JP4794346B2 - Deinking method and deinking agent - Google Patents
Deinking method and deinking agent Download PDFInfo
- Publication number
- JP4794346B2 JP4794346B2 JP2006106690A JP2006106690A JP4794346B2 JP 4794346 B2 JP4794346 B2 JP 4794346B2 JP 2006106690 A JP2006106690 A JP 2006106690A JP 2006106690 A JP2006106690 A JP 2006106690A JP 4794346 B2 JP4794346 B2 JP 4794346B2
- Authority
- JP
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- Prior art keywords
- deinking
- ink
- terpene
- compound
- 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.)
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- 239000002761 deinking Substances 0.000 title claims description 90
- 238000000034 method Methods 0.000 title claims description 39
- 239000003795 chemical substances by application Substances 0.000 title claims description 25
- 239000010893 paper waste Substances 0.000 claims description 37
- -1 terpene alcohols Chemical class 0.000 claims description 37
- 235000007586 terpenes Nutrition 0.000 claims description 32
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229920001131 Pulp (paper) Polymers 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 59
- 238000010998 test method Methods 0.000 description 16
- 238000005188 flotation Methods 0.000 description 15
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 6
- 150000003505 terpenes Chemical class 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 4
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229940116411 terpineol Drugs 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000944 linseed oil Substances 0.000 description 3
- 235000021388 linseed oil Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000003549 soybean oil Substances 0.000 description 3
- 235000012424 soybean oil Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BAVONGHXFVOKBV-UHFFFAOYSA-N Carveol Chemical compound CC(=C)C1CC=C(C)C(O)C1 BAVONGHXFVOKBV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- MVNCAPSFBDBCGF-UHFFFAOYSA-N alpha-pinene Natural products CC1=CCC23C1CC2C3(C)C MVNCAPSFBDBCGF-UHFFFAOYSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N citronellol Chemical compound OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 229930004069 diterpene Natural products 0.000 description 2
- 125000000567 diterpene group Chemical group 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229930003658 monoterpene Natural products 0.000 description 2
- 235000002577 monoterpenes Nutrition 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000010665 pine oil Substances 0.000 description 2
- GRWFGVWFFZKLTI-UHFFFAOYSA-N rac-alpha-Pinene Natural products CC1=CCC2C(C)(C)C1C2 GRWFGVWFFZKLTI-UHFFFAOYSA-N 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- XVULBTBTFGYVRC-HHUCQEJWSA-N sclareol Chemical compound CC1(C)CCC[C@]2(C)[C@@H](CC[C@](O)(C)C=C)[C@](C)(O)CC[C@H]21 XVULBTBTFGYVRC-HHUCQEJWSA-N 0.000 description 2
- 229930004725 sesquiterpene Natural products 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- FQTLCLSUCSAZDY-UHFFFAOYSA-N (+) E(S) nerolidol Natural products CC(C)=CCCC(C)=CCCC(C)(O)C=C FQTLCLSUCSAZDY-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical compound C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- REPVLJRCJUVQFA-UHFFFAOYSA-N (-)-isopinocampheol Natural products C1C(O)C(C)C2C(C)(C)C1C2 REPVLJRCJUVQFA-UHFFFAOYSA-N 0.000 description 1
- BAVONGHXFVOKBV-ZJUUUORDSA-N (-)-trans-carveol Natural products CC(=C)[C@@H]1CC=C(C)[C@@H](O)C1 BAVONGHXFVOKBV-ZJUUUORDSA-N 0.000 description 1
- ODFCWXVQZAQDSO-CMKODMSKSA-N (2s,4as,10ar)-1,1,4a-trimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthrene-2,6-diol Chemical compound CC([C@@H]1CC2)(C)[C@@H](O)CC[C@]1(C)C1=C2C=C(C(C)C)C(O)=C1 ODFCWXVQZAQDSO-CMKODMSKSA-N 0.000 description 1
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 1
- 239000001707 (E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-ol Substances 0.000 description 1
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 1
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 1
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LLKXNMNOHBQSJW-UHFFFAOYSA-N Elemol Natural products CCC(=C)C1CC(C=CC1(C)C)C(C)(C)O LLKXNMNOHBQSJW-UHFFFAOYSA-N 0.000 description 1
- XVULBTBTFGYVRC-UHFFFAOYSA-N Episclareol Natural products CC1(C)CCCC2(C)C(CCC(O)(C)C=C)C(C)(O)CCC21 XVULBTBTFGYVRC-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- BYTORXDZJWWIKR-UHFFFAOYSA-N Hinokiol Natural products CC(C)c1cc2CCC3C(C)(CO)C(O)CCC3(C)c2cc1O BYTORXDZJWWIKR-UHFFFAOYSA-N 0.000 description 1
