JP2022167545A - Effect improvement method of paper-strengthening agent in paper making step - Google Patents
Effect improvement method of paper-strengthening agent in paper making step Download PDFInfo
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- JP2022167545A JP2022167545A JP2021073398A JP2021073398A JP2022167545A JP 2022167545 A JP2022167545 A JP 2022167545A JP 2021073398 A JP2021073398 A JP 2021073398A JP 2021073398 A JP2021073398 A JP 2021073398A JP 2022167545 A JP2022167545 A JP 2022167545A
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- Prior art keywords
- composition
- agent
- paper strength
- paper
- ammonium
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 119
- 230000000694 effects Effects 0.000 title claims abstract description 79
- 238000005728 strengthening Methods 0.000 title abstract 5
- 239000000203 mixture Substances 0.000 claims abstract description 145
- 239000007800 oxidant agent Substances 0.000 claims abstract description 73
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 69
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 65
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 56
- 150000002367 halogens Chemical class 0.000 claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000013054 paper strength agent Substances 0.000 claims description 140
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 67
- 229910001868 water Inorganic materials 0.000 claims description 65
- 239000000460 chlorine Substances 0.000 claims description 26
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 25
- 229910052801 chlorine Inorganic materials 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 14
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 10
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 8
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 239000004155 Chlorine dioxide Substances 0.000 claims description 7
- 235000019398 chlorine dioxide Nutrition 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910001919 chlorite Inorganic materials 0.000 claims description 6
- 229910052619 chlorite group Inorganic materials 0.000 claims description 6
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 13
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 239000000123 paper Substances 0.000 description 65
- 239000002994 raw material Substances 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 22
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000010893 paper waste Substances 0.000 description 18
- 239000003623 enhancer Substances 0.000 description 17
- 239000013055 pulp slurry Substances 0.000 description 15
- 238000004537 pulping Methods 0.000 description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 125000002091 cationic group Chemical group 0.000 description 12
- 229920002401 polyacrylamide Polymers 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- 125000000129 anionic group Chemical group 0.000 description 10
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 9
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- 229920002472 Starch Polymers 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000011144 upstream manufacturing Methods 0.000 description 7
- 230000001954 sterilising effect Effects 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 239000001509 sodium citrate Substances 0.000 description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 5
- 229940038773 trisodium citrate Drugs 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 229920000962 poly(amidoamine) Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 4
- 229960002218 sodium chlorite Drugs 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 3
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229920001131 Pulp (paper) Polymers 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 235000010724 Wisteria floribunda Nutrition 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000009172 bursting Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010411 cooking Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000002761 deinking Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WHQOKFZWSDOTQP-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-aminobenzoate Chemical compound NC1=CC=C(C(=O)OCC(O)CO)C=C1 WHQOKFZWSDOTQP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- ISFLYIRWQDJPDR-UHFFFAOYSA-L barium chlorate Chemical compound [Ba+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ISFLYIRWQDJPDR-UHFFFAOYSA-L 0.000 description 2
- YALMXYPQBUJUME-UHFFFAOYSA-L calcium chlorate Chemical compound [Ca+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O YALMXYPQBUJUME-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical compound [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000000415 inactivating effect Effects 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 description 2
- NNNSKJSUQWKSAM-UHFFFAOYSA-L magnesium;dichlorate Chemical compound [Mg+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O NNNSKJSUQWKSAM-UHFFFAOYSA-L 0.000 description 2
- NWAPVVCSZCCZCU-UHFFFAOYSA-L magnesium;dichlorite Chemical compound [Mg+2].[O-]Cl=O.[O-]Cl=O NWAPVVCSZCCZCU-UHFFFAOYSA-L 0.000 description 2
- YZQBYALVHAANGI-UHFFFAOYSA-N magnesium;dihypochlorite Chemical compound [Mg+2].Cl[O-].Cl[O-] YZQBYALVHAANGI-UHFFFAOYSA-N 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 235000011181 potassium carbonates Nutrition 0.000 description 2
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 2
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 2
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000001729 Ammonium fumarate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004251 Ammonium lactate Substances 0.000 description 1
- 239000001715 Ammonium malate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 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
- 102000006835 Lamins Human genes 0.000 description 1
- 108010047294 Lamins Proteins 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 239000001744 Sodium fumarate Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- 235000019297 ammonium fumarate Nutrition 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- KGECWXXIGSTYSQ-UHFFFAOYSA-N ammonium malate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)CC([O-])=O KGECWXXIGSTYSQ-UHFFFAOYSA-N 0.000 description 1
- 235000019292 ammonium malate Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
- CKKXWJDFFQPBQL-SEPHDYHBSA-N azane;(e)-but-2-enedioic acid Chemical compound N.N.OC(=O)\C=C\C(O)=O CKKXWJDFFQPBQL-SEPHDYHBSA-N 0.000 description 1
- NHJPVZLSLOHJDM-UHFFFAOYSA-N azane;butanedioic acid Chemical compound [NH4+].[NH4+].[O-]C(=O)CCC([O-])=O NHJPVZLSLOHJDM-UHFFFAOYSA-N 0.000 description 1
- XJMWHXZUIGHOBA-UHFFFAOYSA-N azane;propanoic acid Chemical compound N.CCC(O)=O XJMWHXZUIGHOBA-UHFFFAOYSA-N 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- NGPGDYLVALNKEG-UHFFFAOYSA-N azanium;azane;2,3,4-trihydroxy-4-oxobutanoate Chemical compound [NH4+].[NH4+].[O-]C(=O)C(O)C(O)C([O-])=O NGPGDYLVALNKEG-UHFFFAOYSA-N 0.000 description 1
- YNTQKXBRXYIAHM-UHFFFAOYSA-N azanium;butanoate Chemical compound [NH4+].CCCC([O-])=O YNTQKXBRXYIAHM-UHFFFAOYSA-N 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000001362 calcium malate Substances 0.000 description 1
- OLOZVPHKXALCRI-UHFFFAOYSA-L calcium malate Chemical compound [Ca+2].[O-]C(=O)C(O)CC([O-])=O OLOZVPHKXALCRI-UHFFFAOYSA-L 0.000 description 1
- 229940016114 calcium malate Drugs 0.000 description 1
- 235000011038 calcium malates Nutrition 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
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 description 1
- MSJMDZAOKORVFC-SEPHDYHBSA-L disodium fumarate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C\C([O-])=O MSJMDZAOKORVFC-SEPHDYHBSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 238000007429 general method Methods 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 210000005053 lamin Anatomy 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000001139 pH measurement Methods 0.000 description 1
- QLFFCLRSMTUBEZ-UHFFFAOYSA-N phosphoric acid;sodium Chemical compound [Na].[Na].OP(O)(O)=O QLFFCLRSMTUBEZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000013641 positive control Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 229940093956 potassium carbonate Drugs 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000001415 potassium malate Substances 0.000 description 1
- SVICABYXKQIXBM-UHFFFAOYSA-L potassium malate Chemical compound [K+].[K+].[O-]C(=O)C(O)CC([O-])=O SVICABYXKQIXBM-UHFFFAOYSA-L 0.000 description 1
- 235000011033 potassium malate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940083542 sodium Drugs 0.000 description 1
- 235000019265 sodium DL-malate Nutrition 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000019294 sodium fumarate Nutrition 0.000 description 1
- 229940005573 sodium fumarate Drugs 0.000 description 1
- 239000001540 sodium lactate Substances 0.000 description 1
- 235000011088 sodium lactate Nutrition 0.000 description 1
- 229940005581 sodium lactate Drugs 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/64—Paper recycling
Abstract
Description
本発明は製紙工程における紙力増強剤の効果向上方法等に関する。 TECHNICAL FIELD The present invention relates to a method for improving the effect of a paper strength agent in a papermaking process.
従来から、製紙工場では紙に強度を付与する紙力増強剤が使用されている。
近年、製紙工場では古紙の使用比率の増加により古紙由来の短繊維が含まれた紙力強度の弱い原料パルプが使用されている。また、古紙の使用により、抄紙白水中に含まれる金属イオンが抄紙系内の電気伝導度を上昇させ、原料パルプへ添加される紙力増強剤の効果を発揮しにくくしている。このような環境下で、紙力増強剤の効果を向上させる必要が生じているが、紙力増強剤の添加量を多くすることは水質の悪化を招き、環境上好ましくない。
Traditionally, paper mills have used paper strength agents to impart strength to paper.
In recent years, due to the increase in the ratio of waste paper used in paper mills, raw material pulp with low paper strength containing short fibers derived from waste paper is being used. In addition, the use of waste paper increases the electrical conductivity in the papermaking system due to metal ions contained in the papermaking white water, making it difficult for the effect of the paper strength enhancer added to the raw pulp to be exhibited. Under such circumstances, there is a need to improve the effect of the paper strength enhancer, but increasing the amount of the strength enhancer added leads to deterioration of water quality, which is not preferable from an environmental point of view.
また、ティッシュペーパー、洋紙、包装紙等の原料としては、主に針葉樹パルプや広葉樹パルプ等のバージンパルプが用いられるが、最終シートの紙力を保つためには、紙力増強の対策が必要となる。そのため、原料として古紙を用いない場合においても紙力増強剤は用いられており、環境面から、紙力増強剤の添加量を増やすことなく、その効果を向上させる必要が生じている。 In addition, virgin pulp such as softwood pulp and hardwood pulp is mainly used as raw material for tissue paper, paper, and wrapping paper. Become. Therefore, even when waste paper is not used as a raw material, a paper strength agent is used, and from an environmental point of view, it is necessary to improve the effect without increasing the amount of the paper strength agent added.
ここで、紙力増強剤の添加量を低減させる方法としては、例えば、特許文献１に、古紙を主原料とする板紙の製造におけるパルプ化工程水に、次亜塩素酸ナトリウム水溶液のような次亜塩素酸塩の水溶液と硫酸アンモニウム水溶液のような水溶性の無機アンモニウム塩の水溶液またはアンモニア水とを添加することにより、調成工程における紙力増強剤の添加量を効果的に低減できる方法が開示されている。 Here, as a method for reducing the amount of the paper strength agent added, for example, in Patent Document 1, the following water such as sodium hypochlorite aqueous solution is added to the pulping process water in the manufacture of paperboard using waste paper as the main raw material. Disclosed is a method that can effectively reduce the amount of paper strength agent added in the preparation process by adding an aqueous solution of chlorite and an aqueous solution of a water-soluble inorganic ammonium salt such as an aqueous solution of ammonium sulfate or aqueous ammonia. It is
また、特許文献２には、紙の製造工程における澱粉の分解を抑制し、紙製品の強度劣化の生じない紙の製造方法を提供することが開示されている。具体的に、古紙が配合されている紙の製造方法において、（１）連続的又は間欠的に水質測定を行う工程、（２）前記（１）工程で得られた水質測定結果に基づいて澱粉分解能を有する微生物を不活化させる工程を含むことが開示されている。さらに、微生物を不活化させうる薬剤として、各種抗菌剤が開示されている。特許文献３にも、古紙やブロークパルプや内添の澱粉等を栄養源として微生物汚染が進行し、澱粉分解は紙製品の強度劣化を招くため、原料に対し酸化作用を有する殺菌剤を添加することで、微生物汚染による障害を制御することが開示されている。 Further, Patent Literature 2 discloses that the decomposition of starch in the paper manufacturing process is suppressed to provide a paper manufacturing method that does not cause deterioration in the strength of paper products. Specifically, in the method of manufacturing paper containing waste paper, (1) a step of continuously or intermittently measuring water quality, (2) starch based on the water quality measurement results obtained in step (1) It is disclosed to include the step of inactivating the degrading microorganisms. Furthermore, various antibacterial agents have been disclosed as agents capable of inactivating microorganisms. Also in Patent Document 3, microbial contamination progresses using waste paper, broken pulp, internal starch, etc. as a nutrient source, and starch decomposition leads to deterioration of the strength of paper products. It is disclosed to control damage due to microbial contamination.
