JP2023150630A - Method for improving effectiveness of paper strength enhancing agent - Google Patents
Method for improving effectiveness of paper strength enhancing agent Download PDFInfo
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- JP2023150630A JP2023150630A JP2022059841A JP2022059841A JP2023150630A JP 2023150630 A JP2023150630 A JP 2023150630A JP 2022059841 A JP2022059841 A JP 2022059841A JP 2022059841 A JP2022059841 A JP 2022059841A JP 2023150630 A JP2023150630 A JP 2023150630A
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- JP
- Japan
- Prior art keywords
- paper strength
- improving
- effect
- composition
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 98
- 230000002708 enhancing effect Effects 0.000 title abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 110
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000002360 preparation method Methods 0.000 claims abstract description 53
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 239000003623 enhancer Substances 0.000 claims description 116
- 230000000694 effects Effects 0.000 claims description 68
- 239000007800 oxidant agent Substances 0.000 claims description 52
- 150000003863 ammonium salts Chemical class 0.000 claims description 44
- 229910052736 halogen Inorganic materials 0.000 claims description 31
- 150000002367 halogens Chemical class 0.000 claims description 31
- 238000004519 manufacturing process Methods 0.000 claims description 28
- 239000000460 chlorine Substances 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- 239000013054 paper strength agent Substances 0.000 claims description 19
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 11
- 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
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- GEHMBYLTCISYNY-UHFFFAOYSA-N Ammonium sulfamate Chemical compound [NH4+].NS([O-])(=O)=O GEHMBYLTCISYNY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 6
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910001919 chlorite Inorganic materials 0.000 claims description 5
- 229910052619 chlorite group Inorganic materials 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
- 235000019270 ammonium chloride Nutrition 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
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 51
- 230000006872 improvement Effects 0.000 abstract description 4
- 239000000123 paper Substances 0.000 description 175
- 239000002994 raw material Substances 0.000 description 34
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 25
- 125000002091 cationic group Chemical group 0.000 description 14
- 239000010893 paper waste Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000004537 pulping Methods 0.000 description 12
- 239000013055 pulp slurry Substances 0.000 description 11
- 229920002401 polyacrylamide Polymers 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 125000000129 anionic group Chemical group 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000005708 Sodium hypochlorite Substances 0.000 description 8
- 230000009172 bursting Effects 0.000 description 8
- 229940079593 drug Drugs 0.000 description 8
- 239000003814 drug Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 229920002472 Starch Polymers 0.000 description 7
- 239000008107 starch Substances 0.000 description 7
- 235000019698 starch Nutrition 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 244000005700 microbiome Species 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920000962 poly(amidoamine) Polymers 0.000 description 5
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 description 5
- 229960002218 sodium chlorite Drugs 0.000 description 5
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000003899 bactericide agent Substances 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 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
- 239000007787 solid 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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 239000001099 ammonium carbonate Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000007844 bleaching agent Substances 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
- 238000010411 cooking 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
- 230000006866 deterioration Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 230000001590 oxidative 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
- 239000001509 sodium citrate Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 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 3
- 229940038773 trisodium citrate Drugs 0.000 description 3
- 239000002023 wood Substances 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 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
- 150000001450 anions Chemical group 0.000 description 2
- 239000003242 anti bacterial 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
- 238000011109 contamination Methods 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
- 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
- 239000000463 material Substances 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
- 238000004513 sizing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 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
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing 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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 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
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-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
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 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
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 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
- 239000011111 cardboard Substances 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 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
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 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
- 235000011007 phosphoric acid Nutrition 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
- 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
- 239000012744 reinforcing agent Substances 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
- 238000012216 screening 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
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate 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
- 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
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 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
Landscapes
- Paper (AREA)
Abstract
Description
本発明は製紙工程中の調成工程における紙力増強剤の効果向上方法に関する。 The present invention relates to a method for improving the effect of a paper strength agent in a preparation step during a paper manufacturing 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。
Paper strength agents have traditionally been used in paper mills to impart strength to paper.
In recent years, due to an increase in the use of recycled paper in paper mills, raw material pulp that contains short fibers derived from recycled paper and has low paper strength is being used. Furthermore, due to the use of waste paper, metal ions contained in the papermaking white water increase the electrical conductivity within the papermaking system, making it difficult for the paper strength enhancer added to the raw material pulp to exert its effect. Under such circumstances, there is a need to improve the effect of paper strength enhancers, but increasing the amount of paper strength enhancers added leads to deterioration of water quality, which is environmentally undesirable.
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, Western paper, wrapping paper, etc., but in order to maintain the paper strength of the final sheet, measures to increase paper strength are required. Become. Therefore, paper strength enhancers are used even when waste paper is not used as a raw material, and from an environmental perspective, there is a need to improve the effect of paper strength enhancers without increasing the amount of paper strength enhancers 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 paper strength enhancer added, for example, Patent Document 1 describes that a solution of aqueous sodium hypochlorite, etc. Discloses a method that can effectively reduce the amount of paper strength enhancer 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 ammonium sulfate solution or aqueous ammonia has been done.
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 Document 2 discloses that a paper manufacturing method is provided in which the decomposition of starch in the paper manufacturing process is suppressed and the strength of the paper product does not deteriorate. Specifically, in a method for manufacturing paper containing waste paper, (1) a step of continuously or intermittently measuring water quality, (2) a step of measuring starch based on the water quality measurement results obtained in step (1) above, It is disclosed that the method includes a step of inactivating microorganisms having decomposition ability. Furthermore, various antibacterial agents have been disclosed as agents capable of inactivating microorganisms. Patent Document 3 also describes that microbial contamination progresses using waste paper, broken pulp, internally added starch, etc. as a nutrient source, and starch decomposition leads to deterioration of the strength of paper products, so a bactericide with an oxidizing effect is added to the raw material. It is disclosed that disorders caused by microbial contamination can be controlled by this method.