- LAEIZWJAQRGPDA-UHFFFAOYSA-N Manoyloxid Natural products CC1(C)CCCC2(C)C3CC=C(C)OC3(C)CCC21 LAEIZWJAQRGPDA-UHFFFAOYSA-N 0.000 description 1
- FQTLCLSUCSAZDY-ATGUSINASA-N Nerolidol Chemical compound CC(C)=CCC\C(C)=C\CC[C@](C)(O)C=C FQTLCLSUCSAZDY-ATGUSINASA-N 0.000 description 1
- BLUHKGOSFDHHGX-UHFFFAOYSA-N Phytol Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C=CO BLUHKGOSFDHHGX-UHFFFAOYSA-N 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- HNZBNQYXWOLKBA-UHFFFAOYSA-N Tetrahydrofarnesol Natural products CC(C)CCCC(C)CCCC(C)=CCO HNZBNQYXWOLKBA-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- BOTWFXYSPFMFNR-OALUTQOASA-N all-rac-phytol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)=CCO BOTWFXYSPFMFNR-OALUTQOASA-N 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 1
- 229940088601 alpha-terpineol Drugs 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
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- CKDOCTFBFTVPSN-UHFFFAOYSA-N borneol Natural products C1CC2(C)C(C)CC1C2(C)C CKDOCTFBFTVPSN-UHFFFAOYSA-N 0.000 description 1
- 229940116229 borneol Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229930007646 carveol Natural products 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- GFJIQNADMLPFOW-UHFFFAOYSA-N cis-Elemol Natural products CC(=C)C1CC(C(C)(C)O)CCC1(C)C=C GFJIQNADMLPFOW-UHFFFAOYSA-N 0.000 description 1
- 235000000484 citronellol Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- DTGKSKDOIYIVQL-UHFFFAOYSA-N dl-isoborneol Natural products C1CC2(C)C(O)CC1C2(C)C DTGKSKDOIYIVQL-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- GFJIQNADMLPFOW-VNHYZAJKSA-N elemol Chemical compound CC(=C)[C@@H]1C[C@H](C(C)(C)O)CC[C@@]1(C)C=C GFJIQNADMLPFOW-VNHYZAJKSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002773 monoterpene derivatives Chemical class 0.000 description 1
- WASNIKZYIWZQIP-AWEZNQCLSA-N nerolidol Natural products CC(=CCCC(=CCC[C@@H](O)C=C)C)C WASNIKZYIWZQIP-AWEZNQCLSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- GGHMUJBZYLPWFD-CUZKYEQNSA-N patchouli alcohol Chemical compound C1C[C@]2(C)[C@@]3(O)CC[C@H](C)[C@@H]2C[C@@H]1C3(C)C GGHMUJBZYLPWFD-CUZKYEQNSA-N 0.000 description 1
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 description 1
- XQZFXRHLMVBGSW-UHFFFAOYSA-N pogosterol Natural products O1C(O)(C)C(C(C)C)(O)CC11C(C)C2C3(C)CCC(C4(C)C(CC(O)CC4)CC4=O)C4C3CC2O1 XQZFXRHLMVBGSW-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- GGHMUJBZYLPWFD-UHFFFAOYSA-N rac-patchouli alcohol Natural products C1CC2(C)C3(O)CCC(C)C2CC1C3(C)C GGHMUJBZYLPWFD-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 238000007127 saponification reaction Methods 0.000 description 1
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- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
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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)
Description
古紙原料から脱墨パルプを製造する過程で、効果的に脱インキを促進し、いわゆる難脱墨性古紙を含む古紙原料からも高品質な脱墨パルプを製造する脱墨方法及び脱墨剤に関するものである。 The present invention relates to a deinking method and a deinking agent that effectively promotes deinking in the process of producing deinked pulp from used paper raw materials, and produces high-quality deinked pulp from used paper raw materials including so-called hard-to-deink wastepaper. Is.
古紙原料を脱インキ処理し製造される脱墨パルプ(以下DIP)の製紙原料としての利用は古くから行われてきた。近年では資源保護の面から古紙の再利用が重要性を増し、古紙の更なる利用率の拡大に伴い雑誌古紙やオフィス古紙等の、これまでは利用率の低かった低級古紙の利用が進んでいる。また、原料古紙の主流である新聞古紙ではこれまでの酸性抄造から中性抄造への移行が進み、原料古紙自体もその性状が大きく変化しつつある。一方、印刷インキの面では大豆油インキやUVインキ等のエコインキへの移行により再利用される古紙中に含まれる印刷インキも変化している。さらに、DIPの製造過程では脱墨工程で使用する用水の循環率の上昇等、DIPを取り巻く環境は日々大きく変化してきている。 The use of deinked pulp (hereinafter referred to as DIP) produced by deinking waste paper raw materials as a papermaking raw material has been practiced for a long time. In recent years, the reuse of waste paper has become more important from the viewpoint of resource protection, and the use of low-grade waste paper, which has been low so far, such as magazine waste paper and office waste paper, has progressed along with further expansion of the waste paper usage rate. Yes. In addition, newspaper waste paper, which is the mainstream of raw paper, has been shifting from acidic papermaking to neutral papermaking, and the properties of the raw paper itself are changing greatly. On the other hand, in terms of printing ink, printing ink contained in waste paper that is reused by shifting to eco-ink such as soybean oil ink and UV ink is also changing. Further, in the manufacturing process of DIP, the environment surrounding DIP is changing day by day, such as an increase in the circulation rate of water used in the deinking process.