なお、製紙工程の原料を殺菌する方法としては、例えば、特許文献４には、製紙工程の白水ラインに流入するように（ａ）次亜塩素酸ナトリウム水溶液の添加ポイントおよび（ｂ）硫酸アンモニウム水溶液の添加ポイントの順に有効成分の添加ポイントが設けられた希釈水ラインの希釈水に、（ａ）成分と（ｂ）成分とを添加して、前記希釈水ライン中で（ａ）成分と（ｂ）成分との混合水溶液を調製すること、及び、上記混合水溶液のｐＨが８以上であることが開示されている。しかし、本文献には、紙力増強剤の効果を向上させる方法については開示されていない。 As a method for sterilizing raw materials in the papermaking process, for example, Patent Document 4 describes (a) the addition point of the sodium hypochlorite aqueous solution and (b) the ammonium sulfate aqueous solution so that it flows into the white water line of the papermaking process. The components (a) and (b) are added to the dilution water in the dilution water line having the addition points of the active ingredients in order of the addition points, and the components (a) and (b) are added in the dilution water line. It is disclosed to prepare an aqueous mixed solution with the components, and that the pH of the mixed aqueous solution is 8 or higher. However, this document does not disclose a method for improving the effect of the paper strength agent.
また、特許文献５には、紙力増強剤の効果向上方法が開示されており、製紙工程水に酸化剤（ハロゲンを含有する酸化剤及び／又は過酸化水素）を添加する工程と紙力増強剤を添加する工程とを有し、上記酸化剤と上記紙力増強剤が特定の濃度で接触することで、上記紙力増強剤の効果を向上する方法が開示されている。 In addition, Patent Document 5 discloses a method for improving the effect of a paper strength agent. and adding an agent, wherein the oxidizing agent and the paper strength agent are brought into contact at a specific concentration to improve the effect of the paper strength agent.
上記特許文献１では、調成工程で添加される紙力増強剤の添加量を低減させるためにパルプ化工程のパルプ化工程水に薬剤を添加することが開示されている。また、上記特許文献２及び３には、紙の製造工程で微生物による澱粉分解を抑制するために酸化剤等の抗菌剤を添加することで、微生物障害の一種である紙力低下を防止できることが開示されている。これらはいずれも、紙力増強剤を添加する前の製紙工程水に対し薬剤を添加するものであり、紙力増強剤の効果自体を向上させるものではなかった。
また、製紙工程の原料を殺菌する方法が開示されている上記特許文献４にも紙力増強剤自体の効果を向上させる方法は開示されていなかった。
The above Patent Document 1 discloses adding an agent to the pulping process water in the pulping process in order to reduce the amount of the paper strength agent added in the preparation process. Moreover, in Patent Documents 2 and 3 above, by adding an antibacterial agent such as an oxidizing agent to suppress starch decomposition by microorganisms in the paper manufacturing process, it is possible to prevent a decrease in paper strength, which is a type of microbial disorder. disclosed. All of these methods add the agent to the papermaking process water before the addition of the paper strength agent, and do not improve the effect of the paper strength agent itself.
Moreover, the above Patent Document 4, which discloses a method for sterilizing raw materials in the papermaking process, does not disclose a method for improving the effect of the paper strength agent itself.
また、特許文献５は、紙力増強剤の効果向上方法に関する発明が開示されているが、紙力増強剤自体の効果を向上させる方法やそのような組成物についてはさらに検討の余地があった。 In addition, Patent Document 5 discloses an invention related to a method for improving the effect of a paper strength agent, but there is room for further investigation on a method for improving the effect of the paper strength agent itself and such a composition. .
本発明は、製紙工程で使用される紙力増強剤の効果向上用組成物の製造方法、紙力増強剤の効果向上用組成物、及び、紙力増強剤の効果向上方法を提供することを課題とする。 The present invention aims to provide a method for producing a composition for improving the effect of a paper strength agent used in a papermaking process, a composition for improving the effect of a paper strength agent, and a method for improving the effect of a paper strength agent. Make it an issue.
本発明の発明者は、上記の課題を解決するために鋭意研究を重ねた結果、製紙工程で添加される紙力増強剤に、特定の製造方法により製造されたモノクロラミン及び／又はモノブロラミンを接触させることで、紙力増強剤の効果が大きく向上するという事実を見出し、本発明を完成するに至った。 The inventors of the present invention, as a result of extensive research in order to solve the above problems, added monochloramine and/or monobroramine produced by a specific production method to the paper strength enhancer added in the papermaking process. The inventors have found that the effect of the paper strength agent is greatly improved by bringing them into contact with each other, and have completed the present invention.
本発明は、アンモニウム塩及びアルカリ剤を含む第一組成物とハロゲン系酸化剤とを混合する、又は、ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合することを特徴とする紙力増強剤の効果向上用組成物の製造方法である。
アンモニウム塩は、硫酸アンモニウム、硝酸アンモニウム、塩化アンモニウム、リン酸アンモニウム、リン酸二水素アンモニウム、リン酸水素二アンモニウム、臭化アンモニウム及びスルファミン酸アンモニウムからなる群より選択される少なくとも１種であることが好ましい。
ハロゲン系酸化剤は、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩及び二酸化塩素からなる群より選択される少なくとも１種であることが好ましい。
ハロゲン系酸化剤とアンモニウム塩とのモル比は、残留塩素量と窒素とのモル比として１：１～１：２であることが好ましい。
第一組成物のｐＨが、４．５～８．５であることが好ましい。
The present invention is characterized by mixing a first composition containing an ammonium salt and an alkaline agent with a halogen-based oxidizing agent, or mixing a second composition containing a halogen-based oxidizing agent and an alkali agent with an ammonium salt. It is a method for producing a composition for improving the effect of a paper strength agent.
The ammonium salt is preferably at least one selected from the group consisting of ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium bromide and ammonium sulfamate.
The halogen-based oxidizing agent is preferably at least one selected from the group consisting of hypochlorite, chlorite, chlorate, perchlorate and chlorine dioxide.
The molar ratio of the halogen-based oxidizing agent to the ammonium salt is preferably 1:1 to 1:2 in terms of the molar ratio of residual chlorine to nitrogen.
Preferably, the pH of the first composition is between 4.5 and 8.5.
また、本発明は、アンモニウム塩及びアルカリ剤を含む第一組成物とハロゲン系酸化剤とを混合する、又は、ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合する、ことにより生成される紙力増強剤の効果向上用組成物である。
ハロゲン系酸化剤とアンモニウム塩とのモル比（ハロゲン系酸化剤：アンモニウム塩）は、残留塩素量と窒素とのモル比として１：１～１：２であるであることが好ましい。
第一組成物のｐＨが、４．５～８．５であることが好ましい。
In addition, the present invention includes mixing a first composition containing an ammonium salt and an alkaline agent with a halogen-based oxidizing agent, or mixing a second composition containing a halogen-based oxidizing agent and an alkali agent with an ammonium salt. It is a composition for improving the effect of a paper strength agent produced by
The molar ratio of the halogen-containing oxidizing agent to the ammonium salt (halogen-containing oxidizing agent:ammonium salt) is preferably 1:1 to 1:2 in terms of the molar ratio of residual chlorine to nitrogen.
Preferably, the pH of the first composition is between 4.5 and 8.5.
また、本発明は、製紙工程における紙力増強剤の効果向上方法であって、製紙工程水に、本発明の紙力増強剤の効果向上用組成物を添加する組成物添加工程と、紙力増強剤を添加する紙力増強剤添加工程とを有し、前記組成物と前記紙力増強剤とは接触するものであることを特徴とする紙力増強剤の効果向上方法である。
本発明の紙力増強剤の効果向上用組成物と、紙力増強剤とが接触する際の前記組成物の接触濃度が、０．１～３５ｍｇ／Ｌであることが好ましい。
組成物添加工程後の製紙工程水中の残留塩素濃度が、０．１～３５ｍｇ／Ｌであることが好ましい。
The present invention also provides a method for improving the effect of a paper strength agent in a papermaking process, comprising: adding a composition for improving the effect of a paper strength agent of the present invention to papermaking process water; and a step of adding a paper strength agent, wherein the composition and the paper strength agent are in contact with each other.
The contact concentration of the composition for improving the effect of the paper strength agent of the present invention and the paper strength agent when the composition is in contact is preferably 0.1 to 35 mg/L.
The concentration of residual chlorine in the papermaking process water after the step of adding the composition is preferably 0.1 to 35 mg/L.
本発明によれば、製紙工程で使用される紙力増強剤の効果向上用組成物の製造方法、紙力増強剤の効果向上用組成物、及び、紙力増強剤の効果向上方法を提供することができる。 According to the present invention, there are provided a method for producing a composition for improving the effect of a paper strength agent used in a papermaking process, a composition for improving the effect of a paper strength agent, and a method for improving the effect of a paper strength agent. be able to.
以下、本発明の実施形態を説明するが、以下に説明する実施形態は、本発明の代表的な実施形態の一例を示すものであり、これにより本発明の範囲が狭く解釈されることは無い。 Embodiments of the present invention will be described below, but the embodiments described below are examples of typical embodiments of the present invention, and the scope of the present invention should not be interpreted narrowly. .
本明細書中、「Ｘ～Ｙ」は、「Ｘ以上、Ｙ以下」を意味する。 In this specification, "X to Y" means "X or more and Y or less".