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。 In addition, as a method for sterilizing raw materials in the paper manufacturing process, for example, Patent Document 4 describes (a) the addition point of the sodium hypochlorite aqueous solution and (b) the addition point of the ammonium sulfate aqueous solution so that it flows into the white water line of the paper manufacturing process. Component (a) and component (b) are added to dilution water in a dilution water line in which addition points of active ingredients are provided in the order of addition points, and the component (a) and (b) are added in the dilution water line. It is disclosed that a mixed aqueous solution with the components is prepared, and that the pH of the mixed aqueous solution is 8 or more. However, this document does not disclose a method for improving the effect of the paper strength enhancer.
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。 Further, Patent Document 5 discloses a method for improving the effect of a paper strength enhancer, which includes a step of adding an oxidizing agent (halogen-containing oxidizing agent and/or hydrogen peroxide) to papermaking process water, and a process for increasing paper strength. A method is disclosed in which the effect of the paper strength enhancer is improved by bringing the oxidizing agent and the paper strength enhancer into contact at a specific concentration.
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-mentioned Patent Document 1 discloses adding a chemical to the pulping process water of the pulping process in order to reduce the amount of paper strength enhancer added in the preparation process. In addition, Patent Documents 2 and 3 mentioned above disclose that by adding an antibacterial agent such as an oxidizing agent to suppress starch decomposition by microorganisms during the paper manufacturing process, it is possible to prevent paper strength loss, which is a type of microbial damage. Disclosed. All of these methods involve adding chemicals to the papermaking process water before adding the paper strength enhancer, and do not improve the effect of the paper strength enhancer itself.
Moreover, the above-mentioned Patent Document 4, which discloses a method for sterilizing raw materials in the paper manufacturing process, does not disclose a method for improving the effect of the paper strength enhancer itself.
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。 Although Patent Document 5 discloses an invention related to a method for improving the effect of a paper strength enhancer, there is still room for further study on a method for improving the effect of the paper strength enhancer itself and such a composition.
本発明は、製紙工程中の調成工程で使用される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。 An object of the present invention is to provide a method for improving the effect of a paper strength enhancer used in a preparation step in a paper manufacturing process.
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、製紙工程の調成工程で添加される紙力増強剤の効果向上用組成物を特定の方法で添加することで、従来の方法と比較してより紙力増強剤の効果が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。 As a result of extensive research in order to solve the above problems, the inventor of the present invention has discovered that a composition for improving the effect of a paper strength enhancer added in the preparation process of the paper manufacturing process can be added in a specific manner. The present invention was completed based on the discovery that the effect of the paper strength enhancer is improved compared to conventional methods.
本発明は、製紙工程中の調成工程における紙力増強剤の効果向上方法であって、上記調成工程において、紙力増強剤を添加する紙力増強剤添加工程と、上記調成工程に添加される白水に上記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を有することを特徴とする紙力増強剤の効果向上方法である。
紙力増強剤の効果向上用組成物は、アンモニウム塩とハロゲン系酸化剤とを混合することにより生成される、又は、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、若しくは、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、ことが好ましい。
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（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い。
第一組成物のｐＨが、４．５～８．５であることが好ましい。
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紙力増強剤の効果向上用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調成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 is a method for improving the effect of a paper strength enhancer in a preparation step in a paper manufacturing process, and includes a paper strength enhancer addition step in which the paper strength enhancer is added in the preparation step, and a paper strength enhancer addition step in which the paper strength enhancer is added in the preparation step. This is a method for improving the effect of a paper strength enhancer, comprising the step of adding a composition for improving the effect of the paper strength enhancer to white water to be added.
The composition for improving the effect of a paper strength enhancer is produced by mixing an ammonium salt and a halogen-based oxidizing agent, or by mixing a first composition containing an ammonium salt and an alkaline agent with a halogen-based oxidizing agent. It is preferable that the second composition containing the halogenated oxidizing agent and the alkaline agent be mixed with the ammonium salt.
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 (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.
Preferably, the pH of the first composition is 4.5 to 8.5.
It is preferable that the contact concentration of the composition for improving the effect of the paper strength enhancer and the composition for improving the effect of the paper strength enhancer when the paper strength enhancer contacts the composition for improving the effect of the paper strength enhancer is 0.1 to 35 mg/L. .
The residual chlorine concentration in the preparation water after the composition addition step is preferably 0.1 to 35 mg/L.
本発明によれば、製紙工程中の調成工程で使用される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, it is possible to provide a method for improving the effect of a paper strength enhancer used in a preparation step during a paper manufacturing process.
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 construed narrowly thereby. .
本明細書中、「Ｘ～Ｙ」は、「Ｘ以上、Ｙ以下」を意味する。 In the present specification, "X to Y" means "more than or equal to X and less than or equal to Y."
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が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、製紙工程の調成工程で添加される紙力増強剤に対し紙力増強剤の効果向上用組成物を特定の方法で接触させることで、紙力増強剤の効果をより向上させることができるという事実を見出し、本発明の紙力増強剤の効果向上方法を完成させた。 As disclosed in the above-mentioned Patent Document 5, the applicant of the present invention has a process of adding an oxidizing agent and a process of adding a paper strength enhancer to papermaking process water, and has a process of adding an oxidizing agent (halogen and/or hydrogen peroxide) and the paper strength enhancer, and the contact concentration of the oxidant when the paper strength enhancer and the oxidant contact is 0.1. Discloses an invention of a method for improving the effect of a paper strength enhancer characterized by a concentration of ~35 mg/L. As a result of intensive studies on methods for further improving the effect of paper strength enhancers, the present inventors have developed a specific composition for improving the effect of paper strength enhancers for paper strength enhancers added in the preparation step of the papermaking process. The inventors have discovered that the effect of the paper strength enhancer can be further improved by contacting the paper with the paper strength enhancer, and have completed the method of improving the effect of the paper strength enhancer of the present invention.