大豆油インキは従来の亜麻仁油を使用したインキと比べインキの乾燥皮膜強度が低くなり、脱墨工程でのインキの剥離は容易になるものの遊離インキが微細化し易くなる。一方、UVインキやトナーインキ等は印刷後の強度が亜麻仁油等を使用したインキよりも高いことが知られており、これらのインキを使用した印刷物が古紙中に混入するとDIP中に大きなインキ粒子が残存し障害を引き起こす。このような場合は機械的にインキ粒子を砕き微細化するなどの策が講じられるが、これらの硬いインキと混在する亜麻仁油などを使用したインキ分も微細化されるため微細遊離インキ粒子が増加する。現在、DIPの製造工程で主流をなしているフローテーション法では、主に脱インキを行うフローテーターでのインキ除去性が微細インキの増加に伴い低下することが知られており、遊離した微細なインキ粒子の増加はDIPの品質低下に繋がる。
また、フローテーターで除去しきれなかった微細な遊離インキは洗浄工程で除去する事ができるが、昨今の用水循環率の上昇により用水中に流出したインキが再び工程内に戻してしまうため、循環用水中に微細インキが蓄積し、DIP品質の低下を引き起こす。
さらに、DIPの品質が低下すると品質を維持するために過酸化水素等を用いた還元漂白により白色度の改善を図るが、DIP中の微細な遊離インキの増加は漂白剤である過酸化水素等の使用量を増加させ生産コストを上昇させるだけでなく、還元菌など微生物の増加を引き起こしスライムによるトラブルも増加する。
近年、脱墨原料の主流である新聞古紙の中性抄造化への移行が進んでいるが、酸性抄造された新聞古紙と比較し、中性抄造された新聞古紙は使用される薬剤等の影響でインキ剥離性が低下する傾向があり従来の機械応力ではヒゲチリと呼ばれる未剥離インキ量が増加する。未剥離インキを減少させるためには機械応力を強める必要があるが、古紙原料中に混在する酸性抄造された新聞古紙においてはインキ剥離性が過剰となる事、及び遊離インキの微細化を進行し、微細インキが蓄積するため、DIP品質が低下する。
微細インキによるDIP品質低下を改善するためにはインキ微細化を抑制する、または微細化したインキを再凝集させる等でインキをフローテーション法で除去しやすい粒径に調整する必要がある。
Soybean oil ink has a lower dry film strength than the ink using conventional linseed oil, and the ink can be easily peeled off in the deinking process, but the free ink is easily refined. On the other hand, UV ink and toner ink are known to have higher strength after printing than inks using linseed oil, etc. When printed matter using these inks is mixed in waste paper, large ink particles in DIP Remains and causes damage. In such a case, measures such as mechanically crushing the ink particles to make them finer are taken, but the amount of fine free ink particles increases because the ink content using linseed oil mixed with these hard inks is also refined To do. Currently, in the flotation method, which is the mainstream in the manufacturing process of DIP, it is known that the ink removability in the flowator that mainly performs deinking decreases with the increase in fine ink, An increase in ink particles leads to a decrease in the quality of DIP.
In addition, fine free ink that could not be removed by the floatator can be removed by the washing process, but since the ink that has flowed into the working water returns to the process again due to the recent increase in the water circulation rate, Fine ink accumulates in the water, causing a drop in DIP quality.
Furthermore, when the quality of DIP deteriorates, the whiteness is improved by reductive bleaching using hydrogen peroxide to maintain the quality. However, the increase in fine free ink in DIP is such as hydrogen peroxide as a bleaching agent. This not only increases the production cost by increasing the amount of sucrose, but also increases the number of microorganisms such as reducing bacteria, which increases the trouble caused by slime.
In recent years, there has been a shift to neutral paper making, which is the mainstream of deinking raw materials, but compared to acidic paper used for neutral paper, neutral paper used is affected by the chemicals used, etc. Ink releasability tends to decrease, and the amount of unpeeled ink called whisker increases with conventional mechanical stress. In order to reduce the unpeeled ink, it is necessary to increase the mechanical stress, but in the case of the acid-made newspaper wastepaper mixed in the wastepaper raw material, the ink peelability becomes excessive and the free ink has been made finer. DIP quality deteriorates because fine ink accumulates.
In order to improve the DIP quality deterioration due to fine ink, it is necessary to adjust the particle size so that the ink can be easily removed by the flotation method by suppressing the ink fineness or re-aggregating the fine ink.
このように、古紙原料中にいわゆる難脱墨性古紙が増加している状況下においては、従来からの脱墨剤(特許文献1、特許文献2、特許文献3、特許文献4参照)ではフローテーターでのインキ除去性が十分ではなく、さらに季節的な要因や古紙そのものの変動による振れによりDIPの品質のコントロールが困難であった。 Thus, in the situation where so-called hard-to-deink wastepaper is increasing in wastepaper raw materials, conventional deinking agents (see Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4) Ink removability with a rotator was not sufficient, and it was difficult to control the quality of DIP due to fluctuations due to seasonal factors and fluctuations in the waste paper itself.
一方、これまでにテルペンアルコール類またはテルペン炭化水素を古紙再生時に用いる方法が提案されている。例えば、特許文献5、6では脱墨工程において遊離したインキを吸着させる担体の調整用途としてテルペン系物質のパインオイルが使われている。特許文献7では脱墨剤の主成分に使われるSBとSISラバーの混合物を溶解させる有機溶剤としてテルペン炭化水素であるd−リモネンが使われている。これらの特許において、テルペン系物質は他の脱墨剤主成分の調整の目的で使われているに過ぎず、脱インキ性を利用する目的でのテルペン系化合物を使用とは言えない。
また、特許文献8では、脂肪酸や油脂の部分ケン化物による石けん類とテルペンアルコール類を組み合わせることにより石けん類の融点を低下させ扱いやすくできるとしている。しかし、石けん類とテルペンアルコール類の組み合わせによる脱墨剤では低級古紙が増加する昨今においては脱インキ性が十分とはいえない。
また、特許文献9では水溶性フレキソインキ印刷物用脱墨剤としてパインオイル、大豆油、短炭素鎖モノカルボン酸、グリコールエーテル系溶剤の混合物からなる脱墨剤が有用であると記載しているが、水溶性フレキソインキ印刷物は一般にインキ剥離が容易に行われるものの、近年の印刷古紙においては十分なインキ剥離性が得られない。また、グリコールエーテル系の溶剤は遊離インキの微細化を引き起こし、フローテーション性が低下するため、フローテーション法における脱墨剤としては十分な脱インキ性を有しているとは言えない。
Further, in Patent Document 8, it is said that the melting point of soaps can be lowered and handled easily by combining soaps and terpene alcohols by partial saponification of fatty acids and fats and oils. However, deinking agents using a combination of soaps and terpene alcohols cannot be said to have sufficient deinking properties in recent years when low-grade waste paper increases.
