JP2012031043A - Slaked lime particles, light calcium carbonate and paper and coated paper using the same - Google Patents
Slaked lime particles, light calcium carbonate and paper and coated paper using the same Download PDFInfo
- Publication number
- JP2012031043A JP2012031043A JP2011027486A JP2011027486A JP2012031043A JP 2012031043 A JP2012031043 A JP 2012031043A JP 2011027486 A JP2011027486 A JP 2011027486A JP 2011027486 A JP2011027486 A JP 2011027486A JP 2012031043 A JP2012031043 A JP 2012031043A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- paper
- light calcium
- slaked lime
- particle size
- 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
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 312
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 148
- 239000002245 particle Substances 0.000 title claims abstract description 116
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 title claims abstract description 81
- 239000000920 calcium hydroxide Substances 0.000 title claims abstract description 81
- 235000011116 calcium hydroxide Nutrition 0.000 title claims abstract description 81
- 229910001861 calcium hydroxide Inorganic materials 0.000 title claims abstract description 81
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000000049 pigment Substances 0.000 claims abstract description 47
- 239000002002 slurry Substances 0.000 claims abstract description 41
- 239000000945 filler Substances 0.000 claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 25
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 25
- 230000001186 cumulative effect Effects 0.000 claims abstract description 17
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 238000007664 blowing Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 12
- 239000000123 paper Substances 0.000 description 115
- 238000000034 method Methods 0.000 description 36
- 230000000052 comparative effect Effects 0.000 description 34
- 238000000576 coating method Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 23
- 238000004519 manufacturing process Methods 0.000 description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- 238000010298 pulverizing process Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- 238000007639 printing Methods 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000011247 coating layer Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- 239000002585 base Substances 0.000 description 10
- 239000000292 calcium oxide Substances 0.000 description 10
- 235000012255 calcium oxide Nutrition 0.000 description 10
- -1 phosphate compound Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000001254 oxidized starch Substances 0.000 description 6
- 235000013808 oxidized starch Nutrition 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000004816 latex Substances 0.000 description 4
- 229920000126 latex Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
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- 235000019738 Limestone Nutrition 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
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- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000007561 laser diffraction method Methods 0.000 description 3
- 239000006028 limestone Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
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- 239000004576 sand Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229940099112 cornstarch Drugs 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000010893 paper waste Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000011632 Caseins Human genes 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000012717 electrostatic precipitator Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000000411 inducer Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Paper (AREA)
Abstract
Description
本発明は、平滑性、光沢発現性が高い製紙用の填料、顔料として使用するに適した軽質炭酸カルシウムおよびその原料となる消石灰に関する。 The present invention relates to a light calcium carbonate suitable for use as a paper filler and pigment having high smoothness and glossiness, and slaked lime as a raw material thereof.
近年、印刷物のビジュアル化やカラー化が進み、印刷用紙は、高白色で印刷面感が良好なことが求められている。一方で、コスト削減のため印刷用紙の軽量化が進められている。用紙の軽量化は不透明度を低下させるので、その対策要望が多く、白色度、平滑度、光沢度、面感、不透明度等の改善要求に応える必要に迫られている。その一つの手段として、填料、顔料としての高品質の軽質炭酸カルシウムの開発が行われている。 In recent years, with the progress of visualization and colorization of printed materials, printing paper is required to have a high white color and a good printing surface. On the other hand, weight reduction of printing paper is being promoted for cost reduction. Since the lighter weight of paper reduces opacity, there are many demands for countermeasures, and it is necessary to meet demands for improvement in whiteness, smoothness, gloss, surface feel, opacity, and the like. As one of the means, development of high-quality light calcium carbonate as a filler and pigment has been performed.
軽質炭酸カルシウムの製造方法としては、消石灰スラリーに炭酸ガスを吹き込んで反応させる「液−ガス」法および炭酸ナトリウムなどを用いる「液−液」法がある。原料の品質が優れるわが国においては、前者の「液−ガス」法が工業的に広く採用されている。 As a light calcium carbonate production method, there are a “liquid-gas” method in which carbon dioxide gas is blown into a slaked lime slurry to cause a reaction, and a “liquid-liquid” method using sodium carbonate or the like. In Japan, where the quality of raw materials is excellent, the former “liquid-gas” method is widely used industrially.
軽質炭酸カルシウムは数種の結晶構造を持ち、その形状によって紙の品質特性上、様々な特徴を有する。特に、アラゴナイト系炭酸カルシウムを塗被した紙は、高光沢で高不透明度、インキ着肉性およびインキセット性に優れ、剛性および強度も向上する特徴があるため、以下に示すように従来から様々な方法によるアラゴナイト系炭酸カルシウムの製造方法の研究開発が進められてきた。 Light calcium carbonate has several crystal structures and has various characteristics in terms of paper quality characteristics depending on its shape. In particular, paper coated with aragonite-based calcium carbonate is characterized by high gloss, high opacity, excellent ink setting and ink setting properties, and improved rigidity and strength. Research and development of a method for producing aragonite calcium carbonate by various methods has been advanced.
特許文献１には、炭酸化工程で炭酸ガス量を各段階で調整するアラゴナイト系柱状炭酸カルシウムの製造方法が提案されており、特許文献２には、炭酸化の段階で加温するアラゴナイト系針状炭酸カルシウムの製法が提案されている。 Patent Document 1 proposes a method for producing aragonite-based columnar calcium carbonate in which the amount of carbon dioxide gas is adjusted at each stage in the carbonation step, and Patent Document 2 discloses an aragonite-based needle that is heated at the stage of carbonation. A method for producing calcium carbonate has been proposed.
特許文献３には、消石灰スラリーに針状軽質炭酸カルシウムを種結晶として用い、このスラリーに炭酸ガスを導入し炭酸化反応によって該種結晶を所望の粒径まで成長させることを特徴とするアラゴナイト系柱状炭酸カルシウムの製造方法が提案されている。 Patent Document 3 discloses an aragonite system characterized in that acicular light calcium carbonate is used as a seed crystal in a slaked lime slurry, carbon dioxide gas is introduced into the slurry, and the seed crystal is grown to a desired particle size by a carbonation reaction. A method for producing columnar calcium carbonate has been proposed.
特許文献４には、アラゴナイト系針状炭酸カルシウムを消石灰スラリーに添加し、０．２５ｋＷ／ｍ３以上の攪拌動力で撹拌しながら炭酸化反応を行うアラゴナイト系針状炭酸カルシウムの製造方法が提案されている。 Patent Document 4 proposes a method for producing aragonite acicular calcium carbonate in which aragonite acicular calcium carbonate is added to a slaked lime slurry, and carbonation reaction is performed while stirring with a stirring power of 0.25 kW / m 3 or more. ing.
さらに、種々の添加物を用いるアラゴナイト系炭酸カルシウムの製造方法が提案されている。特許文献５には、リン酸化合物を添加するアラゴナイト結晶形炭酸カルシウムの製造方法が提案されており、特許文献６には、硫酸化合物を添加し紡錘形炭酸カルシウムを得る製紙用炭酸カルシウムの製造方法が提案されている。 Furthermore, a method for producing aragonite-based calcium carbonate using various additives has been proposed. Patent Document 5 proposes a method for producing aragonite crystal-type calcium carbonate to which a phosphate compound is added, and Patent Document 6 discloses a method for producing calcium carbonate for papermaking in which a sulfate compound is added to obtain spindle-shaped calcium carbonate. Proposed.
また、特許文献７には、アルカリ性水溶液で調製した消石灰スラリーを用いるアラゴナイト結晶形炭酸カルシウムの製造方法が提案されており、特許文献８には、マグネシウムイオンを含む水で調製した消石灰スラリーを用いるアラゴナイト型炭酸カルシウムの製造方法が提案されている。 Patent Document 7 proposes a method for producing aragonite crystalline calcium carbonate using slaked lime slurry prepared with an alkaline aqueous solution. Patent Document 8 discloses aragonite using slaked lime slurry prepared with water containing magnesium ions. A method for producing type calcium carbonate has been proposed.