通常、製紙工程は、パルプと呼ばれる紙の原料を製造するパルプ化工程と、紙を抄く前にパルプ繊維を物理的に加工したり薬品を添加したりする調成工程と、パルプをシート状に広げ、脱水、乾燥、表面加工などを行う抄紙工程とを有する。
本発明は、上述した製紙工程中の調成工程における紙力増強剤の効果向上方法である。
具体的には、上記調成工程において、紙力増強剤を添加する紙力増強剤添加工程と、上記調成工程に添加される白水に上記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を有する。
Normally, the paper manufacturing process consists of a pulping process to produce the raw material for paper called pulp, a preparation process to physically process pulp fibers and add chemicals before making paper, and a process to convert pulp into sheets. The papermaking process includes spreading, dewatering, drying, and surface treatment.
The present invention is a method for improving the effect of a paper strength enhancer in the preparation step in the papermaking process described above.
Specifically, in the above-mentioned preparation step, there is a paper-strength agent addition step in which a paper-strength agent is added, and a composition for improving the effect of the paper-strength agent is added to the white water added in the above-mentioned preparation step. and a composition addition step.
上記紙力増強剤添加工程は、上記調成工程において紙原料に紙力増強剤を添加する。
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。
In the paper strength agent addition step, a paper strength agent is added to the paper raw material in the preparation step.
As the paper strength enhancer in the present invention, those commonly used in the paper manufacturing process can be used without particular limitation, and any one having ionic properties such as cationic, anionic, amphoteric, and nonionic properties may be used. For example, cationic structures such as polyacrylamide, polyamidoamine/epichlorohydrin, polyamidoamine, glyoxal-modified polyamidoamine/epichlorohydrin, amine polyester polyether, and salts thereof are introduced. Paper strength enhancer; polyacrylamide with anionic group introduced, polyacrylamide-acrylic acid copolymer, polyacrylic acid, polyacrylamide partial hydrate, polyacrylamide-2-acrylamide-2-methylpropanesulfonic acid copolymer paper strength enhancers into which anionic structures are introduced, such as compounds, carboxymethyl cellulose, and their salts; Paper strength enhancers having a structure introduced therein; paper strength enhancers having nonionic structures such as polyacrylamide, starch, polyvinyl alcohol, and salts thereof, and the like. As the paper strength enhancer in the present invention, one of these can be used alone or two or more can be used in combination. Further, these paper strength enhancers may be in any form such as a solution (liquid) or a 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。
上記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。
A commercially available paper strength enhancer can be used as the cationic paper strength enhancer.
Examples of the above-mentioned cationic paper strength enhancers include internal paper strength enhancers and surface paper strength enhancers, and internal paper strength enhancers are further classified into dry paper strength enhancers and wet paper strength enhancers. . Examples of the internal paper strength enhancer include polyacrylamide, polyacrylamide into which a cationic group, an anionic group, or both have been introduced, and polyamidoamine/epichlorohydrin. Examples of the surface paper strength enhancer include polyacrylamide and polyvinyl alcohol. Preferably, the dry paper strength enhancer is polyacrylamide, polyacrylamide into which a cationic group, an anionic group, or both have been introduced, and the wet paper strength enhancer is polyamidoamine/epichlorohydrin.
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、紙力増強効果向上用組成物を特定の方法で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 monobrolamine have traditionally been added to the paper manufacturing process for the purpose of sterilization, and paper strength enhancers have been added for the purpose of improving paper strength. ing. By adding a bactericide to the raw material line of the paper manufacturing process, we can prevent the consumption of paper strength agents derived from raw materials such as starch by microorganisms, and the amount of paper strength agents added in the adjustment process etc. It is known that it is possible to reduce (Patent Documents 1 to 3 above).
In addition, various chemicals are added in the paper manufacturing process depending on the purpose. For example, pH adjusters (alkaline agents), sizing agents, drainage improvers, etc. are also added. These drugs are added so that the effects of each drug are exhibited, and the effects of one drug are not inhibited by the other drugs.
As mentioned above, paper strength enhancers include cationic paper strength enhancers and anionic paper strength enhancers, but the addition position of other agents is not changed depending on the type of paper strength enhancer. The paper strength agent is added in such a way that it does not come into contact with the anionic agent. This is because if the cationic paper strength enhancer and anionic agent (bactericidal agents such as oxidizing agents) react and cause aggregation, the paper strength enhancer may not be dispersed uniformly and the chemical effect may not be fully exerted. This is because Non-uniform dispersion of paper strength enhancers during the paper manufacturing process leads to deterioration of the quality of the paper produced. Conventionally, paper strength enhancers and anionic bactericides (oxidizing agents, etc.) were mixed at a concentration that would allow them to react. It was added to avoid contact.
On the other hand, as a result of studying how to improve the effect of the paper strength enhancer itself, the present invention provides a method for increasing paper strength by bringing a composition for improving paper strength increasing effect into contact with the paper strength enhancer in a specific manner. This was the first time it was discovered that it could improve the effectiveness of drugs.
本発明は、上記調成工程に添加される白水に上記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を有する。
上記白水とは、製紙工程の各工程で生じる脱水、濾過され循環使用される処理水であり、調成工程に添加される白水は工場毎に異なるのが通常である。
The present invention has a composition addition step of adding the composition for improving the effect of the paper strength enhancer to the white water added in the preparation step.