Patent Document 9 describes that a deinking agent comprising a mixture of pine oil, soybean oil, a short carbon chain monocarboxylic acid and a glycol ether solvent is useful as a deinking agent for water-soluble flexographic ink prints. In general, water-soluble flexographic ink prints are easily peeled off, but sufficient ink peelability cannot be obtained on recent printed paper. In addition, glycol ether solvents cause the free ink to become finer and the flotation property is lowered, so that it cannot be said that it has a sufficient deinking property as a deinking agent in the flotation method.
本発明が解決しようとする課題は、いわゆる難脱墨性古紙を含む古紙原料からも高品質なDIPを安定して製造するために、フローテーション法に代表される脱墨方法でフローテーターでのインキ除去性を効果的に改善する脱墨方法およびフローテーターでのインキ除去性を向上させる脱墨剤を提供することである。 The problem to be solved by the present invention is that a deinking method typified by a flotation method is used in a floatator in order to stably produce high-quality DIP from used paper raw materials including so-called hard-to-deink wastepaper. It is an object of the present invention to provide a deinking method for effectively improving ink removability and a deinking agent for improving ink removability with a flowator.
本発明は古紙原料に含まれるインキを脱インキ処理して脱墨パルプを製造する過程で、テルペンアルコール類とポリオキシアルキレン基を有する化合物を工程内に添加することを特徴とする脱墨方法に関する。 The present invention relates to a deinking method characterized by adding a terpene alcohol and a compound having a polyoxyalkylene group in the process in the process of producing a deinked pulp by deinking the ink contained in the waste paper raw material. .
本発明の別の態様に、(a)テルペンアルコール類及び(b)ポリオキシアルキレン基を有する化合物を含有し、それらの重量比が(a):(b)=1:99〜99:1であることを特徴とする脱墨剤がある。 In another embodiment of the present invention, (a) a terpene alcohol and (b) a compound having a polyoxyalkylene group are contained, and the weight ratio thereof is (a) :( b) = 1: 99 to 99: 1. There are deinking agents characterized by being.
本発明の別の態様に、(b)ポリオキシアルキレン基を有する化合物が下記一般式(1)で示される化合物であることを特徴とする前記脱墨剤がある。
R1−O−(AO)p−H (1)
(但し、R1は炭素数1から24のアルキル基、アルケニル基または炭素数6から30のアリール基を表し、AOは炭素数2から4のオキシアルキレン基を表し、pは1から200の整数である。)
In another embodiment of the present invention, there is provided the deinking agent, wherein the compound (b) having a polyoxyalkylene group is a compound represented by the following general formula (1).
R 1 —O— (AO) p—H (1)
(Wherein R 1 represents an alkyl group having 1 to 24 carbon atoms, an alkenyl group, or an aryl group having 6 to 30 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and p is an integer of 1 to 200) .)
本発明で用いるテルペンアルコール類は、(C5H8)nの構造を有するテルペン系化合物であって、かつ、水酸基を有する化合物である。炭素数の違いによりモノテルペン(n=2)、セスキテルペン(n=3)、ジテルペン(n=4)等の分類に分けられ、それぞれの構造に対応したテルペンアルコール類がある。テルペンアルコール類には様々な種類の化合物があるが一例としてモノテルペンアルコールに属する化合物としてテルピネオール、ゲラニオール、シトロネロール、ツヤノール、リナロール、メントール、カルベオール、ボルネオール等やセスキテルペンアルコール類としてはアトラントール、エレモール、カジノール、キャトロール、グロブロール、ネロリドール、パチュロール、バレリアノール、ファネソール、レドール、ポゴステロール等や、ジテルペン類としてはフィトール、スクラレオール、マノール、ヒノキオール等やそれらの異性体がある。この中で、テルピネオールのような常温・常圧下において液体であるテルペンアルコール類が、作業性が容易になる等の点で好ましい。 The terpene alcohols used in the present invention are terpene compounds having a structure of (C5H8) n and are compounds having a hydroxyl group. There are terpene alcohols corresponding to each structure, which are classified into monoterpenes (n = 2), sesquiterpenes (n = 3), diterpenes (n = 4) and the like depending on the difference in carbon number. There are various types of terpene alcohols, but examples include compounds belonging to monoterpene alcohols such as terpineol, geraniol, citronellol, tweenol, linalool, menthol, carveol, borneol, etc. and sesquiterpene alcohols such as atlantol, elemol, There are casinool, catrol, globrol, nerolidol, patchoulol, valeranol, fanesole, redol, pogosterol and the like, and diterpenes include phytol, sclareol, manol, hinokiol and the isomers thereof. Among these, terpene alcohols that are liquid at normal temperature and normal pressure, such as terpineol, are preferable in terms of ease of workability.
