纸、表格用纸、PPC用纸、杯原纸、喷墨用纸、热敏纸等。
实施例
以下列举实施例说明本发明,但本发明并不限于这些。需要说明的是,除非另有说明,实施例和比较例中的“份”和“%”为重量基准。
以下,示出化合物的简称。
AM:丙烯酰胺
DM:甲基丙烯酸N,N-二甲基氨基乙酯
DML:甲基丙烯酸N,N-二甲基氨基乙酯苄基氯化物
IA:衣康酸
AA:丙烯酸
SMAS:甲基烯丙基磺酸钠
DMAA:N,N-二甲基丙烯酰胺
MBAA:N,N′-亚甲基双丙烯酰胺
TAF:1,3,5-三丙烯酰基六氢-1,3,5-三嗪
APS:过硫酸铵
<(A)成分的重均分子量>
通过凝胶渗透色谱(GPC)法,在以下测定条件下测定(A)成分的重均分子量。
色谱柱:东曹(株)制保护柱PWXL 1根以及GMPWXL 2根
洗脱液:磷酸缓冲液(0.05mol/L磷酸(富士胶片和光纯药(株)制)+0.13mol/L磷酸二氢钠(富士胶片和光纯药(株)制)水溶液,pH约2.5)
流速:0.8ml/分钟
温度:40℃
RI检测器:昭和电工(株)制Shodex RI-101
MALS检测器:WYATT公司制DAWN HELEOS-II
测定样品:用上述洗脱液进行稀释使得聚合物的浓度成为0.1%从而进行测定。
<(A)成分和纸力增强剂的粘度>
使用B型粘度计(东机产业(株)制),对调节至温度25℃的(A)成分和纸力增强剂的粘度进行测定。
<pH>
使用市售的测定机(产品名“pH METER F-14”,(株)堀场制作所制),测定浓度1%的纸力增强剂的水溶液在温度25℃的样品的pH。
制造例1
在具备搅拌机、温度计、回流冷凝管、氮气导入管以及2个滴液漏斗的反应装置中,加入离子交换水162份,通氮气去除反应体系内的氧气后,加热至90℃。在滴液漏斗(1)中加入50%AM 512份(92.5摩尔%)、DM 30.6份(5摩尔%)、IA 10.1份(2摩尔%)、SMAS 2.5份(0.4摩尔%)、62.5%硫酸15份、DMAA 0.4份(0.1摩尔%)和离子交换水286份,通过硫酸将pH调节在3.0附近(单体混合液)。在滴液漏斗(2)中加入APS 0.3份和离子交换水180份。接着,历时约3小时通过滴液漏斗(2)滴加体系内催化剂。与此同时,历时约3小时以一定流量滴加滴液漏斗(1)的单体混合液。滴加结束后,加入APS 0.6份和离子交换水10份并保温1小时,投入离子交换水853份,得到固体成分浓度15%的(A-1)成分的水溶液。(A-1)成分的重均分子量和粘度示于表1(下同)。
制造例2~17、比较制造例1~3
以表1所示的组成,与制造例1同样地合成,均分别得到固体成分浓度15%的(A)成分的水溶液。
【表1】
实施例1
将以下物质在室温下混合15分钟:(A-1)成分的水溶液667份(固体成分100份)、硫酸铝十六水合物17.5份(铝离子的重量换算:1.5份)、磷酸二氢钠水合物1.05份、硫酸钠10份、磷酸0.70份和固体成分浓度62.5%的硫酸水溶液2.25份(固体成分1.4份),然后加入离子交换水并混合以使得固体成分浓度成为15%,得到纸力增强剂。纸力增强剂的粘度X1(mpa·s)和pH示于表2(下同)。
实施例2~7、9~27、比较例1~9
以表2所示的组成,与实施例1同样地进行,分别得到固体成分浓度15%的纸力增强剂。需要说明的是,比较例4和5的纸力增强剂在刚合成后的粘度高,另外,比较例7的纸力增强剂的分子量低,因此没有进行以下评价。
实施例8
将以下物质在室温下混合15分钟:(A-1)成分的水溶液667份(固体成分100份)、聚合氯化铝水溶液94.4份(铝离子的重量换算:5.0份)、磷酸二氢钠水合物2.1份、硫酸钠30份、磷酸1.4份和固体成分浓度62.5%的硫酸水溶液13.8份(固体成分8.6份),然后加入离子交换水并混合以使得固体成分浓度成为15%,得到纸力增强剂。
实施例28
将以下物质在室温下混合10分钟:(A-2)成分的水溶液333份(固体成分50份)、(A-3)成分的水溶液333份(固体成分50份)、硫酸铝十六水合物17.5份(铝离子的重量换算:1.5份)、磷酸二氢钠水合物1.05份、硫酸钠10份、磷酸0.7份和固体成分浓度62.5%的硫酸水溶液2.25份(固体成分1.4份),然后加入离子交换水并混合以使得固体成分浓度成为15%,得到纸力增强剂。