The above-mentioned white water is treated water that is generated in each step of the paper manufacturing process and is dehydrated, filtered, and recycled, and the white water added to the preparation process usually differs from factory to factory.
なお、酸化剤を含む組成物を製紙工程水に添加することで作製される紙の強度が向上する詳細は明らかではないが、メカニズムとしては次のようなことが考えられる。但し、本開示はこれらの考え方に限定されるものではない。
１つは、製紙工程水に添加された組成物中の酸化剤が、製紙工程水に含まれるパルプ繊維上のアニオンと結合しているカチオン性のカルシウムイオンなどを剥離させ、繊維のアニオンをむき出しにすることで、カチオン基を有するカチオン性の紙力増強剤の定着を促進させていると考えられる。
もう１つは、製紙工程水に酸化剤が添加されると、塩素や臭素などのマイナスの電荷を帯びた成分を中心に、カチオン基を有する紙力増強剤が引き寄せられ、パルプ繊維と紙力増強剤とが凝集し、紙力増強効果が向上すると考えられる。
本発明では、上記調成工程に添加される白水に上記紙力増強剤の効果向上用組成物を添加する上記組成物添加工程を有することで、上記紙力増強剤の効果向上を十分に図ることができる。この理由は明確ではないが、以下の通りであると考えられる。なお、以下の説明は上記紙力増強剤の効果向上用組成物として後述するモノクロラミンを使用した場合で説明する。
モノクロラミンを添加した白水を調成工程に添加した場合と、調成工程に原料等と合せてモノクロラミンを添加した場合とを比較すると、モノクロラミンを添加した白水を調成工程に添加した場合の方が、調成工程における残留塩素濃度が高くなる。これはモノクロラミンを添加した白水を調成工程に添加した場合の方がモノクロラミンの無駄な消費が抑えられるからと考えられる。
また、白水中にモノクロラミンが分散されている状態で原料と一緒になることで効率よく紙力増強剤やパルプ繊維と接触することで効果が良くなっていると考えられる。
Although the details of how the strength of paper produced by adding a composition containing an oxidizing agent to water in the papermaking process is not clear, the following mechanism may be considered. However, the present disclosure is not limited to these ideas.
One is that the oxidizing agent in the composition added to the papermaking process water separates cationic calcium ions, etc. that are bonded to the anions on the pulp fibers contained in the papermaking process water, exposing the anions on the fibers. It is thought that this promotes fixation of the cationic paper strength agent having a cationic group.
Another problem is that when an oxidizing agent is added to the water in the papermaking process, paper strength enhancers with cationic groups are attracted mainly to negatively charged components such as chlorine and bromine, and the paper strength enhancers are attracted to the pulp fibers and paper strength. It is thought that the paper strength enhancing effect is improved by aggregation of the reinforcing agent.
In the present invention, the effect of the paper strength enhancer is sufficiently improved by including the composition addition step of adding the composition for improving the effect of the paper strength enhancer to the white water added in the preparation step. be able to. Although the reason for this is not clear, it is thought to be as follows. The following description will be made based on the case where monochloramine, which will be described later, is used as a composition for improving the effect of the paper strength enhancer.
Comparing the case where white water to which monochloramine has been added is added to the preparation process and the case where monochloramine is added to the preparation process along with raw materials, etc., the case where white water to which monochloramine has been added is added to the preparation process. In this case, the residual chlorine concentration in the preparation process is higher. This is thought to be because unnecessary consumption of monochloramine can be suppressed when white water to which monochloramine has been added is added to the preparation process.
In addition, it is thought that monochloramine is dispersed in white water and combined with the raw materials to efficiently contact the paper strength agent and pulp fibers, thereby improving the effect.
上記紙力増強剤の効果向上用組成物（以下、単に効果向上用組成物ともいう）としては、特定の方法で製造した組成物が好適に用いられる。
具体的には、上記効果向上用組成物としては、アンモニウム塩とハロゲン系酸化剤とを混合することにより生成される、又は、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、若しくは、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、ことが好ましい。
As the composition for improving the effect of the paper strength enhancer (hereinafter also simply referred to as the composition for improving the effect), a composition produced by a specific method is preferably used.
Specifically, the effect-improving composition is produced by mixing an ammonium salt and a halogen-based oxidizing agent, or a first composition containing an ammonium salt and an alkaline agent and a halogen-based oxidizing agent. or by mixing the second composition containing the halogenated oxidizing agent and the alkaline agent and the ammonium salt.
上記アンモニウム塩とハロゲン系酸化剤とを混合することにより生成される効果向上用組成物としては、具体的には、例えば、モノクロラミン及び／又はモノブロラミンが挙げられる。 Specific examples of the effect-improving composition produced by mixing the ammonium salt and the halogen-based oxidizing agent include monochloramine and/or monobrolamine.
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、上記アンモニウム塩としては、具体的には後述するものが挙げられる。また、上記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 monobrolamine, which are commonly used as oxidizing agents, are mild oxidizing agents produced by 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, and specific examples of the ammonium salt include those mentioned below. It is also known to mix monochloramine or monobrolamine with an alkaline agent for the purpose of stabilizing monochloramine and monobrolamine produced by the above method. It is also known to separately add monochloramine, monobrolamine, and an alkaline agent to a target for the purpose of adjusting the pH of the target to which monochloramine or monobrolamine is added (Patent Document 4 mentioned above).