上述の特許文献５に開示されているように、本発明の出願人は、製紙工程水に、酸化剤を添加する工程と、紙力増強剤を添加する工程とを有し、酸化剤（ハロゲンを有する酸化剤及び／又は過酸化水素）と上記紙力増強剤とは接触するものであり、上記紙力増強剤と上記酸化剤とが接触する際の上記酸化剤の接触濃度が、０．１～３５ｍｇ／Ｌであることを特徴とする紙力増強剤の効果向上方法の発明を開示している。本発明者らは紙力増強剤の更なる効果向上方法を鋭意検討した結果、製紙工程で添加される紙力増強剤に、特定の製造方法により製造されたモノクロラミン及び／又はモノブロラミン（すなわち、本発明の紙力増強剤の効果向上用組成物）を接触させることで、紙力増強剤の効果が大きく向上するという事実を見出し、本発明の紙力増強剤の効果向上用組成物の製造方法を完成させた。 As disclosed in the above-mentioned Patent Document 5, the applicant of the present invention has a step of adding an oxidizing agent and a step of adding a paper strength agent to papermaking process water, and the oxidizing agent (halogen and/or hydrogen peroxide) and the paper strength agent are in contact with each other, and the contact concentration of the oxidant when the paper strength agent and the oxidant are in contact is 0.5. It discloses an invention of a method for improving the effect of a paper strength agent, characterized in that the content is 1 to 35 mg/L. The present inventors have made intensive studies on methods for further improving the effect of paper strength agents. , the composition for improving the effect of the paper strength agent of the present invention), the effect of the paper strength agent is greatly improved, and the composition for improving the effect of the paper strength agent of the present invention perfected the manufacturing process.
以下、一般的なモノクロラミン及びモノブロラミンの製造方法を説明し、次に本発明の紙力増強剤の効果向上用組成物の製造方法を具体的に説明する。 Hereinafter, general methods for producing monochloramine and monobroramine will be described, and then the method for producing the composition for improving the effect of the paper strength agent of the present invention will be specifically described.
一般的に酸化剤として使用されているモノクロラミン及びモノブロラミンは、ＯＣｌ－（Ｂｒ－）＋ＮＨ４ ＋→ＮＨ２Ｃｌ（Ｂｒ）＋Ｈ２Ｏのような反応で生成される穏やかな酸化剤である。例えば、次亜塩素酸ナトリウムとアンモニウム塩とを混合することによりモノクロラミンを生成でき、アンモニウム塩としては、具体的に、硫酸アンモニウム、臭化アンモニウム、塩化アンモニウム、スルファミン酸アンモニウムが挙げられ、これらを単独で又は２種以上を組み合わせて用いることができると知られている。また、通常の手法により製造されたモノクロラミン及びモノブロラミンの安定化を図る目的で、モノクロラミン又はモノブロラミンとアルカリ剤とを混合することが知られている。また、モノクロラミン又はモノブロラミンが添加される対象のｐＨを調製する目的で、モノクロラミン、モノブロラミンとアルカリ剤とを対象に別々に添加することも知られている（上記特許文献４）。 Monochloramine and monobroramine, commonly used as oxidants, are mild oxidants produced in reactions such as OCl − (Br − )+NH 4 + →NH 2 Cl(Br)+H 2 O. . For example, monochloramine can be produced by mixing sodium hypochlorite and an ammonium salt. Examples of ammonium salts include ammonium sulfate, ammonium bromide, ammonium chloride, and ammonium sulfamate. or in combination of two or more. It is also known to mix monochloramine or monobroramine with an alkaline agent for the purpose of stabilizing monochloramine and monobroramine produced by conventional methods. It is also known to separately add monochloramine, monobroramine and an alkaline agent to the object for the purpose of adjusting the pH of the object to which monochloramine or monobroramine is added (Patent Document 4 above).
本発明者らは、モノクロラミン及び／又はモノブロラミンの作成時に、アンモニウム塩にアルカリ剤を含有させ、アンモニウム塩のｐＨをアルカリ側へコントロールしたものをハロゲン系酸化剤と反応させて生成されるモノクロラミン及び／又はモノブロラミンは、アルカリ剤を含有しないアンモニウム塩とハロゲン系酸化剤とを反応させて生成される従来のモノクロラミン及び／又はモノブロラミン、並びに、従来のモノクロラミン及び／又はモノブロラミンにアルカリ剤を含有させたものと比較して、優れた紙力増強剤の効果向上作用を有することを見出した。
また、本発明者らは、モノクロラミン及び／又はモノブロラミンの作成時に、ハロゲン系酸化剤にアルカリ剤を含有させたものをアンモニウム塩と反応させて生成されるモノクロラミン及び／又はモノブロラミンは、アルカリ剤を含有しないハロゲン系酸化剤とアンモニウム塩とを反応させて生成される従来のモノクロラミン及び／又はモノブロラミン、並びに、従来のモノクロラミン及び／又はモノブロラミンにアルカリ剤を含有させたものと比較して、優れた紙力増強剤の効果向上作用を有することを見出した。
すなわち、アンモニウム塩にアルカリ剤を含有させ、アンモニウム塩のｐＨをアルカリ側へコントロールしたものをハロゲン系酸化剤と反応させて生成される組成物、及び、ハロゲン系酸化剤にアルカリ剤を含有させたものをアンモニウム塩と反応させて生成される組成物は、従来のモノクロラミン及び／又はモノブロラミン、並びに、従来のモノクロラミン及び／又はモノブロラミンにアルカリ剤を含有させたものと比較して、優れた紙力増強剤の効果向上作用を有することを見出した。以下、アンモニウム塩にアルカリ剤を含有させ、アンモニウム塩のｐＨをアルカリ側へコントロールしたものをハロゲン系酸化剤と反応させて生成される組成物、及び、ハロゲン系酸化剤にアルカリ剤を含有させたものをアンモニウム塩と反応させて生成される組成物を「紙力増強剤の効果向上用組成物」、又は、単に「効果向上用組成物」と記載する。
The present inventors have found that when monochloramine and/or monobroramine are produced, the ammonium salt contains an alkaline agent, and the pH of the ammonium salt is controlled to the alkaline side, and the resulting monochromate is reacted with a halogen-based oxidizing agent. Lamin and/or monobrolamine are conventional monochloramine and/or monobrolamine produced by reacting an ammonium salt containing no alkaline agent with a halogen-based oxidizing agent, and conventional monochloramine and/or monobrolamine. It has been found to have an effect of improving the effect of the paper strength enhancer, which is superior to that containing an alkali agent.
In addition, the present inventors have found that monochloramine and/or monobroramine produced by reacting a halogen-based oxidizing agent containing an alkaline agent with an ammonium salt during preparation of monochloramine and/or monobroramine, Conventional monochloramine and/or monobrolamine produced by reacting an ammonium salt with a halogen-based oxidizing agent that does not contain an alkaline agent, and conventional monochloramine and/or monobrolamine containing an alkaline agent. In comparison, it was found to have an effect of improving the effect of an excellent paper strength enhancer.
That is, a composition produced by adding an alkaline agent to an ammonium salt, controlling the pH of the ammonium salt to the alkaline side, and reacting it with a halogen-based oxidizing agent, and making the halogen-based oxidizing agent include an alkaline agent. The composition produced by reacting a compound with an ammonium salt is superior to conventional monochloramine and/or monobrolamine and conventional monochloramine and/or monobrolamine containing an alkaline agent. It was found that it has the effect of improving the effect of the paper strength enhancer. Hereinafter, a composition produced by adding an alkaline agent to an ammonium salt and controlling the pH of the ammonium salt to the alkaline side and reacting it with a halogen-based oxidizing agent, and a composition produced by adding an alkaline agent to the halogen-based oxidizing agent. A composition produced by reacting a substance with an ammonium salt is referred to as "a composition for improving the effect of a paper strength agent" or simply as "a composition for improving effect".
本発明は、アンモニウム塩及びアルカリ剤を含む第一組成物とハロゲン系酸化剤とを混合する、又は、ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合することを特徴とする紙力増強剤の効果向上用組成物の製造方法である。 The present invention is characterized by mixing a first composition containing an ammonium salt and an alkaline agent with a halogen-based oxidizing agent, or mixing a second composition containing a halogen-based oxidizing agent and an alkali agent with an ammonium salt. It is a method for producing a composition for improving the effect of a paper strength agent.
また本発明は、アンモニウム塩及びアルカリ剤を含む第一組成物とハロゲン系酸化剤とを混合する、又は、ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合する、ことにより生成される紙力増強剤の効果向上用組成物でもある。 Further, in the present invention, a first composition containing an ammonium salt and an alkaline agent is mixed with a halogen-based oxidizing agent, or a second composition containing a halogen-based oxidizing agent and an alkali agent is mixed with an ammonium salt. It is also a composition for improving the effect of a paper strength agent produced by
本発明に用いられるアンモニウム塩は、無機酸とアンモニアの反応物である無機アンモニウム塩、または有機酸とアンモニアの反応物である有機アンモニウム塩であれば特に限定されない。無機アンモニウム塩としては、硫酸アンモニウム、硝酸アンモニウム、塩化アンモニウム、リン酸アンモニウム、リン酸二水素アンモニウム、リン酸水素二アンモニウム、臭化アンモニウム、スルファミン酸アンモニウム、炭酸アンモニウム、重炭酸アンモニウム、炭酸水素アンモニウム、硫酸鉄(III)アンモニウム、過硫酸アンモニウム、タングステン酸アンモニウム、メタタングステン酸アンモニウム、チオシアン酸アンモニウム、及びポリリン酸アンモニウムからなる群より選択される少なくとも１種であることが好ましい。有機アンモニウム塩としては、ギ酸アンモニウム、酢酸アンモニウム、プロピオン酸アンモニウム、酪酸アンモニウム、クエン酸アンモニウム、リンゴ酸アンモニウム、コハク酸アンモニウム、フマル酸アンモニウム、乳酸アンモニウム、及び酒石酸アンモニウムからなる群より選択される少なくとも１種であることが好ましい。また、上記アンモニウム塩は、硫酸アンモニウム、塩化アンモニウム、リン酸アンモニウム、リン酸二水素アンモニウム、リン酸水素二アンモニウム、臭化アンモニウム及びスルファミン酸アンモニウムからなる群より選択される少なくとも１種であることがより好ましく、硫酸アンモニウム、臭化アンモニウム及びスルファミン酸アンモニウムからなる群より選択される少なくとも１種であることがさらに好ましい。 The ammonium salt used in the present invention is not particularly limited as long as it is an inorganic ammonium salt that is a reaction product of an inorganic acid and ammonia or an organic ammonium salt that is a reaction product of an organic acid and ammonia. Inorganic ammonium salts include ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium bromide, ammonium sulfamate, ammonium carbonate, ammonium bicarbonate, ammonium hydrogen carbonate, iron sulfate. (III) It is preferably at least one selected from the group consisting of ammonium, ammonium persulfate, ammonium tungstate, ammonium metatungstate, ammonium thiocyanate, and ammonium polyphosphate. The organic ammonium salt is at least one selected from the group consisting of ammonium formate, ammonium acetate, ammonium propionate, ammonium butyrate, ammonium citrate, ammonium malate, ammonium succinate, ammonium fumarate, ammonium lactate, and ammonium tartrate. Seeds are preferred. Further, the ammonium salt is more preferably at least one selected from the group consisting of ammonium sulfate, ammonium chloride, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium bromide and ammonium sulfamate. More preferably, it is at least one selected from the group consisting of ammonium sulfate, ammonium bromide and ammonium sulfamate.