細粒の消石灰を用いることを特徴とするアラゴナイト系炭酸カルシウムの製造方法が提案されており、特許文献９には、高温状態で消和することで得られた細粒の消石灰粒子を用いるアラゴナイト結晶形炭酸カルシウムの製造方法が提案されている。また、特許文献１０には、消石灰スラリーを高速せん断攪拌することにより細かくした消石灰粒子を用いるアラゴナイト系柱状炭酸カルシウムの製造方法が提案されており、特許文献１１には、４５μｍ以下の微細消石灰粒子を用いる針状炭酸カルシウムの製造方法が提案されている。 A method for producing aragonite-based calcium carbonate characterized by using fine slaked lime has been proposed. Patent Document 9 discloses an aragonite crystal using fine slaked lime particles obtained by dehydration in a high temperature state. A method for producing shaped calcium carbonate has been proposed. Patent Document 10 proposes a method for producing aragonite-based columnar calcium carbonate using fine slaked lime particles obtained by finely stirring slaked lime slurry at high speed. Patent Document 11 discloses fine slaked lime particles of 45 μm or less. A method for producing acicular calcium carbonate to be used has been proposed.
特許文献１および特許文献２の方法は、各生成条件を厳密に規定する必要があり、かつ合成条件が比較的狭い範囲に限られるという問題がある。また、特許文献３の方法は、操作が複雑であり、生産性が低下する問題がある。特許文献４の方法は、生産性の問題は改善されるものの粒径のバラツキが生じ、品質が不安定であるなどの問題がある。 The methods of Patent Document 1 and Patent Document 2 have a problem that each generation condition needs to be strictly defined, and the synthesis condition is limited to a relatively narrow range. Moreover, the method of patent document 3 has the problem that operation is complicated and productivity falls. Although the method of Patent Document 4 is improved in productivity, there is a problem that the particle size varies and the quality is unstable.
特許文献５および特許文献６の方法は、種々の高価な添加物を要するためコスト高となる上に、濾水を循環利用する場合、反応系内の添加物の濃度調整が困難であるなどの問題がある。また、特許文献７および８の方法も濾水を循環利用する場合、添加物水溶液の濃度調整が困難であるといった問題がある。 The methods of Patent Document 5 and Patent Document 6 require various expensive additives and thus increase the cost. In addition, when circulating filtrate is used, it is difficult to adjust the concentration of the additive in the reaction system. There's a problem. Further, the methods of Patent Documents 7 and 8 also have a problem that it is difficult to adjust the concentration of the aqueous additive solution when the filtrate is recycled.
特許文献９、特許文献１０および特許文献１１の方法は、消石灰スラリーに導入する炭酸ガス量を制御しているため、反応時間が長くなり、生産性が低いといった問題がある。 Since the methods of Patent Document 9, Patent Document 10 and Patent Document 11 control the amount of carbon dioxide introduced into the slaked lime slurry, there is a problem that the reaction time becomes long and the productivity is low.
本発明は、従来技術では困難とされていた微細で粒径の揃った高品質の軽質炭酸カルシウムを簡便かつ効率的に得ることを目的とする。 It is an object of the present invention to easily and efficiently obtain high-quality light calcium carbonate having a fine particle size and uniform, which has been difficult in the prior art.
軽質炭酸カルシウムは、通常、水に生石灰を加えて調製した消石灰スラリーに、炭酸ガスを吹き込む炭酸ガス化合法により工業的に生産されている。しかし、本発明者らは、上記の課題を解決するため鋭意研究を重ねた結果、所望の性状を備えた軽質炭酸カルシウムを得るには、消石灰粒子の形状が重要な技術要素であることを見出した。 Light calcium carbonate is usually industrially produced by a carbon dioxide compound method in which carbon dioxide gas is blown into slaked lime slurry prepared by adding quick lime to water. However, as a result of intensive studies to solve the above problems, the present inventors have found that the shape of slaked lime particles is an important technical element in order to obtain light calcium carbonate with desired properties. It was.
本発明は、このような知見に基づいてなされたものであり、下記（１）〜（５）の消石灰粒子およびそれを原料として製造される軽質炭酸カルシウム、さらには該軽質炭酸カルシウムを用いた紙および塗被紙を要旨とする。 The present invention has been made on the basis of such knowledge. The slaked lime particles of the following (1) to (5), light calcium carbonate produced from the raw material, and paper using the light calcium carbonate And the gist is coated paper.
（１）軽質炭酸カルシウムの原料として用いられる消石灰粒子であって、体積粒度分布における粒径が１．０μｍ以下の粒子の累積体積が２０％以下、かつ１００μｍ以下の粒子の累積体積が９５％以上であることを特徴とする消石灰粒子。 (1) Slaked lime particles used as a raw material for light calcium carbonate, the cumulative volume of particles having a particle size of 1.0 μm or less in the volume particle size distribution is 20% or less, and the cumulative volume of particles of 100 μm or less is 95% or more Slaked lime particles characterized by being.
（２）前記消石灰粒子であって、体積粒度分布における粒径が１．０μｍ以下の粒子の累積体積が１５％以下であることを特徴とする前記（１）に記載の消石灰粒子。 (2) The slaked lime particles according to (1), wherein the slaked lime particles have a cumulative volume of 15% or less with a particle size of 1.0 μm or less in a volume particle size distribution.
（３）前記（１）または（２）に記載の消石灰粒子をスラリー化し、２０〜７０℃の該消石灰スラリーに二酸化炭素含有ガスを吹き込んで炭酸化することにより製造されたことを特徴とする軽質炭酸カルシウム。 (3) A light product produced by slurrying the slaked lime particles according to (1) or (2) above and carbonating the slaked lime slurry at 20 to 70 ° C. by blowing a carbon dioxide-containing gas. Calcium carbonate.
（４）前記（３）に記載の軽質炭酸カルシウムを填料として用いた紙。 (4) Paper using the light calcium carbonate described in (3) as a filler.
（５）前記（３）に記載の軽質炭酸カルシウムを顔料として用いた塗被紙。 (5) Coated paper using the light calcium carbonate described in (3) as a pigment.
本発明の消石灰粒子を原料として用いることで、微細で粒径が均一な軽質炭酸カルシウムが得られ、その軽質炭酸カルシウムを、内添用の填料あるいは塗工用の顔料として用いることによって、表面平滑性、不透明度および印刷品質に優れた紙を得ることができる。 By using the slaked lime particles of the present invention as a raw material, light calcium carbonate having a fine and uniform particle size can be obtained. By using the light calcium carbonate as a filler for internal addition or a pigment for coating, the surface smoothness can be obtained. Paper having excellent properties, opacity and print quality can be obtained.
高品質の軽質炭酸カルシウムを得るためには、原料となる消石灰粒子の形状、とりわけ粒径を厳密に管理することが重要となる。このため本発明者らは、レーザー回折法により消石灰粒子の体積粒度分布を測定することとした。体積粒度分布における粒径が１．０μｍ以下の微細な消石灰粒子の累積体積が２０％を超えると、それを原料として用いた時に紡錘状の軽質炭酸カルシウムが生成される。この生成物である炭酸カルシウムには、粗粒の粒子が混在し、粒径も不均一であるため、填料ないし顔料に用いた場合には品質が劣る。従って、粒径が１．０μｍ以下の消石灰粒子の累積体積は２０％以下とする。１．０μｍ以下の消石灰粒子の累積体積は、１５％以下であることが好ましく、１０％以下であることがより好ましい。 In order to obtain high-quality light calcium carbonate, it is important to strictly control the shape of the slaked lime particles as a raw material, particularly the particle size. For this reason, the present inventors decided to measure the volume particle size distribution of slaked lime particles by a laser diffraction method. When the cumulative volume of fine slaked lime particles having a particle size of 1.0 μm or less in the volume particle size distribution exceeds 20%, spindle-shaped light calcium carbonate is produced when used as a raw material. This product, calcium carbonate, contains coarse particles and has a non-uniform particle size, so that the quality is poor when used as a filler or pigment. Therefore, the cumulative volume of slaked lime particles having a particle size of 1.0 μm or less is set to 20% or less. The cumulative volume of slaked lime particles of 1.0 μm or less is preferably 15% or less, and more preferably 10% or less.