また、モノクロラミン及び／又はモノブロラミンの作製時に、アンモニウム塩にアルカリ剤を含有させ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上記モノクロラミン及び／又はモノブロラミン、並びに、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。
また、上記モノクロラミン及び／又はモノブロラミンの作製時に、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。
In addition, when producing monochloramine and/or monobrolamine, monochloramine and/or monobrolamine produced by reacting an ammonium salt containing an alkaline agent with a halogenated oxidizing agent are ammonium salts that do not contain an alkaline agent. Excellent paper strength enhancement compared to the above-mentioned monochloramine and/or monobrolamine produced by reacting a salt with a halogen-based oxidizing agent, and monochloramine and/or monobrolamine containing an alkaline agent. It has the effect of improving the effectiveness of drugs.
Furthermore, during the production of the monochloramine and/or monobrolamine described above, the monochloramine and/or monobrolamine produced by reacting a halogenated oxidizing agent containing an alkali agent with an ammonium salt does not contain an alkali agent. Superiority compared to conventional monochloramine and/or monobrolamine produced by reacting a halogenated oxidizing agent and ammonium salt, and conventional monochloramine and/or monobrolamine containing an alkali agent. It has the effect of improving the effectiveness of paper strength enhancers.
上述の特定の方法で製造した組成物として具体的に例示した製法のうち、後者の方法で製造した組成物、すなわち、アンモニウム塩にアルカリ剤を含有させ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、前者の方法で製造されたモノクロラミン及び／又はモノブロラミン、並びに、こ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、特に優れた紙力増強剤の効果向上作用を有する。 Among the production methods specifically exemplified as the composition produced by the above-mentioned specific method, the composition produced by the latter method, that is, the composition in which the ammonium salt contains an alkaline agent, is reacted with a halogen-based oxidizing agent. The composition produced by reacting a halogen-based oxidizing agent containing an alkali agent with an ammonium salt is composed of monochloramine and/or monobrolamine produced by the former method, and , has a particularly excellent effect of improving the effect of a paper strength enhancer, compared to monochloramine and/or monobrolamine containing an alkaline agent.
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、又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, and iron sulfate. (III) At least one selected from the group consisting of ammonium, ammonium persulfate, ammonium tungstate, ammonium metatungstate, ammonium thiocyanate, and ammonium polyphosphate is preferable. 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. Preferably it is a seed. The ammonium salt is 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. Preferably, it is more preferably 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 hypochlorites, chlorites, chlorates, perchlorates, 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 above hypochlorite include sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, and magnesium hypochlorite. The above-mentioned hypochlorite is preferably at least one selected from the group consisting of sodium hypochlorite, calcium hypochlorite, potassium hypochlorite, and magnesium hypochlorite, and sodium 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, magnesium chlorite, and the like. The above 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
The above-mentioned chlorine dioxide is an extremely unstable chemical substance, so it is extremely difficult to store and transport it. Therefore, it is preferable to manufacture (generate) chlorine dioxide on the spot by a known method and adjust the concentration before use.
For example, chlorine dioxide can be produced by the following reaction, and a commercially available chlorine dioxide generator (device) can also be used.
(1) Reaction of sodium hypochlorite, hydrochloric acid, and sodium chlorite NaOCl+2HCl+2NaClO 2 → 2ClO 2 +3NaCl+H 2 O
(2) Reaction between sodium chlorite and hydrochloric acid 5NaClO 2 +4HCl → 4ClO 2 +5NaCl+2H 2 O
(3) Reaction with sodium chlorate, hydrogen peroxide and sulfuric acid 2NaClO 3 +H 2 O 2 +H 2 SO 4 → 2ClO 2 +Na 2 SO 4 +O 2 +2H 2 O
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 a 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 alkaline agent used in the present invention is not particularly limited as long as it is an alkali metal salt or alkaline earth metal salt that exhibits 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, and 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 Preferably, it is at least one selected from the group consisting of sodium, sodium succinate, sodium fumarate, sodium lactate, and sodium tartrate. Furthermore, 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 bicarbonate, potassium carbonate, and trisodium citrate. More preferably, it is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, and trisodium citrate.
本発明では、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ことが好ましい。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 present invention, before mixing the ammonium salt and the halogen oxidizing agent, a first composition containing the ammonium salt and the alkaline agent, or a first composition containing the halogen oxidizing agent and the alkaline agent, is prepared. Preferably, two compositions are prepared. The 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 alkaline agent so that the pH of the first composition is 1.08 times or more the pH of the ammonium salt itself. This is because a composition produced by reacting an ammonium salt with a pH within the above range with a halogen-based oxidizing agent has a sufficient effect of improving the effect of a paper strength enhancer.
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 1.2 times or more, relative to the pH of the halogen-based oxidizing agent itself. It is more preferable to include an alkaline agent so that This is because a composition produced by reacting a halogen-based oxidizing agent with a pH within the above range with an ammonium salt has a sufficient effect of improving the effect of a paper strength enhancer.
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。
Further, 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 first composition preferably has a pH of 4.5 to 8.5, and when the ammonium salt is ammonium bromide, the first composition preferably has a pH of 7.5 to 8.5. It is preferably 0 to 8.5. Furthermore, when the ammonium salt is ammonium sulfamate, the pH of the first composition is preferably 5.5 to 8.5.
In the present invention, pH can be measured using a commonly used measuring device, 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 to 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 of the halogen-based oxidizing agent to 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; : More preferably from 1.1 to 1:2, even more preferably from 1:1.2 to 1:2, particularly preferably from 1:1.2 to 1:1.6.
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 of the first composition and the halogen-based oxidizing agent and the weight ratio of the second composition and the ammonium salt are the molar ratio of the halogen-based oxidizing agent and the ammonium salt (halogen-based oxidizing agent: ammonium salt) is preferably determined within the above range.
本発明において、上記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 present invention, it is preferable that the contact concentration of the composition when the effect improving composition and the paper strength enhancer come into contact is 0.1 to 35 mg/L. This is because a more sufficient paper strength enhancing effect can be obtained by bringing the composition of the present invention in the above concentration range into contact with the paper strength enhancing agent.