また、テルペンアルコール類には構造異性体が存在し、例えばテルピネオールではα体、β体、γ体の3種類の異性体が存在するが、構造の違いによる脱墨性の大きな差は確認されなかった。例えばテルピネオール(α体、β体、γ体混合物)とα−テルピネオール(α体)とでは脱インキ性に大きな差は確認されなかった。本結果より各種テルペンアルコールの構造異性体間での大きな差は無いと考えられる。また、一般的にテルペンアルコール類は異性体やテルペン炭化水素等の混合物として販売されているが、テルペンアルコールの含有割合が高いほうが性能向上の面からより好ましい。 Furthermore, terpene alcohols have structural isomers. For example, terpineol has three types of isomers, α-form, β-form, and γ-form, but a large difference in deinking property due to the difference in structure has not been confirmed. It was. For example, there was no significant difference in deinking properties between terpineol (α-form, β-form, γ-form mixture) and α-terpineol (alpha-form). From this result, it is thought that there is no big difference between the structural isomers of various terpene alcohols. Further, terpene alcohols are generally sold as a mixture of isomers and terpene hydrocarbons, but a higher content of terpene alcohol is more preferable from the viewpoint of performance improvement.
フローテーション法による脱墨方法において、テルペンアルコール類を脱墨工程に添加した場合、脱インキ性の大幅な向上が確認される。一方、DIPを清水で遊離しているインキを除去した完全洗浄パルプのDIP品質を比較した場合、テルペンアルコールを用いない場合と品質面での差はほとんど無い。完全洗浄パルプの品質は脱墨剤のインキ剥離性の指標となり、インキ剥離性が優れている場合は完全洗浄パルプの品質は向上する。テルペンアルコールについてはインキ剥離性の向上効果は確認されなかったがインキ剥離性の低下も確認されなかった。この結果よりテルペンアルコールはインキ剥離性を阻害または低下させること無く、微細遊離インキ粒子の捕集性、脱インキ性が向上したものと考えられる。 In the deinking method by the flotation method, when terpene alcohols are added to the deinking step, a significant improvement in deinking properties is confirmed. On the other hand, when comparing the DIP quality of the completely washed pulp from which the ink from which DIP is liberated with fresh water is removed, there is almost no difference in quality from the case where terpene alcohol is not used. The quality of the completely washed pulp is an index of the ink removability of the deinking agent. If the ink removability is excellent, the quality of the completely washed pulp is improved. With regard to terpene alcohol, the effect of improving the ink peelability was not confirmed, but a decrease in the ink peelability was not confirmed. From this result, it is considered that terpene alcohol has improved the collection property and deinking property of fine free ink particles without inhibiting or reducing the ink releasability.
一方、α-ピネンやターピノーレンのような分子中に水酸基を有しないテルペン系化合物を脱墨工程に添加した場合、脱インキ性は低下した。一方、完全洗浄パルプの脱インキ性はテルペン系化合物未添加時と差はほとんどない。本結果についての詳細な機構は不明であるが、恐らく水酸基を持たない事で水への親和性が低下し、インキを取り込んだテルペン系化合物がフローテーションにおいて泡に吸着されず、より疎水性の強いパルプ繊維へ優先的に吸着したためDIP品質が低下したと考えられる。特表平3−504523号公報には高起泡性−低乳化性界面活性剤とテルペン、及び該テルペンに対する溶剤の混合物からなる脱墨剤が記載されており、テルペンとしてd−リモネン、ジペンテン、α−ピネン、β−ピネン、テレピン油またはターペンタイン等のテルペン炭化水素が有効であると記載されているが、本発明者らの検証においてこれらテルペン炭化水素の脱墨剤としての有用性は確認されなかった。 On the other hand, when a terpene compound having no hydroxyl group in the molecule, such as α-pinene and terpinolene, was added to the deinking step, the deinking property was lowered. On the other hand, the deinking property of the completely washed pulp is almost the same as that when no terpene compound is added. Although the detailed mechanism of this result is unknown, the affinity to water is probably reduced due to the absence of a hydroxyl group, and the terpene compound incorporating the ink is not adsorbed by the bubbles in the flotation, making it more hydrophobic. It is thought that the DIP quality was lowered because it preferentially adsorbed to strong pulp fibers. JP-T-3-504523 discloses a deinking agent comprising a mixture of a high foaming-low emulsifying surfactant and a terpene, and a solvent for the terpene. As the terpene, d-limonene, dipentene, Although terpene hydrocarbons such as α-pinene, β-pinene, turpentine oil, and terpentine are described as effective, the effectiveness of these terpene hydrocarbons as deinking agents has been confirmed by the present inventors' verification. Was not.
また、2−エチルヘキサノールのような短い炭素鎖の飽和アルコールを脱墨工程に添加した場合、フローテーション後の洗浄時のインキ除去性は向上しているものの、フローテーション時のインキ除去性は低下し、完成DIPの品質は低下している。本結果よりテルペン系化合物の炭素骨格が遊離インキの凝集性、脱インキ性の向上に大きく寄与していると考えられる。 In addition, when a short carbon chain saturated alcohol such as 2-ethylhexanol is added to the deinking process, ink removability at the time of washing after flotation is improved, but ink removability at the time of flotation is reduced. However, the quality of the completed DIP is decreasing. From this result, it is considered that the carbon skeleton of the terpene compound greatly contributes to the improvement of the aggregation property and the deinking property of the free ink.