一方、粒径が１００μｍを超える粗粒の粒子が多量に含む消石灰を原料として炭酸化反応を行うと、生成物は未反応の消石灰粒子を核としてその表面に針状軽質炭酸カルシウムが生成される毬栗状の構造を呈するようになるため、填料ないし顔料に用いた場合には品質が劣る。従って、生成される軽質炭酸カルシウムの品質を向上させるためには、粒径が１００μｍを超える消石灰粒子の累積体積は５％を超えないようにする。すなわち、粒径が１００μｍ以下の粒子の累積体積は９５％以上とする。 On the other hand, when a carbonation reaction is performed using slaked lime containing a large amount of coarse particles having a particle size exceeding 100 μm as a raw material, acicular light calcium carbonate is generated on the surface of unreacted slaked lime particles as a core. Since it has a brown chestnut-like structure, its quality is poor when used for fillers or pigments. Therefore, in order to improve the quality of the produced light calcium carbonate, the cumulative volume of slaked lime particles having a particle size exceeding 100 μm should not exceed 5%. That is, the cumulative volume of particles having a particle size of 100 μm or less is 95% or more.
このように、消石灰粒子の粒度分布をシャープにすることで、炭酸化反応が均一に進行し、生成される軽質炭酸カルシウムの粒径をより均一にすることができる。さらに、消石灰粒子の平均粒径としては、２〜５０μｍであることが好ましい。より好ましい消石灰粒子の平均粒径の上限値は３５μｍである。 Thus, by sharpening the particle size distribution of the slaked lime particles, the carbonation reaction proceeds uniformly, and the particle size of the produced light calcium carbonate can be made more uniform. Furthermore, the average particle size of the slaked lime particles is preferably 2 to 50 μm. The upper limit of the average particle diameter of the more preferable slaked lime particles is 35 μm.
消石灰の製造方法としては、生石灰すなわち酸化カルシウムに理論水和量の２倍前後の水を加えて水和を行う乾式消和法、および理論水和量を大きく超える量の水の存在下で水和を行う湿式消和法の２種類が挙げられる。本発明においてはいずれの方法を用いても良いが、湿式消和法では消石灰粒子の粒径が不均一になるとともに、微細な粒子が多く形成されるため、乾式消和法を用いる方が好ましい。 As a method for producing slaked lime, quick lime, that is, calcium oxide, is added with water about twice the theoretical hydration amount to perform hydration, and water is added in the presence of water that greatly exceeds the theoretical hydration amount. There are two types of wet decontamination methods for summing. In the present invention, any method may be used, but the wet slaked calcination method makes the particle size of the slaked lime particles non-uniform and many fine particles are formed. .
消石灰粒子は、消和方法だけでなく、石灰石の焼成条件（例えば、焼成温度、焼成時間、生石灰の粒度分布など）、生石灰の消和条件（例えば、使用する消和水質、消和温度、消和時間、消和時の攪拌条件など）などの諸条件を適宜設定することで調整が可能である。また、消石灰粒子を所望の粒径に調整する方法としては、乾式消和および湿式消和で生成した消石灰を篩分けにより粗粒粒子を除去する方法、遠心分離などで微細粒子を分離する方法などがある。 The slaked lime particles are not limited to the saponification method, but also calcining conditions of limestone (for example, calcination temperature, calcination time, quick lime particle size distribution, etc.) It is possible to make adjustments by appropriately setting various conditions such as summing time, stirring conditions at the time of soaking, and the like. Moreover, as a method of adjusting the slaked lime particles to a desired particle size, a method of removing coarse particles by sieving the slaked lime generated by dry-type and wet-type slaked methods, a method of separating fine particles by centrifugation, etc. There is.
消石灰粒子の原料である生石灰中の二酸化炭素含有率が低い方が、針状の軽質炭酸カルシウムが得られやすい。そのため、本発明で使用する生石灰は、ＪＩＳ Ｒ９０１１：２００６に準じて測定された二酸化炭素含有率が１.５％以下であることが好ましい。より好ましくは１．０％以下である。 The one where the carbon dioxide content rate in the quicklime which is a raw material of slaked lime particles is lower, it is easier to obtain acicular light calcium carbonate. For this reason, the quicklime used in the present invention preferably has a carbon dioxide content of 1.5% or less as measured in accordance with JIS R9011: 2006. More preferably, it is 1.0% or less.
炭酸化に供する消石灰スラリーの固形分濃度は、５質量％未満とすると、生産効率が低下し、４０質量％を超えると微細な軽質炭酸カルシウムが生成されて、粘度も上昇して、操業性が劣る。従って、消石灰スラリーの固形分濃度は５〜４０質量％であることが好ましい。消石灰スラリーの固形分濃度のより好ましい下限は８質量％であり、より好ましい上限は２０質量％である。 If the solid content concentration of the slaked lime slurry used for carbonation is less than 5% by mass, the production efficiency decreases, and if it exceeds 40% by mass, fine light calcium carbonate is generated, the viscosity increases, and the operability is improved. Inferior. Therefore, the solid content concentration of the slaked lime slurry is preferably 5 to 40% by mass. The minimum with more preferable solid content concentration of slaked lime slurry is 8 mass%, and a more preferable upper limit is 20 mass%.
また、炭酸化開始時の消石灰スラリー温度は、生成物である軽質炭酸カルシウムの結晶形状に影響を及ぼすため、調整する必要がある。炭酸化開始温度が２０℃未満であると、炭酸ガスまたは炭酸ガス含有ガスを吹き込んだ際、微細な針状結晶が凝集したものになり、一方、７０℃を超えると針状と紡錘状のものが混在して、均一な粒径の炭酸カルシウム粒子が形成されず、品質が発現しないおそれがある。従って、炭酸化開始温度は２０〜７０℃であることが望ましく、３０〜７０℃であることがより望ましい。 Moreover, since the slaked lime slurry temperature at the time of a carbonation start affects the crystal | crystallization shape of the light calcium carbonate which is a product, it is necessary to adjust. When the carbonation start temperature is less than 20 ° C., fine needle-like crystals are aggregated when carbon dioxide or carbon dioxide-containing gas is blown, while when it exceeds 70 ° C., needle-like and spindle-like ones , Calcium carbonate particles having a uniform particle size are not formed, and the quality may not be expressed. Therefore, the carbonation start temperature is desirably 20 to 70 ° C, and more desirably 30 to 70 ° C.
炭酸ガスまたは炭酸ガス含有ガスの吹き込み量は、特に制限はないが、生産性の点から、反応開始前の消石灰１ｋｇ当たり１００％炭酸ガス（１気圧、２０℃換算）を２ｌ／分以上とすることが好ましく、３ｌ／分以上とすることがより好ましく、５ｌ／分以上とすることが最も好ましい。 The amount of carbon dioxide or carbon dioxide-containing gas blown is not particularly limited, but from the viewpoint of productivity, 100% carbon dioxide (1 atm, converted to 20 ° C.) per kg of slaked lime before the start of reaction is 2 l / min or more. It is preferably 3 l / min or more, more preferably 5 l / min or more.
炭酸化反応は、バッチ式または連続式のいずれでもよく、炭酸化反応槽も炭酸ガスを吹き込むことが出来るものであればよい。また、反応槽に攪拌機を備えて、攪拌しながら炭酸化を行うことにより、炭酸ガスが微細になり、スラリー中の消石灰粒子との接触が良くなることにより、反応が均一かつ効率的に行われる。 The carbonation reaction may be either a batch type or a continuous type, and the carbonation reaction tank only needs to be able to blow carbon dioxide. In addition, the reaction tank is equipped with a stirrer, and by performing carbonation while stirring, the carbon dioxide gas becomes finer and the contact with the slaked lime particles in the slurry is improved, so that the reaction is performed uniformly and efficiently. .