本発明に用いられるハロゲン系酸化剤は、次亜塩素酸塩、亜塩素酸塩、塩素酸塩、過塩素酸塩及び二酸化塩素からなる群より選択される少なくとも１種であることが好ましい。 The halogen-based oxidizing agent used in the present invention is preferably at least one selected from the group consisting of hypochlorite, chlorite, chlorate, perchlorate and chlorine dioxide.
上記次亜塩素酸塩は、次亜塩素酸ナトリウム、次亜塩素酸カルシウム、次亜塩素酸カリウム及び次亜塩素酸マグネシウム等が挙げられる。上記次亜塩素酸塩は、次亜塩素酸ナトリウム、次亜塩素酸カルシウム、次亜塩素酸カリウム及び次亜塩素酸マグネシウムからなる群より選択される少なくとも１種が好ましく、次亜塩素酸ナトリウム、次亜塩素酸カルシウム及び次亜塩素酸カリウムからなる群より選択される少なくとも１種がより好ましい。 Examples of the hypochlorite include sodium hypochlorite, calcium hypochlorite, potassium hypochlorite and magnesium hypochlorite. The hypochlorite is preferably at least one selected from the group consisting of sodium hypochlorite, calcium hypochlorite, potassium hypochlorite and magnesium hypochlorite. At least one selected from the group consisting of calcium hypochlorite and potassium hypochlorite is more preferred.
上記亜塩素酸塩としては、亜塩素酸ナトリウム、亜塩素酸カリウム、亜塩素酸カルシウム、亜塩素酸マグネシウム等が挙げられる。上記亜塩素酸塩は、亜塩素酸ナトリウム、亜塩素酸カリウム、亜塩素酸カルシウム、及び亜塩素酸マグネシウムからなる群より選択される少なくとも１種が好ましい。 Examples of the chlorite include sodium chlorite, potassium chlorite, calcium chlorite, and magnesium chlorite. The chlorite is preferably at least one selected from the group consisting of sodium chlorite, potassium chlorite, calcium chlorite, and magnesium chlorite.
上記塩素酸塩としては、塩素酸カリウム、塩素酸ナトリウム、塩素酸カルシウム、塩素酸バリウム、及び、塩素酸マグネシウム等が挙げられる。上記塩素酸塩は、塩素酸カリウム、塩素酸ナトリウム、塩素酸カルシウム、塩素酸バリウム及び塩素酸マグネシウムからなる群より選択される少なくとも１種が好ましい。 Examples of the chlorate include potassium chlorate, sodium chlorate, calcium chlorate, barium chlorate, and magnesium chlorate. The chlorate is preferably at least one selected from the group consisting of potassium chlorate, sodium chlorate, calcium chlorate, barium chlorate and magnesium chlorate.
上記過塩素酸塩としては、過塩素酸ナトリウム、過塩素酸カリウム、過塩素酸カルシウム及び過塩素酸マグネシウム等が挙げられる。上記過塩素酸塩は、過塩素酸ナトリウム、過塩素酸カリウム、過塩素酸カルシウム及び過塩素酸マグネシウムからなる群より選択される少なくとも１種が好ましい。 Examples of the perchlorate include sodium perchlorate, potassium perchlorate, calcium perchlorate and magnesium perchlorate. The perchlorate is preferably at least one selected from the group consisting of sodium perchlorate, potassium perchlorate, calcium perchlorate and magnesium perchlorate.
上記二酸化塩素は、極めて不安定な化学物質であるため、その貯蔵や輸送は非常に困難である。したがって、その場で公知の方法により二酸化塩素を製造（生成）し、添加濃度に調整して用いるのが好ましい。
例えば、次のような反応により二酸化塩素を製造することができ、市販の二酸化塩素発生器（装置）を用いることもできる。
（１）次亜塩素酸ナトリウムと塩酸と亜塩素酸ナトリウムとの反応
ＮａＯＣｌ＋２ＨＣｌ＋２ＮａＣｌＯ２ → ２ＣｌＯ２＋３ＮａＣｌ＋Ｈ２Ｏ
（２）亜塩素酸ナトリウムと塩酸との反応
５ＮａＣｌＯ２＋４ＨＣｌ → ４ＣｌＯ２＋５ＮａＣｌ＋２Ｈ２Ｏ
（３）塩素酸ナトリウム、過酸化水素および硫酸との反応
２ＮａＣｌＯ３＋Ｈ２Ｏ２＋Ｈ２ＳＯ４ → ２ＣｌＯ２＋Ｎａ２ＳＯ４＋Ｏ２＋２Ｈ２Ｏ
Since chlorine dioxide is an extremely unstable chemical substance, its storage and transportation are very difficult. Therefore, it is preferable to manufacture (generate) chlorine dioxide on the spot by a known method and adjust the addition concentration before use.
For example, chlorine dioxide can be produced by the following reaction, and a commercially available chlorine dioxide generator (apparatus) can also be used.
(1) Reaction of sodium hypochlorite, hydrochloric acid and sodium chlorite NaOCl+2HCl+ 2NaClO2 →2ClO2+3NaCl + H2O
(2) Reaction of sodium chlorite and hydrochloric acid 5NaClO 2 +4HCl → 4ClO 2 +5NaCl+2H 2 O
(3) Reaction with sodium chlorate, hydrogen peroxide and sulfuric acid 2NaClO3 + H2O2+H2SO4→ 2ClO2 + Na2SO4 + O2 + 2H2O
本発明に用いられるハロゲン系酸化剤は、次亜塩素酸塩であることがより好ましい。 The halogen-based oxidizing agent used in the present invention is more preferably hypochlorite.
本発明に用いられるアルカリ剤は、水に溶解した際にｐＨがアルカリ性を示す、アルカリ金属塩、及びアルカリ土類金属塩であれば特に限定されない。アルカリ剤は、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化マグネシウム、水酸化カルシウム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウム、炭酸水素カリウム、クエン酸三ナトリウム、リン酸一ナトリウム、リン酸二ナトリウム、リン酸三ナトリウム、リン酸一カリウム、リン酸二カリウム、リン酸三カリウム、リンゴ酸ナトリウム、リンゴ酸カリウム、リンゴ酸カルシウム、ギ酸ナトリウム、酢酸ナトリウム、プロピオン酸ナトリウム、酪酸ナトリウム、クエン酸ナトリウム、コハク酸ナトリウム、フマル酸ナトリウム、乳酸ナトリウム、及び酒石酸ナトリウムからなる群より選択される少なくとも１種であることが好ましい。また、本発明に用いられるアルカリ剤は、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、炭酸水素ナトリウム、炭酸カリウム及びクエン酸三ナトリウムからなる群より選択される少なくとも１種であることがより好ましく、水酸化ナトリウム、水酸化カリウム及びクエン酸三ナトリウムからなる群より選択される少なくとも１種であることがさらに好ましい。 The alkali agent used in the present invention is not particularly limited as long as it is an alkali metal salt or an alkaline earth metal salt that exhibits an alkaline pH when dissolved in water. Alkaline agents include sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, trisodium citrate, monosodium phosphate, phosphoric acid Disodium, Trisodium Phosphate, Monopotassium Phosphate, Dipotassium Phosphate, Tripotassium Phosphate, Sodium Malate, Potassium Malate, Calcium Malate, Sodium Formate, Sodium Acetate, Sodium Propionate, Sodium Butyrate, Citric Acid It is preferably at least one selected from the group consisting of sodium, sodium succinate, sodium fumarate, sodium lactate, and sodium tartrate. The alkaline agent used in the present invention is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium hydrogen carbonate, potassium carbonate and trisodium citrate. more preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide and trisodium citrate.
本発明の製造方法では、上記アンモニウム塩と上記ハロゲン系酸化剤とを混合する前に、上記アンモニウム塩と上記アルカリ剤とを含む第一組成物、又は、上記ハロゲン系酸化剤と上記アルカリ剤とを含む第二組成物が調製されている。第一組成物及び第二組成物の調製方法は特に限定されず、一般的な混合方法を用いることができる。 In the production method of the present invention, before mixing the ammonium salt and the halogen-based oxidizing agent, the first composition containing the ammonium salt and the alkaline agent, or the halogen-based oxidizing agent and the alkaline agent are mixed. A second composition is prepared comprising: A method for preparing the first composition and the second composition is not particularly limited, and a general mixing method can be used.
本発明における第一組成物は、アンモニウム塩自体のｐＨに対し、第一組成物のｐＨが１．０８倍以上となるようにアルカリ剤を含ませることが好ましい。アンモニウム塩のｐＨを上記程度にアルカリ側へコントロールしたものをハロゲン系酸化剤と反応させて生成される組成物は充分な紙力増強剤の効果向上作用を有するためである。 The first composition in the present invention preferably contains an alkali agent so that the pH of the first composition is at least 1.08 times the pH of the ammonium salt itself. This is because a composition produced by reacting an ammonium salt whose pH is controlled to the alkaline side to the above extent with a halogen-based oxidizing agent has a sufficient effect of improving the effect of the paper strength agent.
本発明における第二組成物は、ハロゲン系酸化剤自体のｐＨに対し、第二組成物のｐＨが１．０５倍以上となるようにアルカリ剤を含ませることが好ましく、１．２倍以上となるようにアルカリ剤を含ませることがより好ましい。ハロゲン系酸化剤のｐＨを上記程度にアルカリ側へコントロールしたものをアンモニウム塩と反応させて生成される組成物は充分な紙力増強剤の効果向上作用を有するためである。 The second composition in the present invention preferably contains an alkaline agent so that the pH of the second composition is 1.05 times or more, and preferably 1.2 times or more, the pH of the halogen-based oxidizing agent itself. It is more preferable to contain the alkali agent so that the This is because a composition produced by reacting an ammonium salt with a halogen-based oxidizing agent whose pH is controlled to the alkaline side to the above degree has a sufficient effect of improving the effect of the paper strength agent.
また、本発明において、第一組成物のｐＨが、４．５～８．５であることが好ましい。
具体的に、アンモニウム塩が硫酸アンモニウムである場合の第一組成物のｐＨが、４．５～８．５であることが好ましく、臭化アンモニウムである場合の第一組成物のｐＨが、７．０～８．５であることが好ましい。また、アンモニウム塩がスルファミン酸アンモニウムである場合の第一組成物のｐＨが、５．５～８．５であることが好ましい。
なお、本発明において、ｐＨは、一般的に使用されている測定器を用いて測定することができ、例えば、堀場製作所製のｐＨ計を用いて測定することができる。
Moreover, in the present invention, the pH of the first composition is preferably 4.5 to 8.5.
Specifically, when the ammonium salt is ammonium sulfate, the pH of the first composition is preferably 4.5 to 8.5, and when it is ammonium bromide, the pH of the first composition is preferably 7.5. It is preferably 0 to 8.5. Also, when the ammonium salt is ammonium sulfamate, the pH of the first composition is preferably 5.5 to 8.5.
In the present invention, the pH can be measured using a commonly used measuring instrument, for example, a pH meter manufactured by Horiba, Ltd.