本発明で用いるポリオキシアルキレン基を有する化合物としては、高級アルコールアルキレンオキサイド(以下AO)付加体、脂肪酸AO付加体、油脂のAO付加体、アミンAO付加体、燐酸エステル系AO付加体、多価カルボン酸とアルコール類との混合物(反応物)のAO付加体等がある。ここで、AOにはエチレンオキサイド(以下EO)、プロピレンオキサイド(以下PO)、ブチレンオキサイド(以下BO)を挙げることができるが、経済的な面、及びAOの付加形態により性能を調整できる点でエチレンオキサイドおよびプロピレンオキサイドを共に用いるのが好ましい。また、AOの付加モル数は1〜200モルが好ましく、10〜100モルがより好ましく、30〜50モルがさらに好ましい。 Examples of the compound having a polyoxyalkylene group used in the present invention include higher alcohol alkylene oxide (hereinafter referred to as AO) adduct, fatty acid AO adduct, fat and oil AO adduct, amine AO adduct, phosphate ester AO adduct, polyvalent There are AO adducts of a mixture (reaction product) of carboxylic acid and alcohol. Here, examples of AO include ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and butylene oxide (hereinafter referred to as BO). However, in terms of economy and the ability to adjust performance depending on the addition form of AO. It is preferable to use both ethylene oxide and propylene oxide. Moreover, 1-200 mol is preferable, as for the addition mole number of AO, 10-100 mol is more preferable, and 30-50 mol is further more preferable.
ポリオキシアルキレン基を有する化合物の中で特に前記一般式(1)で示される化合物が脱インキ性の向上効果に優れる点で好ましい。前記一般式(1)においてR1は脱墨性能が向上する点で炭素数8から22のアルキル基またはアルケニル基が好ましく、UVインキ等の難脱墨性古紙の脱墨においては炭素数6から30のアリール基が好ましい。pは10〜100モルが好ましく、30〜50モルがより好ましい。また、該化合物はEOまたはPOの付加形態を変えることによりその特性を変化させる事が可能である。すなわち、各製紙会社の脱墨工程では機械の種類・シェアの変化、及び原料古紙の状態により要求されるインキ剥離性・凝集性が変化してくるが該化合物におけるAOの付加形態を調整することで様々な脱墨条件に対応することが可能となる。
Among the compounds having a polyoxyalkylene group, the compound represented by the general formula (1) is particularly preferable in that it has an excellent deinking effect. In the general formula (1), R 1 is preferably an alkyl group or an alkenyl group having 8 to 22 carbon atoms from the viewpoint of improving the deinking performance. In the deinking of hard-to-deink waste paper such as UV ink, R 1 Thirty aryl groups are preferred. 10-100 mol is preferable and, as for p, 30-50 mol is more preferable. In addition, the properties of the compound can be changed by changing the addition form of EO or PO. In other words, in the deinking process of each paper manufacturer, the required ink peelability and cohesiveness change depending on the change in machine type and share, and the state of the raw paper, but the addition form of AO in the compound should be adjusted. This makes it possible to deal with various deinking conditions.
(a)テルペンアルコール類と(b)ポリオキシアルキレン基を有する化合物の配合割合は、重量比で(a):(b)=1:99〜99:1の範囲であることが好ましく、(a):(b)=10:90〜90:10の範囲がより好ましく、(a):(b)=30:70〜70:30の範囲がさらに好ましい。各成分はそれぞれ混合せずに添加しても、予め混合したものを添加しても特に性能差は確認されなかったが、予め混合したものの方が輸送・保存等の面で好ましい。 The blending ratio of (a) terpene alcohols and (b) a compound having a polyoxyalkylene group is preferably in the range of (a) :( b) = 1: 99 to 99: 1 by weight ratio, ) :( b) = 10: 90 to 90:10 is more preferable, and (a) :( b) = 30: 70 to 70:30 is more preferable. Even if each component was added without being mixed, or a premixed mixture was added, no particular difference in performance was confirmed, but a premixed mixture is preferred in terms of transportation and storage.
また、脱インキ性能を損なわない範囲で、フローテーションでの起泡性、抑泡性を調整する目的でアルキルエーテルサルフェートや脂肪酸石鹸等のアニオン性界面活性剤を使用することもできる。ただし、脂肪酸石鹸等の使用は抑泡性の調整の目的での併用であり、ポリオキシアルキレン基を有する化合物を併用しない場合、DIP品質は大きく低下する。さらに、苛性ソーダ、ケイ酸ソーダ、炭酸ソーダ及びリン酸ソーダ等のアルカリ類、EDTA等のキレート剤も使用することができる。また、過酸化水素等の漂白剤を併用し、DIPの白色度を上げることもできる。 In addition, anionic surfactants such as alkyl ether sulfates and fatty acid soaps can be used for the purpose of adjusting the foaming property and antifoaming property in the flotation as long as the deinking performance is not impaired. However, the use of a fatty acid soap or the like is a combined use for the purpose of adjusting foam suppression properties, and the DIP quality is greatly lowered when a compound having a polyoxyalkylene group is not used together. Furthermore, alkalis such as caustic soda, sodium silicate, sodium carbonate and sodium phosphate, and chelating agents such as EDTA can also be used. In addition, a whitening degree of DIP can be increased by using a bleaching agent such as hydrogen peroxide together.
テルペンアルコール類とポリオキシアルキレン基を有する化合物は古紙離解工程、漂白工程、フローテーション工程等の各工程で添加することができる。また、従来からある公知の脱墨剤と組み合わせた脱墨剤についても同様の場所に添加できる。 A compound having a terpene alcohol and a polyoxyalkylene group can be added in each step such as a waste paper disaggregation step, a bleaching step, and a flotation step. Further, a deinking agent combined with a known deinking agent can be added in the same place.