炭酸化反応前の消石灰スラリーに種晶を添加してもよい。種晶としてアラゴナイト系針状軽質炭酸カルシウムを予め添加しておくことで、類似の針状結晶が効率よく生成される。種晶の添加率は、水酸化カルシウム：アラゴナイト系針状軽質炭酸カルシウム＝９９．７：０．３〜９５：５となるようにするのが好ましい。 You may add a seed crystal to the slaked lime slurry before carbonation reaction. By adding aragonite acicular light calcium carbonate as a seed crystal in advance, similar acicular crystals are efficiently produced. The seed crystal addition rate is preferably calcium hydroxide: aragonite-based acicular light calcium carbonate = 99.7: 0.3 to 95: 5.
炭酸化反応の炭酸ガス含有ガスの好適なものとしては、二酸化炭素を含有する混合ガス、例えば、石灰石焼成排ガス、パルプ製造プラントの石灰焼成排ガス、セメント製造キルン排ガス、発電ボイラー排ガス、ゴミ焼却排ガスなどが挙げられる。炭酸ガス含有ガスとして上記排ガスを用いる場合、排ガス中の石灰石、石灰、硫黄酸化物、未燃カーボン等のダストをバグフィルター、電気集塵機、乾式スクラバー、湿式スクラバーもしくはこれらの組合せを用いることによって排ガスを浄化することが好ましい。 Suitable examples of carbon dioxide-containing gas for carbonation reaction include mixed gas containing carbon dioxide, such as limestone calcined exhaust gas, lime calcined exhaust gas of pulp production plant, cement production kiln exhaust gas, power generation boiler exhaust gas, waste incineration exhaust gas, etc. Is mentioned. When the above exhaust gas is used as the carbon dioxide-containing gas, the exhaust gas is removed by using dust such as limestone, lime, sulfur oxide, and unburned carbon in the exhaust gas, using a bag filter, an electrostatic precipitator, a dry scrubber, a wet scrubber, or a combination thereof. It is preferable to purify.
このようにして得られた炭酸カルシウムスラリーにおいて、炭酸化処理によって生じた微細な軽質炭酸カルシウムの１次粒子が凝集して、２次粒子が形成される。この炭酸カルシウムスラリーは、製紙用填料として適度な粒径であるため、そのまま用いることができる。製紙用填料として用いる場合、炭酸カルシウムスラリーの平均粒径が１．５μｍ未満は、歩留り低下、強度低下などを起すおそれがあり、一方、１５μｍを超えると不透明度の悪化や粉落ちなどの印刷トラブルを引き起こすおそれがある。従って、平均粒径は１．５〜１５μｍであることが好ましい。より好ましくは２〜１０μｍである。 In the calcium carbonate slurry thus obtained, primary particles of fine light calcium carbonate generated by the carbonation treatment are aggregated to form secondary particles. Since this calcium carbonate slurry has an appropriate particle size as a filler for papermaking, it can be used as it is. When used as a filler for papermaking, if the average particle size of the calcium carbonate slurry is less than 1.5 μm, there is a risk of decreasing the yield and strength. On the other hand, if it exceeds 15 μm, printing troubles such as deterioration of opacity and powder falling May cause. Therefore, the average particle size is preferably 1.5 to 15 μm. More preferably, it is 2-10 micrometers.
炭酸カルシウムスラリーを塗工用顔料として用いる場合、脱水して脱水組成物とする脱水工程と、該脱水工程により得られる脱水組成物に水分を加えてスラリー状の分散組成物とする分散工程と、所望の粒径に調整する粉砕工程を備えてもよい。 When a calcium carbonate slurry is used as a coating pigment, a dehydration step of dehydrating to make a dehydrated composition, a dispersion step of adding water to the dehydrated composition obtained by the dehydration step to make a slurry-like dispersion composition, You may provide the grinding | pulverization process adjusted to a desired particle size.
脱水工程は、濾過、遠心分離、加圧脱水、圧搾などの操作により、固形分濃度７０％程度まで脱水を行うことができる。好適な脱水装置としては、フィルタープレス、ベルトプレスなどがある。脱水工程後の脱水ケーキの固形分濃度が低い場合は、乾燥工程を付加して所望の固形分濃度まで上げることができる。乾燥機としては、ロータリードライヤー、ディスクドライヤー気流乾燥機、流動乾燥機などがある。また、脱水工程と乾燥工程が一体となった乾燥機能付きフィルタープレスを用いることもできる。 In the dehydration step, dehydration can be performed to a solid content concentration of about 70% by operations such as filtration, centrifugation, pressure dehydration, and pressing. Suitable dewatering devices include filter presses and belt presses. When the solid content concentration of the dehydrated cake after the dehydration step is low, a drying step can be added to increase the desired solid content concentration. Examples of the dryer include a rotary dryer, a disk dryer airflow dryer, and a fluid dryer. A filter press with a drying function in which the dehydration step and the drying step are integrated can also be used.
分散工程は、脱水工程により得られる脱水組成物に水分を加えてスラリー状の分散組成物とするものであればよい。分散工程時に水分以外に、分散剤を添加することで、軽質炭酸カルシウムを良好に分散することができ、製紙用材料としての品質が向上すると共に、取り扱いも容易になるので好ましい。分散剤としては、例えば、ポリアクリル酸ナトリウム等の合成高分子系の分散剤など、一般的な分散剤を使用することができる。 The dispersion process may be any process as long as water is added to the dehydrated composition obtained by the dehydration process to form a slurry-like dispersion composition. It is preferable to add a dispersing agent in addition to moisture during the dispersion step, because light calcium carbonate can be dispersed well, quality as a papermaking material is improved, and handling is facilitated. As the dispersant, for example, a general dispersant such as a synthetic polymer-based dispersant such as sodium polyacrylate can be used.
分散工程で使用される分散機としては、コーレスミキサ、攪拌式ディスパーサーまたは混合容器を自転させ、アジテータのような攪拌工具を別駆動で回転させる構成の高せん断分散機、例えば、日本アイリッヒ（株）製のインテンシブミキサなどが挙げられる。高せん断分散機を用いることで、高濃度かつ粘度の低い分散スラリーを調製することができるので好ましい。 As a disperser used in the dispersion process, a high shear disperser configured to rotate a coreless mixer, a stirring-type disperser, or a mixing vessel and rotate a stirring tool such as an agitator by another drive, for example, Nihon Eirich Co., Ltd. Intensive mixers made by the manufacturer are listed. It is preferable to use a high shear disperser because a dispersion slurry having a high concentration and a low viscosity can be prepared.
本発明において、軽質炭酸カルシウムの粒径を微細化するために、粉砕処理工程を分散工程後に備えても良い。粉砕工程に用いる粉砕機としては、サンドミル、ビーズミル、湿式ボールミル、振動ミル、攪拌槽型ミル、流通管型ミル、コボールミルなどの湿式粉砕機を使用することができる。また、粉砕処理は炭酸化処理工程において、二酸化炭素を吹き込みながら行ってもよい。 In the present invention, a pulverization step may be provided after the dispersion step in order to reduce the particle size of the light calcium carbonate. As a pulverizer used in the pulverization step, a wet pulverizer such as a sand mill, a bead mill, a wet ball mill, a vibration mill, a stirring tank mill, a flow tube mill, or a coball mill can be used. Further, the pulverization treatment may be performed while blowing carbon dioxide in the carbonation treatment step.