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、上記効果向上用組成物と紙力増強剤とが接触する際の該効果向上用組成物の調成工程におけるパルプスラリーに対する濃度を意味するものである。白水に上記組成物を添加する際には、調成工程におけるパルプスラリーに対する上記組成物の接触濃度が所定の範囲内となるように、添加する。 In this specification, "contact concentration of the composition when the composition for improving the effect of the paper strength enhancer and the paper strength enhancer contact" means that the composition for improving the effect of the paper strength enhancer contacts the composition for improving the effect of the paper strength enhancer. It means the concentration relative to the pulp slurry in the preparation process of the effect-improving composition at the time of contact. When adding the composition to white water, it is added so that the concentration of the composition in contact with the pulp slurry in the preparation step is within a predetermined range.
本発明において、組成物添加工程後の調成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, it is preferable that the residual chlorine concentration (concentration in terms of residual chlorine) of the preparation water after the composition addition step is 0.1 to 35 mg/L. In addition, the residual chlorine concentration in the papermaking process water after the composition addition step is more preferably 0.5 to 30 mg/L, even more preferably 1 to 30 mg/L, from the economic point of view. , 1 to 25 mg/L or 1 to 20 mg/L is preferred.
本発明において、紙力増強剤添加工程により紙原料に添加される紙力増強剤は、組成物添加工程で添加される白水と同一箇所及び／又は調成工程の上流側に添加されることが好ましい。上記効果向上用組成物を含む白水が調成工程に添加されると同時に、調成工程水中の微生物により効果向上用組成物が消費され始める可能性があるため、紙力増強剤を上記白水と同一箇所及び／又は調成工程の上流側に添加することで、上記調成工程水中の微生物により分解される前に効率よく上記効果向上用組成物を紙力増強剤に接触させることができる。
なお、本明細書においては、「上流側」は、調成工程水の流れ方向に対する上流側を意味する。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 added to the paper raw material in the paper strength agent addition step may be added at the same location as the white water added in the composition addition step and/or on the upstream side of the preparation step. preferable. At the same time that the white water containing the above-mentioned effect-improving composition is added to the preparation process, the effect-improving composition may begin to be consumed by microorganisms in the preparation process water. By adding it at the same location and/or upstream of the preparation process, the effect-improving composition can be efficiently brought into contact with the paper strength enhancer before being decomposed by microorganisms in the preparation process water.
In addition, in this specification, "upstream side" means the upstream side with respect to the flow direction of preparation process water. In addition, in this specification, the same location means the same equipment, the same tank, and the same piping (piping between equipment).
また、本発明において紙力増強剤添加工程により紙原料に添加される紙力増強剤が、組成物添加工程で添加される白水と同一箇所で添加され、及び／又は調成工程の上流側に添加される場合、上記紙力増強剤及び効果向上用組成物の添加が開始されるタイミングは、調成工程水の流速によって決定されることが好ましい。調成工程の上流側で添加された紙力増強剤が効果向上用組成物の添加位置に到達したタイミングで、効果向上用組成物を添加することにより、より濃度の濃い紙力増強剤と、より濃度の濃い効果向上用組成物とを、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, the paper strength agent added to the paper raw material in the paper strength agent addition step is added at the same location as the white water added in the composition addition step, and/or on the upstream side of the preparation step. When added, the timing at which the addition of the paper strength enhancer and effect improving composition is started is preferably determined by the flow rate of the preparation process water. By adding the effect-improving composition at the timing when the paper strength-enhancing agent added on the upstream side of the preparation process reaches the addition position of the effect-improving composition, a paper strength-enhancing agent with a higher concentration can be obtained. This is because it is possible to more reliably contact the composition with a higher concentration of the composition for improving effects.
なお、上記効果向上用組成物の添加量は、該効果向上用組成物と紙力増強剤とが接触する際の効果向上用組成物の接触濃度が、０．１～３５ｍｇ／Ｌとなるよう設定されることが好ましい。例えば、紙力増強剤が効果向上用組成物の残留濃度（残留塩素換算濃度）が０．１～３５ｍｇ／Ｌの調成工程水と接触するように、効果向上用組成物の添加量が設定されることが好ましい。なお、紙力増強剤と効果向上用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 effect-improving composition added is such that the contact concentration of the effect-improving composition when the effect-improving composition and the paper strength enhancer come into contact is 0.1 to 35 mg/L. It is preferable that this is set. For example, the amount of the effect-improving composition added is set so that the paper strength enhancer comes into contact with the preparation process water in which the residual concentration of the effect-improving composition (concentration in terms of residual chlorine) is 0.1 to 35 mg/L. It is preferable that Note that the paper strength enhancing effect can be obtained by contacting the paper strength enhancing agent and the effect improving composition at a concentration that allows them to 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。 The paper strength enhancer is preferably added in an amount of 0.01 to 2.0% by weight, and preferably 0.05 to 1.0% by weight, based on 100% by weight of the solid content of the pulp. Preferably, it is added in an amount of 0% by weight. If the amount of the paper strength enhancer added is less than the above 0.01% by weight, there is a possibility that the paper strength enhancing effect will not be sufficiently obtained, and if it exceeds 2.0% by weight, it may be difficult to obtain the pulp sheet or final product. This is because the paper strength agent may adhere to the paper being used, causing 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。 In addition, the description of "amount of residual chlorine" in the present invention means "value in terms of amount of residual chlorine" when the halogen-based oxidizing agent is not a chlorine-based oxidizing agent.