本発明において、第二組成物のｐＨが、１０．５～１２．５であることが好ましい。 In the present invention, the pH of the second composition is preferably 10.5-12.5.
本発明において、ハロゲン系酸化剤とアンモニウム塩とのモル比（ハロゲン系酸化剤：アンモニウム塩）は、残留塩素量と窒素とのモル比として１：１～１：２であることが好ましく、１：１．１～１：２であることがより好ましく、１：１．２～１：２であることがさらに好ましく、１：１．２～１：１．６であることが特に好ましい。 In the present invention, the molar ratio between the halogen-based oxidizing agent and the ammonium salt (halogen-based oxidizing agent:ammonium salt) is preferably 1:1 to 1:2 as the molar ratio of the amount of residual chlorine to nitrogen. : 1.1 to 1:2 is more preferred, 1:1.2 to 1:2 is even more preferred, and 1:1.2 to 1:1.6 is particularly preferred.
本発明において、第一組成物とハロゲン系酸化剤との重量比、及び、第二組成物とアンモニウム塩との重量比は、ハロゲン系酸化剤とアンモニウム塩とのモル比（ハロゲン系酸化剤：アンモニウム塩）が、上記範囲となるように決定されることが好ましい。 In the present invention, the weight ratio between the first composition and the halogen-based oxidizing agent and the weight ratio between the second composition and the ammonium salt are the molar ratio between the halogen-based oxidizing agent and the ammonium salt (halogen-based oxidizing agent: ammonium salt) is preferably determined so as to fall within the above range.
本発明における紙力増強剤としては、製紙工程で通常用いられているものを特に制限なく用いることができ、カチオン性、アニオン性、両性、非イオン性いずれのイオン性を持つものでもよい。例えば、カチオン性基が導入されたポリアクリルアミド、ポリアミドアミン・エピクロロヒドリン、ポリアミドアミン、グリオキサール変性ポリアミドアミン・エピクロロヒドリン、アミンポリエステルポリエーテル及びこれらの塩等のカチオン性の構造が導入された紙力増強剤；アニオン性基が導入されたポリアクリルアミド、ポリアクリルアミド－アクリル酸共重合体、ポリアクリル酸、ポリアクリルアミド部分加水物、ポリアクリルアミド－２－アクリルアミド－２－メチルプロパンスルホン酸共重合物、カルボキシメチルセルロース及びこれらの塩等のアニオン性の構造が導入された紙力増強剤；ポリアクリルアミドやデンプンにカチオン性基とアニオン性基の両方が導入された化合物及びこれらの塩等の両性の構造が導入された紙力増強剤；ポリアクリルアミド、澱粉、ポリビニルアルコール及びこれらの塩等の非イオン性の構造をもつ紙力増強剤等が挙げられる。本発明における紙力増強剤としては、これらの１種を単独で又は２種以上を組み合わせて用いることができる。また、これら紙力増強剤は溶液（液体）および粉体（固体）などどのような形態であっても良い。特に紙力増強効果を促進させる観点から、紙力増強剤としては、カチオン性紙力増強剤を用いることが好ましい。 As the paper strength agent in the present invention, those commonly used in the papermaking process can be used without particular limitation, and may be cationic, anionic, amphoteric, or nonionic. For example, cationic structures such as polyacrylamide, polyamidoamine/epichlorohydrin, polyamidoamine, glyoxal-modified polyamidoamine/epichlorohydrin, amine polyester polyether, and salts thereof into which cationic groups have been introduced are introduced. paper strength agent: polyacrylamide with an anionic group introduced, polyacrylamide-acrylic acid copolymer, polyacrylic acid, polyacrylamide partial hydrate, polyacrylamide-2-acrylamide-2-methylpropanesulfonic acid copolymer paper strength agents into which anionic structures such as carboxymethylcellulose and salts thereof are introduced; compounds in which both cationic groups and anionic groups are introduced into polyacrylamide and starch, and amphoteric compounds such as salts thereof Structure-introduced paper strength agents; paper strength agents having nonionic structures such as polyacrylamide, starch, polyvinyl alcohol and salts thereof; As the paper strength agent in the present invention, one of these can be used alone or two or more of them can be used in combination. These paper strength agents may be in any form such as solution (liquid) and powder (solid). In particular, from the viewpoint of promoting the paper strength enhancing effect, it is preferable to use a cationic paper strength enhancing agent as the paper strength enhancing agent.
上記カチオン性紙力増強剤として、市販の紙力増強剤を用いることができる。
カチオン性紙力増強剤として、例えば、内添紙力増強剤及び表面紙力増強剤が挙げられ、内添紙力増強剤はさらに乾燥紙力増強剤と湿潤紙力増強剤に分類される。内添紙力増強剤としてはポリアクリルアミド、ポリアクリルアミドにカチオン性基、アニオン性基またはその両方を導入したもの及びポリアミドアミン・エピクロロヒドリン等が挙げられる。表面紙力増強剤としてはポリアクリルアミド及びポリビニルアルコール等が挙げられる。好ましくは、乾燥紙力増強剤としてポリアクリルアミド、ポリアクリルアミドにカチオン性基、アニオン性基またはその両方を導入したもの、湿潤紙力増強剤としてポリアミドアミン・エピクロロヒドリンが好ましい。
Commercially available paper strength agents can be used as the cationic paper strength agent.
Cationic strength agents include, for example, internal strength agents and surface strength agents, and internal strength agents are further classified into dry strength agents and wet strength agents. Examples of internal paper strength enhancers include polyacrylamide, polyacrylamide into which a cationic group, an anionic group, or both have been introduced, polyamidoamine/epichlorohydrin, and the like. Surface strength agents include polyacrylamide and polyvinyl alcohol. Preferred dry paper strength agents are polyacrylamide, polyacrylamide into which a cationic group or an anionic group or both are introduced, and polyamidoamine-epichlorohydrin as a wet paper strength agent.
ここで、従来から紙の製造工程である製紙工程には、殺菌を目的としてモノクロラミンやモノブロラミン等の酸化剤が添加されており、また、紙力向上を目的として紙力増強剤が添加されている。そして、製紙工程の原料ラインに殺菌剤を添加することにより、微生物により澱粉等の原料由来の紙力剤が消費されることを防止し、調整工程等で添加される紙力増強剤の添加量を低減できることが知られている（上記特許文献１～３）。また、製紙工程では様々な薬剤がその目的に応じて添加されており、例えば、ｐＨ調整剤（アルカリ剤）、サイズ剤、濾水性向上剤等も添加されている。これらの薬剤は、各薬剤の効果が発揮されるように添加されており、一つの薬剤の効果が他の薬剤により阻害されないように添加されている。
上述の通り、紙力増強剤には、カチオン性紙力増強剤とアニオン性紙力増強剤があるが、紙力増強剤の種類に応じて他の薬剤の添加位置を変更することは行われておらず、紙力増強剤は、アニオン性薬剤と接触しないように添加されている。なぜなら、カチオン性紙力増強剤とアニオン性薬剤（酸化剤等の殺菌剤）とが反応して凝集が生じると、紙力増強剤が均一に分散せずに薬剤効果が充分に発揮されない可能性が生じるためである。製紙工程における紙力増強剤の不均一分散は、製造される紙の品質悪化を招くため、従来は、紙力増強剤とアニオン系殺菌剤（酸化剤等）とは、反応する程度の濃度で接触しないように添加されていた。
一方、本発明は、紙力増強剤そのものの効果を向上させることを検討した結果、紙力増強剤に対し、特定の製造方法により製造されたモノクロラミン及び／又はモノブロラミンである効果向上用組成物（アニオン系酸化剤）を接触させることにより、紙力増強剤の効果を向上できることを初めて見出し完成されたものである。
Here, oxidizing agents such as monochloramine and monobroramine have been added for the purpose of sterilization in the papermaking process, which is a process for manufacturing paper, and paper strength enhancers have been added for the purpose of improving paper strength. ing. Then, by adding a bactericide to the raw material line of the paper manufacturing process, it is possible to prevent the consumption of the paper strength agent derived from the raw material such as starch by microorganisms, and the amount of the paper strength enhancer added in the adjustment process etc. can be reduced (Patent Documents 1 to 3 above). In the papermaking process, various agents are added according to the purpose, such as pH adjusters (alkaline agents), sizing agents, and drainage improvers. These drugs are added so that the effect of each drug is exhibited, and the effect of one drug is not inhibited by another drug.
As described above, paper strength agents include cationic paper strength agents and anionic paper strength agents, but the addition position of other agents is not changed according to the type of paper strength agent. The paper strength agent is added so that it does not come into contact with the anionic agent. This is because if a cationic paper strength agent and an anionic agent (bactericide such as an oxidizing agent) react and cause aggregation, the paper strength agent may not be uniformly dispersed and the drug effect may not be fully exhibited. This is because Inhomogeneous dispersion of the paper strength agent in the papermaking process leads to deterioration of the quality of the paper produced. It was added so as not to touch.
On the other hand, as a result of studying how to improve the effect of the paper strength agent itself, the present invention has found that the effect-improving composition is monochloramine and/or monobroramine produced by a specific manufacturing method for the paper strength agent. It was completed for the first time after discovering that the effect of a paper strength agent can be improved by bringing it into contact with a substance (anionic oxidizing agent).
本発明は、製紙工程における紙力増強剤の効果向上方法であって、製紙工程水に、本発明の紙力増強剤の効果向上用組成物を添加する組成物添加工程と、紙力増強剤を添加する紙力増強剤添加工程とを有し、前記組成物と前記紙力増強剤とは接触するものであることを特徴とする紙力増強剤の効果向上方法でもある。 The present invention is a method for improving the effect of a paper strength agent in a papermaking process, comprising a composition addition step of adding a composition for improving the effect of a paper strength agent of the present invention to papermaking process water, and a paper strength agent It is also a method for improving the effect of a paper strength agent, wherein the composition and the paper strength agent are in contact with each other.
本発明において上記製紙工程は、パルプに薬剤配合を行う調成工程、抄紙工程、仕上げ工程を含み、上記調成工程の前に、紙原料からパルプを得るパルプ化工程を有していてもよい。本発明の紙力増強剤の効果向上方法は、紙原料から紙を製造するまでの製紙工程、又は、パルプから紙を製造するまでの製紙工程のいずれの場合にも用いることができる。なお、上記紙原料は、古紙及び木材のいずれであってもよい。 In the present invention, the papermaking process includes a preparation process of adding chemicals to pulp, a papermaking process, and a finishing process, and may have a pulping process of obtaining pulp from paper raw materials before the preparation process. . The method for improving the effect of the paper strength agent of the present invention can be used in either the papermaking process from paper raw materials to papermaking or the papermaking process from pulp to papermaking. The paper raw material may be either waste paper or wood.