軽質炭酸カルシウムの粒径を微細化することによって、紙に仕上げた際に不透明度、白色度、光沢度、平滑度および印刷適性が極めて優れたものが得られる。本発明の軽質炭酸カルシウムの粒度分布は、レーザー回折法により測定される。平均粒径が０．７μｍを超えると平滑度、光沢度が低下し、印刷適性が劣る。従って、平均粒径は、０．７μｍ以下とするのが好ましく、０．６μｍ以下とするのがより好ましい。他方、平均粒径が０．１μｍ未満とするためには過大なエネルギーを要し、紙での品質向上効果も小さく、印刷適性、特に強度が低下する難点が生じる。従って、平均粒径は、０．１μｍ以上とするのが好ましく、０．２μｍ以上とするのがより好ましい。また、累積体積９５％の粒径（以下、Ｄ９５）も重要な要素となり得る。粗粒の粒子が多量に混在し、Ｄ９５が３．０μｍを超えると平滑度や光沢度が低下し、塗工層強度も低下する。従って、Ｄ９５が３．０μｍ以下であることが好ましい。Ｄ９５は２．５μｍ以下であることがより好ましい。 By reducing the particle size of the light calcium carbonate, a paper having excellent opacity, whiteness, glossiness, smoothness and printability when finished into paper can be obtained. The particle size distribution of the light calcium carbonate of the present invention is measured by a laser diffraction method. When the average particle diameter exceeds 0.7 μm, the smoothness and glossiness are lowered, and the printability is inferior. Therefore, the average particle size is preferably 0.7 μm or less, and more preferably 0.6 μm or less. On the other hand, in order to make the average particle size less than 0.1 μm, excessive energy is required, the effect of improving the quality on paper is small, and the printability, particularly the strength is lowered. Therefore, the average particle diameter is preferably 0.1 μm or more, and more preferably 0.2 μm or more. In addition, a particle size having a cumulative volume of 95% (hereinafter, D 95 ) can be an important factor. Coarse particles in large amounts mixed, D 95 is more than 3.0μm when reduces the smoothness and gloss, the coating layer strength decreases. Therefore, it is preferable that D 95 is 3.0μm or less. D 95 is more preferably 2.5 μm or less.
なお、軽質炭酸カルシウムを上記所望の粒径とするために脱水工程後に分散工程および粉砕工程を設けることが好ましいが、分散処理後の平均粒子が所望の平均粒径の範囲にある場合、粉砕を行わずに、そのまま塗工用顔料として使用してもよい。 In order to make the light calcium carbonate have the desired particle size, it is preferable to provide a dispersion step and a pulverization step after the dehydration step. However, if the average particle after the dispersion treatment is in the range of the desired average particle size, the pulverization is performed. You may use as a pigment for coating as it is, without performing.
また、分散工程において、軽質炭酸カルシウムの脱水組成物を重質炭酸カルシウムスラリーに混合して、混合スラリーとして湿式粉砕機で粉砕することで、高濃度なスラリーを調製することも可能である。なお、軽質炭酸カルシウムと重質炭酸カルシウムの比率は、塗被紙の白紙品質などに応じて、適宜調整することが可能である。 In the dispersion step, it is also possible to prepare a high-concentration slurry by mixing a dehydrated composition of light calcium carbonate with a heavy calcium carbonate slurry and pulverizing it as a mixed slurry with a wet pulverizer. The ratio of light calcium carbonate to heavy calcium carbonate can be appropriately adjusted according to the blank paper quality of the coated paper.
本発明による軽質炭酸カルシウムは、以下のような用途に用いることができる。 The light calcium carbonate by this invention can be used for the following uses.
一般的に紙を製造する工程には、例えば、パルプを製造する工程、パルプを混合、叩解し、填料等の薬品を添加する調成工程、紙を抄いて乾燥させる抄紙工程、紙の表面に顔料等を塗工する塗工工程、そして仕上げ加工工程がある。本発明の軽質炭酸カルシウムは、上記調成工程における填料または上記塗工工程における顔料として用いることができる。 In general, the process for producing paper includes, for example, a process for producing pulp, a preparation process for mixing and beating pulp, and adding chemicals such as filler, a paper making process for making paper and drying, and a paper surface. There are a coating process for coating pigments and a finishing process. The light calcium carbonate of the present invention can be used as a filler in the preparation step or a pigment in the coating step.
（１）填料としての用途
本発明で得られた軽質炭酸カルシウムは、一般的に使用されている填料、例えば、重質炭酸カルシウム、軽質炭酸カルシウム、亜硫酸カルシウム、石膏、タルク、カオリン、クレー、焼成カオリン、ホワイトカーボン、非晶質シリカ、デラミネートカオリン、ケイソウ土、炭酸マグネシウム、二酸化チタン、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、水酸化亜鉛等の無機系填料や尿素ホルマリン樹脂微粒子、微小中空粒子等の有機系填料等と混合して使用することもできる。填料は２種以上の混合使用も可能である。混合比率は紙の品質に応じて調整することが可能であり、特に限定はない。填料の配合量は、一般に、紙（原紙）灰分が３〜２０質量％の範囲となるように添加される。
(1) Use as filler The light calcium carbonate obtained in the present invention is generally used as a filler, for example, heavy calcium carbonate, light calcium carbonate, calcium sulfite, gypsum, talc, kaolin, clay, and baking. Kaolin, white carbon, amorphous silica, delaminated kaolin, diatomaceous earth, magnesium carbonate, titanium dioxide, aluminum hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide and other inorganic fillers, urea formalin resin fine particles, fine It can also be used by mixing with organic fillers such as hollow particles. Two or more fillers can be used in combination. The mixing ratio can be adjusted according to the quality of the paper and is not particularly limited. The blending amount of the filler is generally added so that the paper (base paper) ash content is in the range of 3 to 20% by mass.
パルプとしては、例えば、一般に使用されているＬＢＫＰやＮＢＫＰ等の漂白化学パルプ、砕木パルプ（ＧＰ）、加圧式砕木パルプ（ＰＧＷ）、リファイナ砕木パルプ（ＲＧＰ）、サーモメカニカルパルプ（ＴＭＰ）等の機械パルプ、脱墨古紙パルプ（ＤＩＰ）、損紙などが適宜混合使用される。また、ケナフ等の非木材繊維原料から得られるパルプ繊維、合成パルプ、無機繊維等の１種以上を原紙に配合することもできる。機械パルプやＤＩＰは、必要に応じて漂白して使用することもでき、漂白の程度も任意に行うことができる。なお、パルプの漂白には、塩素ガスのような分子状塩素や二酸化塩素のような塩素化合物を使用しない漂白工程を採用することが、環境保全の観点から好ましく、このような漂白工程を経たパルプとしては、ＥＣＦ（Elemental Chlorine Free）パルプやＴＣＦ（Totally Chlorine Free）パルプを挙げることができる。 Examples of the pulp include commonly used bleached chemical pulp such as LBKP and NBKP, ground pulp (GP), pressurized ground wood pulp (PGW), refined ground wood pulp (RGP), and thermomechanical pulp (TMP). Pulp, deinked waste paper pulp (DIP), waste paper, and the like are appropriately mixed and used. Moreover, 1 or more types, such as a pulp fiber obtained from non-wood fiber raw materials, such as kenaf, a synthetic pulp, an inorganic fiber, can also be mix | blended with a base paper. Mechanical pulp and DIP can be used after being bleached if necessary, and the degree of bleaching can be arbitrarily performed. For bleaching pulp, it is preferable to use a bleaching process that does not use molecular chlorine such as chlorine gas or chlorine compounds such as chlorine dioxide from the viewpoint of environmental conservation. Pulp that has undergone such bleaching process is used. Examples thereof include ECF (Elemental Chlorine Free) pulp and TCF (Totally Chlorine Free) pulp.
また、紙中にはパルプや填料の他に、内添サイズ剤、アニオン性、ノニオン性、カチオン性もしくは両性の歩留り向上剤、濾水性向上剤、紙力増強剤等で例示される各種の抄紙用内添助剤を、必要に応じて添加することができる。内添サイズ剤の具体例としては、アルキルケテンダイマー系、アルケニル無水コハク酸系、スチレン−アクリル系、高級脂肪酸系、石油樹脂系サイズ剤、ロジン系サイズ剤等が挙げられる。また、歩留り向上剤、濾水性向上剤、紙力増強剤の具体例としては、アルミニウム等の多価金属化合物（具体的には、硫酸バンド、塩化アルミニウム、アルミン酸ソーダ、塩基性アルミニウム化合物等）、各種澱粉類、ポリアクリルアミド、尿素樹脂、ポリアミド・ポリアミン樹脂、ポリエチレンイミン、ポリアミン、ポリビニルアルコール、ポリエチレンオキサイド等が挙げられる。 In addition to pulp and fillers, various papermaking materials exemplified by internal sizing agents, anionic, nonionic, cationic or amphoteric yield improvers, drainage improvers, paper strength enhancers, etc. The internal additive aid can be added as necessary. Specific examples of the internally added sizing agent include alkyl ketene dimer, alkenyl succinic anhydride, styrene-acrylic, higher fatty acid, petroleum resin sizing agent, rosin sizing agent and the like. Specific examples of yield improvers, drainage improvers, and paper strength enhancers include polyvalent metal compounds such as aluminum (specifically, sulfate bands, aluminum chloride, sodium aluminate, basic aluminum compounds, etc.) And various starches, polyacrylamide, urea resin, polyamide-polyamine resin, polyethyleneimine, polyamine, polyvinyl alcohol, polyethylene oxide and the like.