本発明において、上述した紙力増強剤や効果向上用組成物を含む白水が添加される紙原料は、上記調成工程の前工程であるパルプ化工程において製造されるものであり、古紙及び木材のいずれであってもよい。 In the present invention, the paper raw material to which white water containing the above-mentioned paper strength enhancer and effect-improving composition is added is produced in the pulping process, which is a pre-process of the above-mentioned preparation process, and is made of waste paper and wood. It may be either.
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・精選工程及び脱水・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 a 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 disintegration process, a rough selection/selection process, and a dehydration/washing process. Furthermore, it may also include a deinking step to remove ink contained in the waste paper and a bleaching step to chemically bleach the pulp. To explain each process in detail, there is a disintegration (pulper) process in which waste paper as a raw material is mixed with water and mechanically turned into pulp slurry, a rough selection (dust removal) process to remove foreign substances contained in waste paper, and a deinking agent. A deinking process in which ink components are removed by adding a bleaching agent, a screening process in which foreign substances contained in waste paper and pulp are separated using a screen, a cleaning process in which the pulp slurry is washed with water, a dehydration process in which the pulp is dehydrated, and a bleaching agent is added. This is a bleaching process in which the pulp is bleached. The water used in each of the above steps and the water drained are called white water, and the mixture of waste paper, which is a raw material, and white water in the pulper step 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。 Moreover, when wood is used as a paper raw material, the paper manufacturing process may include a pulping process of chemical pulp or a pulping process of mechanical pulp as the pulping process. The pulping process of chemical pulp mainly includes a wood preparation process, a cooking process, a sorting/washing process, and a dehydration process. Furthermore, it may also include a bleaching step in which the pulp is chemically bleached. In the above-mentioned cooking process, chemicals are added to the chips and boiled at high temperature and pressure to dissolve the resin (lignin) and extract the fibers, turning the chips into pulp. That is, the pulp raw material becomes pulp slurry through a cooking process. Moreover, the pulping process of mechanical pulp mainly includes a crushing process, a dust removal process, and a concentration process. Furthermore, it may also include a bleaching step in which the pulp is chemically bleached. In the above process, pulp slurry is obtained by mechanically forming fibers.
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。 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１～６、比較例１）
［原料の作製］
（１）段ボールを３ｃｍ×３ｃｍの大きさに裁断したものを固形分濃度３％になるように上水に浸した後、実験室用離解機を用いて２０００ｒｐｍの回転数で２０分間離解を行った。
（２）得られたパルプスラリーから未離解物を取り除くため、実験室用フラットスクリーンに通し、得られたパルプスラリーのパルプ濃度が３％となるように調成し、これを原料とした。
［模擬白水の作製］
得られた原料を一部採取し、固形分濃度０．２％となるように上水で希釈し、これを模擬白水とした。
［原料の調成、紙力測定用シートの作製・紙力の測定］
（１）模擬白水に予め下記製法で得られた効果向上用組成物（１）又は効果向上用組成物（２）を、最終的に原料と模擬白水を混ぜてパルプ濃度１％のスラリーとなったものに対して、表１に示した濃度となるように添加し、スリーワンモーターを用いて１５０ｒｐｍで３０秒間攪拌し、これを模擬白水（効果向上用組成物含）とした。なお、効果向上用組成物（１）又は（２）は、下記工程（２）で全ての薬剤を添加し、攪拌し終わって最終的に得られる調成した原料の一部を採取し、全残留塩素濃度を測定するために、対１％パルプスラリーの濃度で添加した。
＜効果向上用組成物（１）＞
硫酸アンモニウム（キシダ化学社製試薬）３．５ｍｏｌ／Ｌと次亜塩素酸ナトリウム（キシダ化学社製試薬）１．７ｍｏｌ／Ｌとを混合した反応物。
＜効果向上用組成物（２）＞
硫酸アンモニウム（キシダ化学社製試薬）３．５ｍｏｌ／Ｌ及び水酸化ナトリウム（富士フィルム和光純薬社製試薬）２．７×１０－３ｍｏｌ／Ｌを含む第一組成物（ｐＨ６．８）と次亜塩素酸ナトリウム（キシダ化学社製試薬）１．７ｍｏｌ／Ｌを含む第二組成物とを混合した反応物。
（２）原料をスリーワンモーターを用いて１５０ｒｐｍで攪拌しながら１５秒おきに硫酸バンド（硫酸アルミニウム）（対パルプ３０ｋｇ／ｔｏｎ）、サイズ剤（対パルプ６．０ｋｇ／ｔｏｎ）、下記紙力増強剤（対パルプ１６ｋｇ／ｔｏｎ）を添加し、最後にパルプ濃度が１%になるように模擬白水（効果向上用組成物含）を加え、さらに６０秒間攪拌した。得られた調成した原料の残留塩素濃度を測定した。結果を表１に示した。
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）
（３）上記工程（２）で調成した原料を用いＪＩＳ Ｐ８２２２に準じてシートを作製した。
（４）得られたシートを用いＪＩＳ Ｐ８１１２の方法で比破裂強度を測定した。結果を表１に示した。
(Examples 1 to 6, Comparative Example 1)
[Preparation of raw materials]
(1) Cardboard was cut into pieces of 3 cm x 3 cm and soaked in tap water to a solid content concentration of 3%, and then disintegrated for 20 minutes at a rotation speed of 2000 rpm using a laboratory disintegrator. Ta.
(2) In order to remove undisintegrated materials from the obtained pulp slurry, it was passed through a laboratory flat screen, and the obtained pulp slurry was adjusted to have a pulp concentration of 3%, and this was used as a raw material.
[Preparation of simulated white water]
A portion of the obtained raw material was collected and diluted with tap water to a solid content concentration of 0.2%, which was used as simulated white water.