例えば、古紙を紙原料とする場合、製紙工程は、上記パルプ化工程として、古紙のパルプ化工程を含んでもよい。古紙のパルプ化工程は、主として離解工程、粗選・精選工程および脱水・洗浄工程を含んでなる。さらに、古紙に含まれるインクを除去する脱墨工程及びパルプを化学的に漂白する漂白工程を含む場合もある。各工程について具体的に説明すると、原料となる古紙を水と混合しながら機械力でパルプスラリーとする離解（パルパー）工程、古紙に含まれる異物を除去する粗選（除塵）工程、脱墨剤を加えてインキ成分を除去する脱墨工程、古紙に含まれる異物とパルプ分とをスクリーンで分離する精選工程、パルプスラリーを水洗する洗浄工程、及びパルプの脱水を行う脱水工程、漂白剤を加えてパルプの漂白を行う漂白工程である。上記各工程で用いられる水、及び排水される水を白水といい、上記パルパー工程において原料である古紙と白水とが混合されたものをパルプスラリーという。 For example, when waste paper is used as the paper raw material, the paper manufacturing process may include a waste paper pulping process as the pulping process. The waste paper pulping process mainly includes a defibering process, a rough screening/cleaning process, and a dehydration/washing process. Furthermore, in some cases, a deinking process for removing ink contained in waste paper and a bleaching process for chemically bleaching pulp are included. To explain each process in detail, the pulping (pulper) process, which mechanically turns waste paper into pulp slurry while mixing it with water, the rough screening (dust removal) process, which removes foreign substances contained in the waste paper, and the deinking agent. A deinking process to remove the ink component by adding a bleaching agent, a screening process to separate the pulp from the foreign matter contained in the waste paper with a screen, a washing process to wash the pulp slurry with water, and a dehydration process to dehydrate the pulp. This is a bleaching process in which the pulp is bleached. The water used in each of the above processes and the water discharged is called white water, and the mixture of waste paper, which is the raw material, and white water in the pulper process is called pulp slurry.
また、木材を紙原料とする場合、製紙工程は、上記パルプ化工程として、化学パルプのパルプ化工程や機械パルプのパルプ化工程を含んでもよい。化学パルプのパルプ化工程は、主として調木工程、蒸解工程、精選・洗浄工程及び脱水工程を含んでなる。さらに、パルプを化学的に漂白する漂白工程を含む場合もある。上記蒸解工程では、チップに薬品を加え、高温・高圧で煮て、樹脂（リグニン）を溶かし繊維分を取り出し、チップをパルプ化する。すなわち、パルプ原料は蒸解工程を経てパルプスラリーとなる。また、機械パルプのパルプ化工程は、主として砕木工程、除塵工程及び濃縮工程を含んでなる。さらに、パルプを化学的に漂白する漂白工程を含む場合もある。上記工程では機械的に繊維化することでパルプスラリーとなる。 When wood is used as the raw material for paper, the papermaking process may include a chemical pulping process or a mechanical pulping process as the pulping process. The pulping process of chemical pulp mainly comprises a wood preparation process, a cooking process, a screening/washing process and a dehydration process. In addition, it may also include a bleaching step in which the pulp is chemically bleached. In the cooking process, chemicals are added to the chips, which are then boiled at high temperature and high pressure to dissolve the resin (lignin), remove the fibers, and turn the chips into pulp. That is, the pulp raw material becomes a pulp slurry through a cooking process. Also, the pulping process of mechanical pulp mainly comprises a groundwood process, a dust removal process and a thickening process. Furthermore, it may include a bleaching step in which the pulp is chemically bleached. In the above process, a pulp slurry is obtained by mechanical fiberization.
本発明において上記製紙工程水とは、紙原料であるパルプを含む水である。ここで、製紙工程では大量の水を媒体として各工程が進行するため、水の再利用が行われている。本発明において紙原料であるパルプを含む水とは、各工程の原料ラインを移動する水（以下、パルプスラリーともいう）であって、各工程の原料ラインから排出される水ではない。ただし、原料ラインから排出された水であっても、白水ピット等に貯留され、製紙工程で再利用される水（白水）は、原料ラインに戻ってくるため、これも上記製紙工程水に含まれる。すなわち、再利用される白水のうち白水ピット等のタンクから原料ラインまでの循環ラインを移動する白水も上記製紙工程水に含まれる。 In the present invention, the water used in the papermaking process is water containing pulp, which is a raw material for paper. Here, in the paper manufacturing process, since each process proceeds using a large amount of water as a medium, water is reused. In the present invention, water containing pulp, which is a raw material for paper, is water that moves through the raw material line of each process (hereinafter also referred to as pulp slurry), and is not water that is discharged from the raw material line of each process. However, even if the water is discharged from the raw material line, the water (white water) that is stored in the white water pit or the like and reused in the paper manufacturing process returns to the raw material line, so this is also included in the paper manufacturing process water. be That is, of the white water to be reused, white water that moves through a circulation line from a tank such as a white water pit to a raw material line is also included in the papermaking process water.
上記製紙工程水に、上述の本発明の紙力増強剤の効果向上用組成物を添加する組成物添加工程と、紙力増強剤を添加する紙力増強剤添加工程とは、各工程の前後は問わず、本発明の組成物と紙力増強剤とが接触するものであれば同時又は別々に行われてもよい。
詳細に説明すると、本発明の組成物と紙力増強剤とが直接接触する場合であっても、製紙工程水中で接触する場合であっても、本発明の組成物と紙力増強剤とが反応する濃度で接触するように添加されるものであればよい。
The composition addition step of adding the composition for improving the effect of the paper strength agent of the present invention and the paper strength agent addition step of adding the paper strength agent to the papermaking process water are performed before and after each step. Regardless, as long as the composition of the present invention and the paper strength agent come into contact with each other, they may be carried out simultaneously or separately.
More specifically, whether the composition of the present invention and the paper strength agent come into direct contact with each other or in the water during the papermaking process, the composition of the present invention and the paper strength agent What is necessary is just to add so that it may contact at the density|concentration which reacts.
本発明の紙力増強剤の効果向上方法において、本発明の紙力増強剤の効果向上用組成物と、紙力増強剤とが接触する際の上記組成物の接触濃度が、０．１～３５ｍｇ／Ｌであることが好ましい。上記濃度範囲の本発明の組成物と、紙力増強剤とを接触させることにより、より充分な紙力増強効果が得られるためである。 In the method for improving the effect of the paper strength agent of the present invention, the contact concentration of the composition when the composition for improving the effect of the paper strength agent of the present invention and the paper strength agent are in contact with each other is 0.1 to 35 mg/L is preferred. This is because, by bringing the composition of the present invention in the concentration range described above into contact with the paper strength agent, a more sufficient paper strength strength effect can be obtained.
本明細書において、「紙力増強剤の効果向上用組成物と、紙力増強剤とが接触する際の上記組成物の接触濃度」は、本発明の組成物と紙力増強剤とが接触する際の該組成物の製紙工程水に対する濃度を意味するものである。具体的に説明すると、本発明の組成物と紙力増強剤とが直接接触するように、組成物添加工程と紙力増強剤添加工程とを有する場合は、添加される該組成物の、製紙工程水に対する添加濃度を示す。また、本発明の組成物と紙力増強剤とが製紙工程水中で接触するように、組成物添加工程の後に紙力増強剤添加工程を有する場合は、紙力増強剤と接触する製紙工程水中の該組成物の残留塩素濃度を示す。また、紙力増強剤添加工程の後に組成物添加工程を有する場合は、紙力増強剤が添加された製紙工程水に添加される該組成物の、製紙工程水に対する添加濃度を示す。なお、本発明の組成物の接触濃度は、残留塩素濃度に換算して得られる値（残留塩素濃度換算値）である。 As used herein, "the contact concentration of the composition when the composition for improving the effect of the paper strength agent and the paper strength agent are in contact with each other" means It means the concentration of the composition with respect to the papermaking process water. Specifically, when the composition of the present invention and the paper strength agent addition step are included so that the composition and the paper strength agent are in direct contact, the composition to be added is used in papermaking. Addition concentration to process water is shown. Further, when the composition of the present invention has a paper strength agent addition step after the composition addition step so that the composition and the paper strength agent come into contact with each other in the paper manufacturing process water, shows the residual chlorine concentration of the composition. In addition, when the composition addition step is performed after the paper strength agent addition step, the addition concentration of the composition added to the papermaking process water to which the paper strength agent has been added is shown. The contact concentration of the composition of the present invention is a value obtained by converting the residual chlorine concentration (residual chlorine concentration conversion value).
本発明において、組成物添加工程後の製紙工程水の残留塩素濃度（残留塩素換算濃度）が０．１～３５ｍｇ／Ｌであることが好ましい。また、組成物添加工程後の製紙工程水の残留塩素濃度が、残留塩素量として、０．５～３０ｍｇ／Ｌであることがより好ましく、１～３０ｍｇ／Ｌがさらに好ましく、経済性の点から、１～２５ｍｇ／Ｌまたは１～２０ｍｇ／Ｌが好ましい。 In the present invention, the residual chlorine concentration (concentration in terms of residual chlorine) in the papermaking process water after the composition addition step is preferably 0.1 to 35 mg/L. In addition, the concentration of residual chlorine in the papermaking process water after the composition addition step is more preferably 0.5 to 30 mg/L, more preferably 1 to 30 mg/L, in terms of residual chlorine content, from the viewpoint of economy. , 1-25 mg/L or 1-20 mg/L.
本発明において製紙工程水に本発明の組成物を添加する組成物添加工程と紙力増強剤を添加する紙力増強剤添加工程とが行われるタイミングは、上述の通り、本発明の組成物と紙力増強剤とが反応する濃度で接触するタイミングであれば特に問わないが、例えば、製紙工程水の条件によって設定することができる。
例えば、製紙工程水のＯＲＰが－４００ｍＶ以下の過酷な条件である場合は、組成物添加工程と紙力増強剤添加工程とは、同時、又は、各工程が１分以内に行われることが好ましい。一方、製紙工程水において本発明の組成物の消費が少ない環境下（例えば、製紙工程水に対して清水の供給量が豊富な系）では、組成物添加工程と紙力増強剤添加工程とは、１２０分以内に行われてもよい。本発明において、組成物添加工程と紙力増強剤添加工程とは、同時又は各工程が６０分以内に行われることが好ましく、同時又は各工程が１０分以内に行われることがより好ましく、同時又は各工程が５分以内に行われることがさらに好ましく、同時又は各工程が１分以内に行われることが特に好ましい。より濃度の濃い紙力増強剤と、より濃度の濃い本発明の組成物とを、接触させることができるためである。
In the present invention, the timing of performing the composition addition step of adding the composition of the present invention to the papermaking process water and the paper strength agent addition step of adding the paper strength agent are as described above. The timing of contact at a concentration at which the paper strength agent reacts is not particularly limited, but can be set according to the conditions of the water used in the papermaking process, for example.