紙の抄造条件は特に限定はなく、抄紙機としては、例えば、長網式抄紙機、ギャップフォーマー型抄紙機、円網式抄紙機、短網式抄紙機等の商業規模の抄紙機が、目的に応じて適宜選択して使用できる。抄紙方式としては、酸性抄紙、中性抄紙、弱アルカリ性抄紙等のいずれの方式も使用することができる。紙上に各種サイズプレス機およびロールコーターなどで澱粉等の天然接着剤やポリビニルアルコール等の合成接着剤を用いてサイズ処理を行なうことも可能である。 The paper making conditions are not particularly limited, and examples of the paper machine include a commercial paper machine such as a long net paper machine, a gap former type paper machine, a circular net paper machine, and a short net paper machine. It can be appropriately selected and used according to the purpose. As the papermaking system, any system such as acidic papermaking, neutral papermaking, and weak alkaline papermaking can be used. It is also possible to perform size treatment on paper using a natural adhesive such as starch or a synthetic adhesive such as polyvinyl alcohol with various size presses and roll coaters.
本発明で得られた軽質炭酸カルシウムを填料として使用した紙は、不透明度、平滑性を付与することができ、従来の填料を内添した紙であれば特に限定はないが、紙の種類としては、包装用紙、紙容器、インクジェット用紙、ＰＰＣ用紙などの記録用紙、新聞用紙、上質紙、中質紙、各種塗工用原紙、壁紙、繊維板、写真用原紙、含浸用原紙、難燃紙などが挙げられる。 Paper using light calcium carbonate obtained in the present invention as a filler can provide opacity and smoothness, and is not particularly limited as long as it is a paper internally added with a conventional filler. Recording paper such as wrapping paper, paper containers, ink jet paper, PPC paper, newsprint paper, fine paper, medium paper, various coating base paper, wallpaper, fiberboard, photographic base paper, impregnating base paper, flame retardant paper Etc.
本発明の軽質炭酸カルシウムを填料として内添した紙の坪量については、特に限定はないが、所望する効果が発揮されるのは、３０〜５００ｇ／ｍ２程度の範囲である。なお、本発明の軽質炭酸カルシウムはこの範囲を超えた板紙、カード等の厚紙にも添加できる。 The basis weight of the paper internally added with the light calcium carbonate of the present invention as a filler is not particularly limited, but the desired effect is exhibited in a range of about 30 to 500 g / m 2 . In addition, the light calcium carbonate of this invention can be added also to cardboards, such as paperboard and a card | curd exceeding this range.
（２）塗工用顔料としての用途
原紙の少なくとも片面に、本発明で得られた軽質炭酸カルシウムを含有する顔料と接着剤を主成分とする塗被層を１層以上形成させることで製造することができる。本発明で得られた軽質炭酸カルシウムは、顔料として用いた場合、平滑性、光沢発現性、不透明度、インキセット性に優れた性質をもっており、これら効果を発現させるために、塗被層中の全顔料の５質量％以上含有させるのが好ましい。本方法で得られた軽質炭酸カルシウムを含有した塗被層を原紙と接触させることで、平滑性、インキセット性の向上効果をより一層発現させることができる。また、従来の軽質炭酸カルシウムより光沢発現性に優れるため、最外塗被層中に配合されているカオリン配合量の削減が可能となる。
(2) Use as a coating pigment Manufactured by forming one or more coating layers mainly composed of a pigment containing light calcium carbonate obtained in the present invention and an adhesive on at least one side of a base paper. be able to. When used as a pigment, the light calcium carbonate obtained in the present invention has excellent properties such as smoothness, glossiness, opacity, and ink setting properties. In order to express these effects, It is preferable to contain 5% by mass or more of the total pigment. By bringing the coating layer containing light calcium carbonate obtained by this method into contact with the base paper, the effect of improving the smoothness and ink setting properties can be further exhibited. Moreover, since it is more excellent in gloss expression than conventional light calcium carbonate, the amount of kaolin compounded in the outermost coating layer can be reduced.
本発明において、塗被層中に含有する本方法で得られた軽質炭酸カルシウム以外の顔料としては、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、硫酸カルシウム、硫酸バリウム、水酸化アルミニウム、二酸化チタン、酸化亜鉛、アルミナ、炭酸マグネシウム、酸化マグネシウム、シリカ、アルミナ珪酸マグネシウム、珪酸カルシウム、ベントナイト、ゼオライト、セリサイト、スクメタイト等の無機顔料や、密実型、中空型、貫通孔型のプラスチックピグメント、バインダーピグメント等の有機顔料等、通常の塗被紙分野に使用される顔料を使用することが可能であり、これらの中から１種以上を適宜選択して使用できる。 In the present invention, pigments other than the light calcium carbonate obtained by the present method contained in the coating layer include heavy calcium carbonate, light calcium carbonate, talc, calcium sulfate, barium sulfate, aluminum hydroxide, titanium dioxide, Inorganic pigments such as zinc oxide, alumina, magnesium carbonate, magnesium oxide, silica, alumina magnesium silicate, calcium silicate, bentonite, zeolite, sericite, and scumite, solid type, hollow type, through-hole type plastic pigments, binder pigments It is possible to use pigments used in the ordinary coated paper field, such as organic pigments, etc., and one or more of these can be appropriately selected and used.
以上のような顔料を含む塗被層の接着剤成分には、通常は分散型接着剤を使用する。分散型接着剤としては、スチレン−ブタジエン共重合体、メチルメタクリレート−ブタジエン共重合体などの共役ジエン系重合体ラテックス、アクリル系重合体ラテックス、エチレン−酢酸ビニル共重合体などのビニル系重合体ラテックスなどが例示できる。 A dispersion-type adhesive is usually used for the adhesive component of the coating layer containing the pigment as described above. Dispersion type adhesives include conjugated diene polymer latexes such as styrene-butadiene copolymers and methyl methacrylate-butadiene copolymers, acrylic polymer latexes, and vinyl polymer latexes such as ethylene-vinyl acetate copolymers. Etc. can be exemplified.
上記の分散型接着剤と共に少量の水溶性接着剤を併用することができる。水溶性接着剤としては、酸化澱粉、エステル化澱粉、冷水可溶性澱粉などの各種澱粉類、カゼイン、大豆蛋白、合成蛋白などの蛋白質類、カルボキシメチルセルロース、メチルセルロースなどのセルロース誘導体、ポリビニルアルコールやその変性品などが例示できる。 A small amount of water-soluble adhesive can be used in combination with the above dispersion-type adhesive. Examples of water-soluble adhesives include various starches such as oxidized starch, esterified starch and cold water soluble starch, proteins such as casein, soy protein and synthetic protein, cellulose derivatives such as carboxymethylcellulose and methylcellulose, polyvinyl alcohol and its modified products. Etc. can be exemplified.
本発明の塗被紙の塗被層には、必要に応じて、青系統あるいは紫系統の染料や有色顔料、蛍光増白染料、増粘剤、保水剤、酸化防止剤、老化防止剤、導電誘導剤、消泡剤、紫外線吸収剤、分散剤、ｐＨ調整剤、離型剤、耐水化剤、撥水剤等の各種助剤を適宜配合することができる。 For the coated layer of the coated paper of the present invention, a blue or purple dye or colored pigment, a fluorescent whitening dye, a thickener, a water retention agent, an antioxidant, an anti-aging agent, a conductive material, if necessary. Various auxiliaries such as an inducer, an antifoaming agent, an ultraviolet absorber, a dispersant, a pH adjuster, a mold release agent, a water-proofing agent, and a water repellent can be appropriately blended.