[Preparation of raw materials, preparation of sheets for measuring paper strength, measurement of paper strength]
(1) Add the effect-improving composition (1) or effect-improving composition (2) obtained in advance by the following manufacturing method to the simulated white water, and finally mix the raw materials and the simulated white water to form a slurry with a pulp concentration of 1%. The mixture was added to the concentration shown in Table 1 and stirred for 30 seconds at 150 rpm using a three-one motor to obtain simulated white water (containing an effect-improving composition). In addition, the effect-improving composition (1) or (2) is prepared by adding all the drugs in the following step (2), collecting a part of the final prepared raw material obtained after stirring, and adding all the drugs. To measure the residual chlorine concentration, it was added at a concentration of 1% pulp slurry.
<Composition for improving effects (1)>
A reaction product obtained by mixing 3.5 mol/L of ammonium sulfate (reagent manufactured by Kishida Chemical Co., Ltd.) and 1.7 mol/L of sodium hypochlorite (reagent manufactured by Kishida Chemical Co., Ltd.).
<Composition for improving effects (2)>
A first composition (pH 6.8) containing 3.5 mol/L of ammonium sulfate (reagent manufactured by Kishida Chemical Co., Ltd.) and 2.7 x 10 -3 mol/L of sodium hydroxide (reagent manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) and a second composition A reaction product mixed with a second composition containing 1.7 mol/L of sodium chlorite (reagent manufactured by Kishida Chemical Co., Ltd.).
(2) While stirring the raw materials at 150 rpm using a three-one motor, add sulfuric acid band (aluminum sulfate) (30 kg/ton for pulp), sizing agent (6.0 kg/ton for pulp), and the following paper strength agents. (16 kg/ton of pulp) was added, and finally, simulated white water (containing an effect improving composition) was added so that the pulp concentration was 1%, and the mixture was further stirred for 60 seconds. The residual chlorine concentration of the obtained prepared raw material was measured. The results are shown in Table 1.
Paper strength enhancer: Internally added type dry paper strength enhancer (cationic polyacrylamide dry paper strength enhancer)
(3) A sheet was produced according to JIS P8222 using the raw materials prepared in step (2) above.
(4) Using the obtained sheet, the specific bursting strength was measured according to the method of JIS P8112. The results are shown in Table 1.
上記工程（２）で調製したパルプスラリーの残留塩素濃度、上記工程（４）で測定した比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
（比破裂強度の測定）
比破裂試験機：日本Ｔ．Ｍ．Ｃ社製
The residual chlorine concentration of the pulp slurry prepared in step (2) above and the specific bursting strength measured in step (4) above were measured using the following equipment.
(Measurement of residual chlorine concentration)
Residual chlorine measuring device: Kasahara Kogyo Co., Ltd. (measurement of specific bursting strength)
Specific burst tester: Japan T. M. Made by company C
（紙力向上率）
（１）得られた各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、表１に示した。
［式］（紙力向上率）＝（各実施例の比破裂強度）／（比較例１の比破裂強度）×１００
(Paper strength improvement rate)
(1) The paper weight of each obtained pulp sheet was measured, and the basis weight was calculated.
(2) The pulp sheet in (1) was ruptured using the JIS P 8112 "Mullen low-pressure bursting tester for paper and paperboard" specified in JIS P 8223 "Handmade paper for testing - Test method for physical properties". It was measured in accordance with the method described in "Strength Test Method".
(3) The specific bursting strength was calculated from the basis weight obtained in (1) above and the bursting strength obtained in (2) above.
(4) The paper strength improvement rate was calculated based on the following formula and is shown in Table 1.
[Formula] (Paper strength improvement rate) = (Specific bursting strength of each example) / (Specific bursting strength of Comparative example 1) x 100
（実施例７～１０、比較例２）
［原料］
現場（某板紙工場）で採取した調成前原料（パルプ濃度３％）を準備した。
［白水］
現場（某板紙工場）で採取した白水を準備した。
［原料の調製、紙力測定用シートの作製・紙力の測定］
準備した白水に予め上記効果向上用組成物（２）を、最終的に原料と白水を混ぜてパルプ濃度１％のスラリーとなったものに対して、表２に示した濃度となるように添加し、スリーワンモーターを用いて１５０ｒｐｍで３０秒間攪拌し、これを白水（効果向上用組成物含）とした。
模擬白水（効果向上用組成物含）に代えて得られた白水（効果向上用組成物含）を用いた以外は、実施例１と同様にして原料を調成し、シートの作製及び比破裂強度の測定をした。結果を表２に示した。
(Examples 7 to 10, Comparative Example 2)
[material]
Raw materials before preparation (pulp concentration 3%) collected at the site (a certain paperboard factory) were prepared.
[Hakusui]
We prepared white water collected at the site (a certain paperboard factory).
[Preparation of raw materials, production of sheets for measuring paper strength, measurement of paper strength]
Add the above-mentioned effect improving composition (2) to the prepared white water in advance so that the concentration shown in Table 2 is obtained by mixing the raw material and white water to form a slurry with a pulp concentration of 1%. The mixture was stirred for 30 seconds at 150 rpm using a three-one motor to obtain white water (containing an effect-improving composition).
Raw materials were prepared in the same manner as in Example 1, except that the obtained white water (containing an effect-improving composition) was used instead of the simulated white water (containing an effect-improving composition), and sheet production and specific rupture were performed. I measured the strength. The results are shown in Table 2.
Claims (8)
前記調成工程において、紙力増強剤を添加する紙力増強剤添加工程と、前記調成工程に添加される白水に前記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を有する
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 enhancer in a preparation step during a paper manufacturing process, the method comprising:
In the preparation step, a paper strength enhancer addition step of adding a paper strength enhancer, and a composition addition step of adding a composition for improving the effect of the paper strength agent to white water added in the preparation step. A method for improving the effect of a paper strength enhancer, comprising:
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