For example, when the ORP of papermaking process water is under severe conditions of −400 mV or less, the composition addition step and the paper strength agent addition step are performed at the same time, or each step is preferably performed within 1 minute. . On the other hand, in an environment where the consumption of the composition of the present invention is small in the papermaking process water (for example, in a system in which fresh water is supplied abundantly with respect to the papermaking process water), the composition addition step and the paper strength agent addition step are different. , may be performed within 120 minutes. In the present invention, the composition addition step and the paper strength agent addition step are preferably performed simultaneously or each step within 60 minutes, more preferably simultaneously or each step within 10 minutes. Alternatively, it is more preferable that each step is performed within 5 minutes, and it is particularly preferable that the simultaneous or each step is performed within 1 minute. This is because the paper strength agent having a higher concentration and the composition of the present invention having a higher concentration can be brought into contact with each other.
本発明において、紙力増強剤添加工程は、組成物添加工程と同一箇所及び／又は組成物添加工程の上流側に、設けられることが好ましい。本発明の組成物は、製紙工程水に添加されると同時に、製紙工程水中の微生物により消費され始める可能性があるためである。なお、本明細書においては、「上流側」は、製紙工程水の流れ方向に対する上流側を意味する。具体的に、製紙工程水に、組成物工程と紙力増強剤添加工程とが、原料ラインに構成されている場合、上流側とは古紙や木材などの原料（又は原料パルプ）に近い方を意味する。一方、製紙工程水に、酸化剤添加工程と紙力増強剤添加工程とが白水を再利用するための循環ラインに構成されている場合、上流側とは、白水ピット等のタンクに近い方を意味する。また、本明細書において、同一箇所とは、同一の機器、同一のタンク、同一の配管（機器と機器との間の配管）を意味する。 In the present invention, the paper strength agent addition step is preferably provided at the same location as the composition addition step and/or upstream of the composition addition step. This is because the composition of the present invention may begin to be consumed by microorganisms in the papermaking process water as soon as it is added to the papermaking process water. In this specification, "upstream side" means the upstream side with respect to the flow direction of water in the papermaking process. Specifically, when the composition step and the paper strength agent addition step are configured in the raw material line in the papermaking process water, the upstream side is the one closer to the raw material (or raw material pulp) such as waste paper and wood. means. On the other hand, when the oxidizing agent addition step and the paper strength agent addition step are configured in a circulation line for reusing the white water in the papermaking process water, the upstream side means the side near the tank such as the white water pit. means. Moreover, in this specification, the same location means the same equipment, the same tank, and the same piping (piping between equipments).
また、本発明において組成物添加工程と紙力増強剤添加工程とが、製紙工程の同一箇所で行われ、紙力増強剤添加工程が組成物添加工程よりも上流側である場合、上記２つの工程で薬剤添加が開始されるタイミングは、製紙工程水の流速によって決定されることが好ましい。製紙工程の上流側で添加された紙力増強剤が酸化剤の添加位置に到達したタイミングで、酸化剤を添加することにより、より濃度の濃い紙力増強剤と、より濃度の濃い本発明の組成物とを、より確実に接触させることができるためである。 Further, in the present invention, when the composition addition step and the paper strength agent addition step are performed at the same place in the papermaking process, and the paper strength agent addition step is upstream of the composition addition step, the above two The timing at which chemical addition is initiated in the process is preferably determined by the flow rate of the papermaking process water. By adding an oxidizing agent at the timing when the paper strength agent added on the upstream side of the papermaking process reaches the addition position of the oxidizing agent, a higher concentration of the paper strength agent and a higher concentration of the present invention are obtained. This is because the composition can be brought into contact more reliably.
なお、本発明の組成物の添加量は、本発明の組成物と紙力増強剤とが接触する際の酸化剤の接触濃度が、０．１～３５ｍｇ／Ｌとなるよう設定されればよい。例えば、紙力増強剤と本発明の組成物とが製紙工程水中で接触する場合、紙力増強剤が本発明の組成物の残留濃度（残留塩素換算濃度）が０．１～３５ｍｇ／Ｌの製紙工程水と接触するように、本発明の組成物の添加量が設定される。なお、紙力増強剤と本発明の組成物とが反応する濃度で接触することにより、紙力増強効果を得ることができる。 The amount of the composition of the present invention to be added may be set so that the contact concentration of the oxidizing agent when the composition of the present invention and the paper strength agent come into contact is 0.1 to 35 mg/L. . For example, when the paper strength agent and the composition of the present invention are brought into contact with each other in papermaking process water, the paper strength agent has a residual concentration of the composition of the present invention (concentration converted to residual chlorine) of 0.1 to 35 mg/L. The amount of the composition of the present invention added is set so as to contact the papermaking process water. The paper strength enhancing effect can be obtained by contacting the paper strength agent and the composition of the present invention at a concentration at which they react.
また、上記紙力増強剤は、対パルプ固形分１００重量％に対して、紙力増強剤の固形分として０．０１～２．０重量％添加されることが好ましく、０．０５～１．０重量％添加されることが好ましい。紙力増強剤の添加量が上記０．０１重量％未満であると、紙力増強効果が充分に得られない可能性があり、２．０重量％を超えると、パルプシートや最終製品として得られる紙に紙力増強剤が付着し、欠点が生じる可能性があるためである。 Further, the above-mentioned paper strength enhancer is preferably added in an amount of 0.01 to 2.0% by weight, and 0.05 to 1.0% by weight, as a solid content of the paper strength enhancer with respect to 100% by weight of the solid content of the pulp. It is preferably added at 0% by weight. If the amount of the paper strength enhancer added is less than 0.01% by weight, the paper strength enhancement effect may not be sufficiently obtained. This is because the paper strength agent may adhere to the paper to which it is applied, resulting in defects.
なお、本発明における「残留塩素量」の記載は、ハロゲン系酸化剤が塩素系酸化剤ではない場合には、「残留塩素量換算値」を意味する。 The description of "residual chlorine amount" in the present invention means "residual chlorine amount conversion value" when the halogen-based oxidizing agent is not a chlorine-based oxidizing agent.
（殺菌剤について）
上述の本発明の紙力増強剤の効果向上用組成物は、本発明の殺菌用組成物と言い換えることができる。
すなわち、本発明は、アンモニウム塩及びアルカリ剤を含む第一組成物とハロゲン系酸化剤とを混合する、又は、ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合することを特徴とする殺菌用組成物の製造方法であってもよい。
また、本発明は、アンモニウム塩及びアルカリ剤を含む第一組成物とハロゲン系酸化剤とを混合する、又は、ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合する、ことにより生成される殺菌用組成物であってもよい。
本発明の殺菌用組成物は、上述の本発明の紙力増強剤の効果向上用組成物における、アンモニウム塩、アルカリ剤、ハロゲン系酸化剤及び紙力増強剤及びこれらの好適な態様と同様にすることができ、第一組成物、第二組成物の構成やｐＨについても同様にすることができる。
(About disinfectant)
The above composition for improving the effect of the paper strength agent of the present invention can be rephrased as the composition for sterilization of the present invention.
That is, the present invention involves mixing a first composition containing an ammonium salt and an alkaline agent with a halogen-based oxidizing agent, or mixing a second composition containing a halogen-based oxidizing agent and an alkali agent with an ammonium salt. It may be a method for producing a sterilizing composition characterized by
In addition, the present invention includes mixing a first composition containing an ammonium salt and an alkaline agent with a halogen-based oxidizing agent, or mixing a second composition containing a halogen-based oxidizing agent and an alkali agent with an ammonium salt. It may also be a bactericidal composition produced by
The composition for sterilization of the present invention includes an ammonium salt, an alkaline agent, a halogen-based oxidizing agent, a paper strength agent, and preferred embodiments thereof in the above-described composition for improving the effect of a paper strength agent of the present invention. The same can be applied to the configurations and pH of the first composition and the second composition.
以下、実施例及び比較例に基づいて本発明を具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited to these Examples.
（実施例１～４、比較例１～３、参考例１）（実施例５～８、比較例４～７、参考例２）
［古紙パルプを用いた紙の調製］
（１）パルプ濃度３％の原料（パルプスラリー）を、１０００ｍＬビーカーに６９０ｇ量りとった。（絶乾パルプ重量として、２０．７ｇ）
（２）用意した１０００ｍＬビーカー内のパルプスラリーを攪拌機（スリーワンモーター：新東科学社製）で攪拌（３５０ｒｐｍ）し、攪拌開始から１分後に紙力増強剤を添加し、さらに３０秒後に、下記表１及び表２に記載の紙力増強剤の効果向上用組成物を下記調整例１もしくは調整例２に記載のとおり調整後、対パルプスラリー濃度として、表１にかかる試験では５ｐｐｍ、表２にかかる試験では１０ｐｐｍになるように添加し、２分間攪拌した。
なお、比較例１、比較例４、参考例１及び参考例２にかかる試験例では、効果向上用組成物を添加することなく紙力増強剤のみを添加した。参考例１は比較例１、参考例２は比較例４で添加された紙力増強剤の１．３倍の量の紙力増強剤が添加されており、これを、紙力向上率（％）を確認する上でのポジティブコントロールとした。
また、比較例２にかかる試験例では、パルプスラリーにアルカリ剤（水酸化ナトリウム）を添加し、パルプスラリーのｐＨを９．２に調整した後に、攪拌を開始し、他の試験例と同様に比較例２にかかる紙力増強剤と効果向上用組成物とを順に添加した。
（３）得られた各試験例にかかる効果向上用組成物と接触した紙力増強剤を含むパルプスラリーの残留塩素濃度及びｐＨを測定した。各試験例の残留塩素濃度、ｐＨを下記表３及び表４に示す。（参考例１及び２、比較例１及び４を除く試験例）
（４）（３）のパルプスラリーを３等分し、３回手すき抄紙を行い、角形（２５０ｍｍ×２５０ｍｍ）の各試験例にかかるパルプシートを３枚得た。
(Examples 1-4, Comparative Examples 1-3, Reference Example 1) (Examples 5-8, Comparative Examples 4-7, Reference Example 2)
[Preparation of paper using waste paper pulp]
(1) 690 g of raw material (pulp slurry) having a pulp concentration of 3% was weighed into a 1000 mL beaker. (20.7 g as absolute dry pulp weight)
(2) The pulp slurry in the prepared 1000 mL beaker is stirred (350 rpm) with a stirrer (three one motor: manufactured by Shinto Kagaku Co., Ltd.), 1 minute after the start of stirring, a paper strength agent is added, and after 30 seconds, the following After adjusting the composition for improving the effect of the paper strength agent shown in Tables 1 and 2 as described in Preparation Example 1 or Preparation Example 2 below, the concentration relative to the pulp slurry was 5 ppm in the test of Table 1, and 5 ppm in Table 2. In this test, it was added to 10 ppm and stirred for 2 minutes.
In the test examples of Comparative Example 1, Comparative Example 4, Reference Example 1 and Reference Example 2, only the paper strength agent was added without adding the effect-improving composition. Reference Example 1 is Comparative Example 1, and Reference Example 2 is 1.3 times the amount of the paper strength enhancer added in Comparative Example 4, which is the paper strength improvement rate (% ) was used as a positive control to confirm.