原紙上に設ける塗被層は、１層または２層以上の多層にするかは特に限定はない。多層の場合、全てが同一である必要はなく、要求される品質レベルに応じて適宜調整することが可能である。また、塗被層の塗被量も、特に限定されるものではなく、塗被紙の白紙品質、印刷品質などに応じて調整することが可能であるが、一般的には、片面あたり５〜４０ｇ／ｍ２程度である。 There is no particular limitation on whether the coating layer provided on the base paper is a single layer or a multilayer of two or more layers. In the case of multiple layers, they need not all be the same, and can be appropriately adjusted according to the required quality level. Further, the coating amount of the coating layer is not particularly limited, and can be adjusted according to the blank paper quality, printing quality, etc. of the coated paper, but generally 5 to 5 per side. It is about 40 g / m 2 .
本発明における塗被層を設ける際の塗工方式については、通常の塗被紙製造分野で使用されている各種の塗工装置、例えばエアーナイフコーター、各種のブレードコーター、ゲートロールコーター、ロールコーター、ダイコーター、カーテンコーター等を適宜使用することができる。 As for the coating method for providing the coating layer in the present invention, various coating apparatuses used in the ordinary coated paper manufacturing field, such as air knife coaters, various blade coaters, gate roll coaters, roll coaters. A die coater, a curtain coater, or the like can be used as appropriate.
このようにして得られた塗被紙は、各種公知公用の仕上げ装置、例えばスーパーカレンダ、グロスカレンダ、ソフトカレンダ、マットカレンダ等に通紙して製品仕上げを施してもよい。 The coated paper thus obtained may be finished by passing the paper through various known and official finishing devices such as a super calender, gloss calender, soft calender, mat calender and the like.
また、本発明の軽質炭酸カルシウムを填料として使用した原紙と、本発明の軽質炭酸カルシウムを原料とする無機粒子を含有する塗被層とを組み合わせて、塗被紙としてもよい。 The base paper using the light calcium carbonate of the present invention as a filler may be combined with the coating layer containing inorganic particles made from the light calcium carbonate of the present invention as a coated paper.
以下に、具体例を挙げて本発明を説明するが、それらに限定されるものではない。なお、以下の説明において、特に断らない限り、「部」および「％」は、それぞれ「質量部」および「質量％」を意味する。 Hereinafter, the present invention will be described with specific examples, but is not limited thereto. In the following description, “part” and “%” mean “part by mass” and “% by mass”, respectively, unless otherwise specified.
１．軽質炭酸カルシウムの作製
下記の本発明例１〜８および比較例１、２の要領において、軽質炭酸カルシウムを作製し、評価を行った。
1. Production of Light Calcium Carbonate Light calcium carbonate was produced and evaluated in the manner of the following Invention Examples 1 to 8 and Comparative Examples 1 and 2.
（本発明例１）
本発明例１では、工業用生石灰（ＣＯ２含有率０．３％）１ｋｇあたり、消和水として３０℃の水を０．５ｋｇ添加して、ニーダーを用いて３０分間消化した。得られた消石灰を４４０メッシュ（３２μｍ）の篩で分級した後、４０℃の水と混合させて、１２％の消石灰スラリー１０ｋｇを調製した。次に、攪拌周速５．０ｍ／ｓ、炭酸ガス（ガス濃度１００％）を１２ｌ／分の流量で、ｐＨが７〜８となるまで炭酸化させ、軽質炭酸カルシウムを得た。
(Invention Example 1)
In Inventive Example 1, 0.5 kg of 30 ° C. water was added per 1 kg of industrial quicklime (CO 2 content: 0.3%) and digested for 30 minutes using a kneader. The obtained slaked lime was classified with a 440 mesh (32 μm) sieve and then mixed with water at 40 ° C. to prepare 10 kg of 12% slaked lime slurry. Next, carbonation was carried out at a stirring peripheral speed of 5.0 m / s and carbon dioxide gas (gas concentration 100%) at a flow rate of 12 l / min until the pH reached 7 to 8 to obtain light calcium carbonate.
（本発明例２）
本発明例２では、本発明例１において、消和水を０．８ｋｇとした以外は、本発明例１と同様にして軽質炭酸カルシウムを得た。
(Invention Example 2)
In Inventive Example 2, light calcium carbonate was obtained in the same manner as in Inventive Example 1 except that the soaking water was changed to 0.8 kg in Inventive Example 1.
（本発明例３）
本発明例３では、本発明例１において、消化後分級せず得られた１２％の消石灰スラリーを、解砕メディアである直径１．０〜１．４ｍｍのガラスビーズを充填してサンドグラインダーで湿式粉砕処理を１０分間行った以外は、本発明例１と同様にして軽質炭酸カルシウムを得た。
(Invention Example 3)
In Invention Example 3, the 12% slaked lime slurry obtained without classification after digestion in Invention Example 1 was filled with glass beads having a diameter of 1.0 to 1.4 mm, which is a crushing medium, and a sand grinder. Light calcium carbonate was obtained in the same manner as in Example 1 except that the wet pulverization was performed for 10 minutes.
（本発明例４）
本発明例４では、本発明例１において、得られた消石灰を１００メッシュ（１５０μｍ）の篩で分級した以外は、本発明例１と同様にして軽質炭酸カルシウムを得た。
(Invention Example 4)
In Inventive Example 4, light calcium carbonate was obtained in the same manner as in Inventive Example 1, except that the obtained slaked lime in Invented Example 1 was classified with a 100 mesh (150 μm) sieve.
（本発明例５）
本発明例５では、本発明例４において、工業用生石灰（ＣＯ２含有率２．１％）とした以外は、本発明例４と同様にして軽質炭酸カルシウムを得た。
(Invention Example 5)
In Inventive Example 5, light calcium carbonate was obtained in the same manner as in Inventive Example 4 except that in the Invented Example 4, industrial quicklime (CO 2 content 2.1%) was used.
（本発明例６）
本発明例６では、本発明例１において、消石灰スラリーに種結晶として針状軽質炭酸カルシウム（商品名：ＴＰ１２３ＣＳ、奥多摩工業社製）を固形分換算で消石灰：針状軽質炭酸カルシウム＝９９：１となる比率で添加した以外は、本発明例１と同様にして軽質炭酸カルシウムを得た。
(Invention Example 6)
In Invention Example 6, in Example 1 of the present invention, acicular light calcium carbonate (trade name: TP123CS, manufactured by Okutama Kogyo Co., Ltd.) is used as a seed crystal in the slaked lime slurry as slaked lime: acicular light calcium carbonate = 99: 1. A light calcium carbonate was obtained in the same manner as in Inventive Example 1 except that it was added in the ratio as follows.
（本発明例７）
本発明例７では、工業用生石灰（ＣＯ２含有率０．３％）１ｋｇあたり、消和水として６０℃の水を９ｋｇ添加して、ニーダーを用いて１２０分間消化した。得られた消石灰を３３０メッシュ（４５μｍ）の篩で分級した後、遠心分離機を用いて、微粒スラリーと粗粒スラリーに分離した。分離した粗粒消石灰スラリーを４０℃まで冷却し、１２％の消石灰スラリー１０ｋｇを調製した。次に、消石灰スラリーに種結晶として針状軽質炭酸カルシウム（商品名：ＴＰ１２３ＣＳ、奥多摩工業社製）を固形分換算で消石灰：針状軽質炭酸カルシウム＝９９：１となる比率で添加した。攪拌周速５．０ｍ／ｓ、炭酸ガス（ガス濃度１００％）を１２ｌ／ｍｉｎの流量でｐＨ＝７〜８となるまで炭酸化させ、軽質炭酸カルシウムを得た。
(Invention Example 7)
In Example 7 of the present invention, 9 kg of 60 ° C. water was added as a soaking water per 1 kg of industrial quicklime (CO 2 content: 0.3%), and digested for 120 minutes using a kneader. The obtained slaked lime was classified with a 330 mesh (45 μm) sieve and then separated into a fine slurry and a coarse slurry using a centrifuge. The separated coarse slaked lime slurry was cooled to 40 ° C. to prepare 10 kg of 12% slaked lime slurry. Next, acicular light calcium carbonate (trade name: TP123CS, manufactured by Okutama Kogyo Co., Ltd.) was added as a seed crystal to the slaked lime slurry at a ratio of slaked lime: acicular light calcium carbonate = 99: 1 in terms of solid content. Stirring speed was 5.0 m / s, carbon dioxide (gas concentration 100%) was carbonized at a flow rate of 12 l / min until pH = 7-8, and light calcium carbonate was obtained.