<保存稳定性>
将各纸力增强剂在60℃的恒温机中静置3天。对调节至温度25℃后的各纸力增强剂的粘度分别进行测定,将其值设为X2(mpa·s),计算X2/X1。结果示于表2。
<造纸评价>
加入离子交换水进行稀释,以使得表2所示的各纸力增强剂(A)成为固体成分浓度1.0%。之后,进行了以下的造纸评价。需要说明的是,对于上述保存稳定性试验中X2/X1超过2的纸力增强剂(比较例3、6和8)未进行评价。
利用尼亚加拉(Niagara)式打浆机对旧瓦楞纸板进行打浆,并在调整为加拿大标准打浆度(C.S.F.)350mL的纸浆浆料中添加氯化钙,从而将电导率调节为4.0mS/cm。相对于纸浆浆料固体成分重量,向该浆料液中添加固体成分0.5%的硫酸铝,然后相对于纸浆浆料固体成分重量,以(A)成分的固体成分成为0.5%的量分别添加实施例1的纸力增强剂。将各纸浆浆料的pH调节至6.5。利用TAPPI造纸器进行脱水,以5kg/cm2进行2分钟加压,进行造纸使得单位面积重量成为150g/m2。接着,用旋转型干燥机在105℃干燥4分钟,在温度23℃、湿度50%的条件下进行24小时调湿,测定破裂强度。另外,对实施例2~24和比较例1~2的纸力增强剂也进行了同样的评价。需要说明的是,电导率、过滤水量、破裂强度通过以下方法测定。结果示于表2。
<电导率>
使用pH/COND METER D-54((株)堀场制作所制)进行测定。
<过滤水量>
使用加拿大标准打浆度(C.S.F.),根据J1S P 8121进行测定。
<比破裂强度>
使用上述所得的纸,根据JIS P 8131,测定比破裂强度(kPa·m2/g)。
【表2】
※1:用相对于(A)成分100重量份(固体成分)的铝离子的重量份表示。
※2:用相对于(A)成分100重量份(固体成分)的(C)成分和(D)成分的重量份表示。
Claims (9)
1.一种纸力增强剂,其为包含(甲基)丙烯酰胺系聚合物(A)、水溶性铝化合物(B)、无机酸盐(C)以及无机酸(D)的混合液,其中,所述(甲基)丙烯酰胺系聚合物(A)包含(甲基)丙烯酰胺(a1)、具有阳离子性基团的聚合性单体(a2)、具有阴离子性基团的聚合性单体(a3)以及交联性单体(a4)作为反应成分,属于(B)成分的不包括在无机酸盐(C)中;
将刚制备好的固体成分浓度15重量%、温度25℃的混合液的粘度设为X1mPa·s,并且将在温度60℃保管3天后的固体成分浓度15重量%、温度25℃的混合液的粘度设为X2mPa·s时,30≤X1≤30,000且0.8≤X2/X1≤2。
2.根据权利要求1所述的纸力增强剂,其中,所述反应成分的摩尔比率为:(a1)成分55摩尔%~98摩尔%、(a2)成分0.5摩尔%~20摩尔%、(a3)成分0.5摩尔%~20摩尔%以及(a4)成分0.002摩尔%~2摩尔%。
3.根据权利要求1或2所述的纸力增强剂,其中,(B)成分为硫酸铝和/或其水合物。
4.根据权利要求1~3中任一项所述的纸力增强剂,其中,(B)成分的含量以固体成分重量计,相对于(A)成分100重量份以铝离子量的形式计为0.3重量份~20重量份。
5.根据权利要求1~4中任一项所述的纸力增强剂,其中,(C)成分包含选自磷酸钠、磷酸钾、磷酸氢二钠、磷酸氢二钾、磷酸二氢钠、磷酸二氢钾、硫酸钠、硫酸钾、硫酸氢钠和硫酸氢钾组成的组中的1种以上。
6.根据权利要求1~5中任一项所述的纸力增强剂,其中,(C)成分的含量以固体成分重量计,相对于(A)成分100重量份,为1重量份~70重量份。
7.根据权利要求1~6中任一项所述的纸力增强剂,其中,(D)成分为硫酸和/或磷酸。
8.根据权利要求1~7中任一项所述的纸力增强剂,其固体成分浓度1重量%的水溶液在温度25℃的pH为2~3.5。
9.一种纸,其使用权利要求1~8中任一项所述的纸力增强剂而得到。
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