In addition, in the test example according to Comparative Example 2, an alkaline agent (sodium hydroxide) was added to the pulp slurry, and after adjusting the pH of the pulp slurry to 9.2, stirring was started, and the same as the other test examples. The paper strength agent according to Comparative Example 2 and the effect-improving composition were added in that order.
(3) The concentration of residual chlorine and the pH of the pulp slurry containing the paper strength enhancer which was in contact with the effect-improving composition according to each test example obtained were measured. Tables 3 and 4 below show the residual chlorine concentration and pH of each test example. (Test examples excluding Reference Examples 1 and 2 and Comparative Examples 1 and 4)
(4) The pulp slurry of (3) was divided into three equal parts and hand-made three times to obtain three rectangular (250 mm×250 mm) pulp sheets of each test example.
［調整例１］
残留塩素量と窒素のモル比が１：１．５となるように、イオン交換水で６０倍に希釈した第二組成物と、第一組成物を混合した。調整例１は、実施例１乃至５、７及び８、比較例２、３、５及び７にかかる試験例における供試薬剤とした。
[Adjustment example 1]
The first composition was mixed with the second composition diluted 60 times with deionized water so that the molar ratio of residual chlorine to nitrogen was 1:1.5. Preparation Example 1 was used as a test reagent in the test examples of Examples 1 to 5, 7 and 8 and Comparative Examples 2, 3, 5 and 7.
［調整例２］
残留塩素量と窒素のモル比が１：１．３となるように、イオン交換水で６０倍に希釈した第二組成物のハロゲン系酸化剤に水酸化ナトリウム水溶液を所定のｐＨになるように加えた後、第一組成物を混合した。調整例２は、実施例６にかかる試験例における供試薬剤とした。
[Adjustment example 2]
Sodium hydroxide aqueous solution is added to the halogen-based oxidizing agent of the second composition diluted 60 times with deionized water so that the molar ratio of residual chlorine and nitrogen is 1:1.3. After addition, the first composition was mixed. Preparation Example 2 was used as a test reagent in the test example according to Example 6.
各試験例で用いた薬剤は下記のとおりである。
（紙力増強剤）
内添タイプの乾燥紙力増強剤（カチオン性ポリアクリルアミド乾燥紙力増強剤）
（アンモニウム塩）
硫酸アンモニウム：キシダ化学社製試薬
臭化アンモニウム：キシダ化学社製試薬
スルファミン酸アンモニウム：キシダ化学社製試薬
（アルカリ剤）
水酸化Ｎａ：水酸化ナトリウム、富士フィルム和光純薬社製試薬
水酸化Ｋ：水酸化カリウム、富士フィルム和光純薬社製試薬
クエン酸三Ｎａ：クエン酸三ナトリウム、富士フィルム和光純薬社製試薬
（ハロゲン系酸化剤）
次亜塩素酸Ｎａ：次亜塩素酸ナトリウム、キシダ化学社製試薬
The drugs used in each test example are as follows.
(paper strength agent)
Internal addition type dry paper strength agent (cationic polyacrylamide dry paper strength agent)
(ammonium salt)
Ammonium sulfate: reagent manufactured by Kishida Chemical Co., Ltd. Ammonium bromide: reagent manufactured by Kishida Chemical Co., Ltd. Ammonium sulfamate: reagent manufactured by Kishida Chemical Co., Ltd. (alkaline agent)
Na hydroxide: Sodium hydroxide, Fuji Film Wako Pure Chemical reagent K hydroxide: Potassium hydroxide, Fuji Film Wako Pure Chemical reagent Trisodium citrate: Trisodium citrate, Fuji Film Wako Pure Chemical reagent (Halogen-based oxidizing agent)
Sodium hypochlorite: sodium hypochlorite, reagent manufactured by Kishida Chemical Co., Ltd.
また、各試験例の残留塩素濃度、ｐＨ、破裂強度は下記の機器を用いて測定した。
（残留塩素濃度の測定）
残留塩素測定器：笠原工業社製
（ｐＨの測定）
ｐＨ計：堀場製作所社製
（比破裂強度の測定）
比破裂試験機：日本Ｔ．Ｍ．Ｃ社製
In addition, the residual chlorine concentration, pH and bursting strength of each test example were measured using the following equipment.
(Measurement of residual chlorine concentration)
Residual chlorine measuring instrument: manufactured by Kasahara Kogyo Co., Ltd. (measurement of pH)
pH meter: manufactured by Horiba Ltd. (measurement of specific burst strength)
Specific burst tester: Japan T. M. Made by C company
（紙力向上率）
（１）得られた各試験例にかかるパルプシートの紙重量を測定し、坪量を算出した。
（２）（１）のパルプシートを、ＪＩＳ Ｐ ８２２３「試験用手抄き紙－物理的特性の試験方法」に規定されている、ＪＩＳ Ｐ ８１１２「紙及び板紙のミューレン低圧破裂試験機による破裂強さ試験方法」に記載の方法に準拠して測定した。
（３）上記（１）で得られた坪量と上記（２）で得られた破裂強度から、比破裂強度を算出した。
（４）下記式に基づいて紙力向上率を算出し、下記表３及び表４に記載した。
［式］（紙力向上率）＝（各試験例の比破裂強さ）／（酸化剤無添加の試験例の比破裂強さ※）×１００
※表３においては比較例１の比破裂強さ、表４においては比較例４の比破裂強さを（酸化剤無添加の試験例の比破裂強さ）として用いた。
(Paper strength improvement rate)
(1) The paper weight of the obtained pulp sheet according to each test example was measured to calculate the basis weight.
(2) The pulp sheet of (1) is ruptured by JIS P 8112 "Paper and paperboard Mullen low pressure burst tester" specified in JIS P 8223 "Handmade paper for testing - Physical property test method" strength test method”.
(3) The specific burst strength was calculated from the basis weight obtained in (1) above and the burst strength obtained in (2) above.
(4) The paper strength improvement rate was calculated based on the following formula and shown in Tables 3 and 4 below.
[Formula] (paper strength improvement rate) = (relative bursting strength of each test example) / (relative bursting strength of test example without oxidizing agent added *) x 100
*In Table 3, the relative burst strength of Comparative Example 1 was used, and in Table 4, the relative burst strength of Comparative Example 4 was used as (the relative burst strength of test examples with no oxidant added).
上記表３の結果から、実施例１～４は比較例１と同量の紙力増強剤が用いられているものの、特定の製造方法により製造された紙力増強剤の効果向上用組成物が添加されており、比較例１に対し紙力増強剤が１．３倍添加されている参考例１と同様に、紙力向上率が大きく向上していた。
一方、比較例２（アンモニウム塩とハロゲン系酸化剤とを混合して生じる従来のモノクロラミンを、ｐＨ調製されたパルプスラリーに添加）は、比較例１と同量の紙力増強剤が用いられているものの、比較例１に対し紙力向上率が大きく下がっていた。
また、比較例３（アンモニウム塩とハロゲン系酸化剤とを混合して生じる従来のモノクロラミンを、パルプスラリーに添加）は、比較例１に対し紙力向上率が向上しているものの、その効果は大きなものではなかった。
よって、アンモニウム塩及びアルカリ剤を含む第一組成物と、ハロゲン系酸化剤とを混合することにより得られる紙力増強剤の効果向上用組成物は、優れた紙力増強剤の効果向上作用を有することを確認した。
上記表４の結果から、実施例５、７及び８は比較例４と同量の紙力増強剤が用いられているものの、特定の製造方法により製造された紙力増強剤の効果向上用組成物が添加されており、比較例４に対し紙力増強剤が１．３倍添加されている参考例２と同様に、紙力向上率が大きく向上していた。また、実施例６（ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合することにより製造される効果向上用組成物）は、実施例５と同様に優れた紙力増強剤の効果向上作用を有することを確認した。
From the results in Table 3 above, although the same amount of paper strength agent as in Comparative Example 1 is used in Examples 1 to 4, the composition for improving the effect of the paper strength agent manufactured by a specific manufacturing method is used. As in Reference Example 1, in which 1.3 times the paper strength enhancer was added as compared to Comparative Example 1, the paper strength improvement rate was greatly improved.
On the other hand, in Comparative Example 2 (conventional monochloramine produced by mixing an ammonium salt and a halogen-based oxidizing agent was added to the pH-adjusted pulp slurry), the same amount of paper strength agent as in Comparative Example 1 was used. However, compared with Comparative Example 1, the paper strength improvement rate was greatly reduced.
In Comparative Example 3 (conventional monochloramine produced by mixing an ammonium salt and a halogen-based oxidizing agent was added to the pulp slurry), the paper strength improvement rate was improved compared to Comparative Example 1, but the effect was was not big.
Therefore, the composition for improving the effect of the paper strength agent obtained by mixing the first composition containing an ammonium salt and an alkali agent with the halogen-based oxidizing agent has an excellent effect of improving the effect of the paper strength agent. I confirmed that I have
From the results in Table 4 above, although the same amount of paper strength agent as in Comparative Example 4 is used in Examples 5, 7 and 8, the composition for improving the effect of the paper strength agent manufactured by a specific manufacturing method The paper strength improvement rate was greatly improved in the same manner as in Reference Example 2 in which the paper strength enhancer was added 1.3 times as much as in Comparative Example 4. In addition, Example 6 (an effect-improving composition produced by mixing a second composition containing a halogen-based oxidizing agent and an alkaline agent with an ammonium salt) has excellent paper strength enhancement as in Example 5. It was confirmed that it has the effect of improving the effect of the agent.
Claims (11)
ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合する、
ことを特徴とする紙力増強剤の効果向上用組成物の製造方法。 mixing a first composition containing an ammonium salt and an alkaline agent with a halogen-based oxidizing agent, or
mixing a second composition containing a halogen-based oxidizing agent and an alkaline agent with an ammonium salt;
A method for producing a composition for improving the effect of a paper strength agent, characterized by:
ハロゲン系酸化剤及びアルカリ剤を含む第二組成物とアンモニウム塩とを混合する、
ことにより生成される紙力増強剤の効果向上用組成物。 mixing a first composition containing an ammonium salt and an alkaline agent with a halogen-based oxidizing agent, or
mixing a second composition containing a halogen-based oxidizing agent and an alkaline agent with an ammonium salt;
A composition for improving the effect of a paper strength agent produced by
製紙工程水に、請求項６、７又は８に記載の紙力増強剤の効果向上用組成物を添加する組成物添加工程と、紙力増強剤を添加する紙力増強剤添加工程とを有し、
前記組成物と前記紙力増強剤とは接触するものである
ことを特徴とする紙力増強剤の効果向上方法。 A method for improving the effect of a paper strength agent in a papermaking process, comprising:
A composition addition step of adding the composition for improving the effect of the paper strength agent according to claim 6, 7 or 8 to the papermaking process water, and a paper strength agent addition step of adding the paper strength agent. death,
A method for improving the effect of a paper strength agent, wherein the composition and the paper strength agent are in contact with each other.
11. The method for improving the effect of a paper strength agent according to claim 9 or 10, wherein the concentration of residual chlorine in the papermaking process water after the step of adding the composition is 0.1 to 35 mg/L.
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