本発明に係る脱墨方法及び脱墨剤は新聞古紙に対してだけでなく上質古紙、OA古紙等のいわゆる難脱墨性古紙の脱墨において優れた脱インキ性を示し、DIP品質が向上する。 The deinking method and the deinking agent according to the present invention show excellent deinking properties not only for newspaper wastepaper but also for deinking so-called hard-to-deink wastepaper such as high-quality wastepaper and OA wastepaper, and the DIP quality is improved. .
以下、本発明の実施例を示すが、これに限定されるものではない。
Examples of the present invention are shown below, but are not limited thereto.
(成分A テルペンアルコール類)
表1に示したテルペンアルコール類は市販品を使用した。
(Component A terpene alcohol)
Commercially available terpene alcohols shown in Table 1 were used.
(成分B ポリオキシアルキレン基を有する化合物)
表2に示したポリオキシアルキレン基を有する化合物は公知の方法で製造したものを使用した。また、燐酸エステル系脱墨剤には東邦化学工業(株)製ネオスコアFW−425(2−エチルヘキサノール燐酸エステルの2.5molEO付加体NaOH中和物)を使用した。
(Component B Compound having a polyoxyalkylene group)
The compound having a polyoxyalkylene group shown in Table 2 was prepared by a known method. Further, Neoscore FW-425 (2.5 mol EO adduct NaOH neutralized product of 2-ethylhexanol phosphate ester) manufactured by Toho Chemical Industry Co., Ltd. was used as the phosphate ester deinking agent.
(成分C 比較例化合物)
テルペンアルコール類との性能比較を行う為、表3に示した比較例化合物を使用した。また、表1に示した市販品以外の化合物は公知の方法で製造したものを使用した。
(Component C Comparative Example Compound)
In order to compare the performance with terpene alcohols, the comparative compounds shown in Table 3 were used. Moreover, what was manufactured by the well-known method was used for compounds other than the commercial item shown in Table 1.
(成分D 実施例脱墨剤)
表4に示した処方で成分A及び成分Bを組み合わせて使用した。表中の「併用」とは各成分を混合せずに、表中に示した重量割合で添加して試験に供したことを示し、「配合」とは各成分を表中に示した重量割合で予め混合したものを添加して試験に供したことを示す。
(Component D Example Deinking Agent)
Component A and component B were used in combination in the formulation shown in Table 4. “Combination” in the table indicates that each component was not mixed, but was added at the weight ratio shown in the table, and was used for the test. “Combination” was the weight ratio indicated for each component in the table. It shows that it added to what was mixed beforehand by and was used for the test.
(成分E 比較例脱墨剤)
表5に示した処方で成分Bと成分Cを組み合わせて使用した。表中の「単独」とは表中に記載の脱墨剤を単独で添加して試験に供したことを示す。
(Component E Comparative Example Deinking Agent)
Component B and component C were used in combination in the formulation shown in Table 5. “Individual” in the table indicates that the deinking agent described in the table was added alone and used for the test.
脱墨試験方法1
原料古紙を3cm×3cmに切断し卓上離解機に入れ、苛性ソーダを1.5重量%(対古紙)、3号ケイ酸ソーダを3重量%(対古紙)、35%過酸化水素水を3重量%(対古紙)、実施例または比較例に示した脱墨剤をその合計量が0.2重量%(対古紙)となるよう加えた後、水を加え、古紙濃度を5重量%とし、55℃に昇温後15分間離解した。離解後同温度で2時間熟成してから試験用原料(以下脱墨前原料)を得た。
得られた脱墨前原料をパルプ濃度1重量%に希釈した後、株式会社IHIフォイトペーパーテクノロジー製MT5Lフローテーターを使用してフローテーション処理を10分間行い、フローテーション後原料(以下脱墨後原料)を得た。得られた脱墨後原料を0.5重量%濃度にした後、硫酸アルミニウムにてpH5.0に調整し、JIS P−8209に規定したシートマシンにて手抄きシートを作成した。さらにフローテーション処理を行ったパルプを200倍量のイオン交換水で3回洗浄を行った。このパルプ(完全洗浄パルプ)について同様の方法で手抄きシートを作成した。
Deinking test method 1
Raw paper is cut into 3cm x 3cm and placed in a desktop disintegrator. Caustic soda is 1.5% by weight (against old paper), No. 3 sodium silicate is 3% by weight (against old paper), and 35% hydrogen peroxide is 3% by weight. % (Against used paper), after adding the deinking agent shown in the examples or comparative examples so that the total amount becomes 0.2 wt% (versus used paper), water is added to make the used paper concentration 5 wt%, After raising the temperature to 55 ° C., it was disaggregated for 15 minutes. After the disaggregation and aging at the same temperature for 2 hours, a test material (hereinafter, a material before deinking) was obtained.
After diluting the obtained pre-deinking raw material to a pulp concentration of 1% by weight, it is subjected to a flotation treatment for 10 minutes using an MT5L floatator manufactured by IHI Voith Paper Technology Co., Ltd. ) The obtained raw material after deinking was adjusted to a concentration of 0.5% by weight, adjusted to pH 5.0 with aluminum sulfate, and a handsheet was prepared with a sheet machine defined in JIS P-8209. Further, the pulp subjected to the flotation treatment was washed three times with 200 times the amount of ion-exchanged water. A handsheet was prepared in the same manner for this pulp (fully washed pulp).
脱墨試験方法2(搾取白水調整)
脱墨試験方法1で得られた脱墨後原料を10%に脱水濃縮する事で搾取白水(以下白水)を得た。
Deinking test method 2 (Exploitation white water adjustment)
Extracted white water (hereinafter, white water) was obtained by dehydrating and concentrating the post-deinking raw material obtained in Deinking Test Method 1 to 10%.
脱墨試験方法3(用水循環試験)
脱墨試験方法1で得られた脱墨前原料を脱墨試験方法2で得られた白水で1%に希釈した後、脱墨試験方法1と同様の方法で脱墨試験を行った。本試験は実機での用水循環を想定した試験である。
Deinking test method 3 (Water cycle test)
The raw material before deinking obtained by the deinking test method 1 was diluted to 1% with the white water obtained by the deinking test method 2, and then the deinking test was performed in the same manner as the deinking test method 1. This test is based on the assumption that water is circulated in actual equipment.
脱墨試験方法4(性能評価)
手抄きシートは乾燥後、JIS P−8148に規定した方法に準じてISO白色度を測定し、完全洗浄パルプについて画像解析装置を使用し、視野100mm2中に存在する径20μm以上のインキ個数を測定した。
Deinking test method 4 (performance evaluation)
After the handsheet is dried, the ISO whiteness is measured according to the method defined in JIS P-8148, and the number of inks having a diameter of 20 μm or more existing in a field of view 100 mm 2 is measured using an image analysis apparatus for the completely washed pulp. Was measured.
1.新聞系古紙の脱墨
新聞古紙60重量%、折込広告40重量%からなる原料古紙を用いて脱墨試験方法1に記載した方法で試験を行い、脱墨試験方法4に記載した方法で評価を実施した。
1. Deinking newspaper waste paper Using the method described in Deinking Test Method 1 using raw material wastepaper consisting of 60% by weight newspaper wastepaper and 40% by weight insert advertisement, the method described in Deinking Test Method 4 was used for evaluation. Carried out.
2.上質系古紙の脱墨
色上古紙50重量%、模造古紙50重量%からなる原料古紙を用いて脱墨試験方法1に記載した方法で試験を行い、脱墨試験方法4に記載した方法で評価を実施した。
2. Deinking high-quality waste paper Using the raw waste paper consisting of 50% by weight colored waste paper and 50% by weight imitation waste paper, the test described in Deinking Test Method 1 was performed, and the evaluation was performed using the method described in Deinking Test Method 4. Carried out.
3.難脱墨性古紙の脱墨
PPC古紙80重量%、UVインキ印刷古紙20重量%からなる原料古紙を用いて脱墨試験方法1に記載した方法で試験を行い、脱墨試験方法4に記載した方法で評価を実施した。
3. Deinking of hard-to-deink waste paper Using raw material waste paper consisting of 80% by weight of PPC waste paper and 20% by weight of UV ink printed waste paper, the test was performed according to the method described in Deinking Test Method 1, and was described in Deinking Test Method 4. Evaluation was carried out by the method.
4.用水循環試験
新聞古紙60重量%、折込広告40重量%からなる原料古紙を用いて脱墨試験方法3に記載した方法で試験を行い、脱墨試験方法4に記載した方法で評価を実施した。
4). Water Circulation Test A test was performed by the method described in Deinking Test Method 3 using raw paper consisting of 60% by weight newspaper wastepaper and 40% by weight insert advertisement, and the evaluation was performed by the method described in Deinking Test Method 4.
表6の結果からテルペンアルコールとポリオキシアルキレン基を有する化合物を工程内に添加することでフローテーション後のISO白色度は大きく向上し、高いフローテーション性を有することがわかる。特に、高級アルコールAO付加体と組み合わせた時に最も高い効果を示す傾向が確認された。
また、表8、表9の結果から、本発明の脱墨方法がいわゆる難脱墨性古紙と呼ばれる様々な古紙に対しても高い脱墨効果を奏することがわかる。表9に用水循環試験の結果を示したが一般に用水循環を行った場合、ワンパスの試験と比較し品質は低下傾向となるが、テルペンアルコールとポリオキシアルキレン基を有する化合物を工程内に添加により品質低下を抑制する事が可能となる。
From the results of Table 6, it can be seen that by adding a compound having a terpene alcohol and a polyoxyalkylene group in the process, the ISO whiteness after flotation is greatly improved, and high flotation properties are obtained. In particular, the tendency to show the highest effect when combined with a higher alcohol AO adduct was confirmed.
Further, from the results of Tables 8 and 9, it can be seen that the deinking method of the present invention has a high deinking effect on various used papers called so-called hard-to-deink old paper. Table 9 shows the results of the irrigation cycle test. In general, when the irrigation cycle is performed, the quality tends to be lower than that of the one-pass test, but by adding a compound having a terpene alcohol and a polyoxyalkylene group in the process. It is possible to suppress the quality deterioration.
Claims (3)
R1−O−(AO)p−H (1)
(但し、R1は炭素数1から24のアルキル基、アルケニル基または炭素数6から30のアリール基を表し、AOは炭素数2から4のオキシアルキレン基を表し、pは1から200の整数である。) (B) The deinking agent according to claim 2, wherein the compound having a polyoxyalkylene group is a compound represented by the following general formula (1).
R 1 —O— (AO) p—H (1)
(Wherein R 1 represents an alkyl group having 1 to 24 carbon atoms, an alkenyl group, or an aryl group having 6 to 30 carbon atoms, AO represents an oxyalkylene group having 2 to 4 carbon atoms, and p is an integer of 1 to 200) .)
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