（比較例１）
比較例１では、本発明例１において、得られた消石灰を分級せずに炭酸化した以外は、本発明例１と同様にして軽質炭酸カルシウムを得た。
(Comparative Example 1)
In Comparative Example 1, light calcium carbonate was obtained in the same manner as in Inventive Example 1, except that the obtained slaked lime in Inventive Example 1 was carbonated without classification.
（比較例２）
比較例２では、本発明例３において、消和水として６０℃の水を９ｋｇ添加し、１２０分間消化した以外は、本発明例３と同様にして軽質炭酸カルシウムを得た。
(Comparative Example 2)
In Comparative Example 2, light calcium carbonate was obtained in the same manner as in Inventive Example 3, except that 9 kg of 60 ° C. water was added as a soaking water in Example 3 of the invention and digested for 120 minutes.
上記の本発明例および比較例で得られた軽質炭酸カルシウムを下記の粉砕処理を行った後、顔料評価紙を作製した。 The light calcium carbonate obtained in the above examples of the present invention and comparative examples was subjected to the following pulverization treatment, and a pigment evaluation paper was prepared.
（顔料評価用炭酸カルシウムの粉砕処理）
前記本発明例および比較例で得られた炭酸カルシウムスラリーをフィルタープレス・ドライヤーロールフィット（株式会社宇野澤組鐵工所製）により脱水・操作操作を行い、固形分濃度７３％のケーキを得た。次いで、インテンシブミキサを用いて炭酸カルシウムに対し１．０％ポリアクリル酸ソーダ分散剤（商品名：アロンＴ−５０、東亜合成社製）を加えて分散し、炭酸カルシウムスラリーを調製した。さらに、上記炭酸カルシウムスラリーを、解砕メディアとして直径１．０〜１．４ｍｍのガラスビーズを用いてサンドグラインダーで湿式粉砕処理を５０分間行い、固形分濃度７１％の顔料評価用炭酸カルシウムスラリーを調製した。
(Crushing of calcium carbonate for pigment evaluation)
The calcium carbonate slurry obtained in the inventive examples and comparative examples was subjected to dehydration and operation using a filter press / dryer roll fit (manufactured by Unosawa Gumi Co., Ltd.) to obtain a cake having a solid content concentration of 73%. Next, 1.0% sodium polyacrylate dispersant (trade name: Aron T-50, manufactured by Toa Gosei Co., Ltd.) was added to the calcium carbonate using an intensive mixer and dispersed to prepare a calcium carbonate slurry. Further, the calcium carbonate slurry is subjected to a wet grinding process with a sand grinder for 50 minutes using glass beads having a diameter of 1.0 to 1.4 mm as a crushing medium, and a calcium carbonate slurry for pigment evaluation having a solid content concentration of 71% is obtained. Prepared.
（顔料評価紙の作製）
上記の方法により調製された炭酸カルシウムスラリーに対して、スチレン−ブタジエン共重合体ラテックス（商品名：Ｔ２６２８Ｇ、ＪＳＲ社製）６部（固形分）、予め糊化した酸化澱粉（商品名：王子エースＢ、王子コーンスターチ社製）３部（固形分）を添加して混合攪拌し、塗料を調製した。そして、得られた塗料を米坪７０ｇ／ｍ２の上質原紙に、片面当り乾燥重量で１２ｇ／ｍ２となるように手塗りブレードコーターを使用して両面に塗被を行い、乾燥後、４０℃のスーパーカレンダに２回通紙処理して顔料評価紙を得た。
(Preparation of pigment evaluation paper)
6 parts (solid content) of styrene-butadiene copolymer latex (trade name: T2628G, manufactured by JSR), pre-gelatinized oxidized starch (trade name: Oji Ace) with respect to the calcium carbonate slurry prepared by the above method B (manufactured by Oji Cornstarch Co., Ltd.) (3 parts) (solid content) was added and mixed and stirred to prepare a paint. The obtained coating material was coated on both sides of a high-quality base paper of 70 g / m 2 using a hand-painted blade coater so that the dry weight per side was 12 g / m 2. A paper for paper evaluation was obtained by passing the paper twice through a super calendar at 0 ° C.
上記本発明例および比較例で得られた消石灰、炭酸化後、粉砕後に得られた軽質炭酸カルシウムおよび顔料評価紙について、下記の評価を行い、その結果を表１に示した。 The slaked lime obtained in the above examples of the present invention and comparative examples, light calcium carbonate obtained after carbonation and pulverization, and pigment evaluation paper were evaluated as follows, and the results are shown in Table 1.
（粒径測定）
レーザー回折法（日機装社製マイクロトラックＨＲＡＸ−１００）による粒度分布を測定した。消石灰粒子においては、１μｍ以下および１００μｍ以下の累積体積、ならびに平均粒径を求めた。また、炭酸化後の炭酸カルシウムスラリーにおいては、平均粒径を求めた。粉砕により微細化された軽質炭酸カルシウムにおいては、平均粒径および累積体積が９５％に相当する粒径をＤ９５として求めた。なお、累積体積５０％に相当する粒径を平均粒径とした。
(Particle size measurement)
The particle size distribution was measured by a laser diffraction method (Microtrack HRAX-100 manufactured by Nikkiso Co., Ltd.). For slaked lime particles, the cumulative volume of 1 μm or less and 100 μm or less and the average particle size were determined. Moreover, the average particle diameter was calculated | required in the calcium carbonate slurry after carbonation. In light calcium carbonate which is reduced by grinding, the particle size average particle diameter and the cumulative volume equivalent to 95% was determined as D 95. In addition, the particle size corresponding to the cumulative volume of 50% was defined as the average particle size.
（白紙光沢度）
ＪＩＳ Ｐ８１４２に準拠して、７５度における白紙面の光沢度を測定した。
(Blank gloss)
Based on JIS P8142, the glossiness of the white paper surface at 75 degrees was measured.
（印刷強度）
ＲＩ印刷試験機（明製作所製）で、印刷インキ（商品名：紙試験用ＳＤ５０紅、東洋インキ社製）を、０．６ｍｌ使用して印刷を行い、印刷面のピッキングの程度を目視評価した。
○：ピッキングが全く発生せず、良好。
△：ピッキングが少し発生し、やや劣る。実用上は許容レベル。
×：ピッキングが多く発生し、劣る。
(Print strength)
Using an RI printing tester (manufactured by Meisei Seisakusho), printing was performed using 0.6 ml of printing ink (trade name: SD50 for paper testing, manufactured by Toyo Ink Co., Ltd.), and the degree of picking on the printed surface was visually evaluated. .
○: Good with no picking.
Δ: A little picking occurs and slightly inferior. In practical use, acceptable level.
X: Many pickings occur and are inferior.
表１より、請求項１に規定の範囲内にある本発明例１〜７によって得られた軽質炭酸カルシウムは、顔料評価紙の品質において白色光沢度および表面強度ともに良好な結果を示した。 From Table 1, the light calcium carbonate obtained by Examples 1 to 7 of the present invention within the range specified in claim 1 showed good results in both the white glossiness and the surface strength in the quality of the pigment evaluation paper.
特に、乾式消和法により生成した消石灰粒子を細粒の篩によって分級した後に炭酸化を行った本発明例１、および本発明例１の炭酸化の際に種晶を用いた本発明例６では、微細な針状の炭酸カルシウムが得られ、顔料評価紙品質においても良好な結果が得られた。 In particular, the present invention example 1 in which the slaked lime particles produced by the dry slaked method were classified by a fine sieve and then carbonized, and the present invention example 6 in which seed crystals were used in the carbonation of the present invention example 1 Then, fine acicular calcium carbonate was obtained, and good results were obtained in terms of pigment evaluation paper quality.
また、本発明例１の分級を比較的粗粒の篩によって行った本発明例４では、わずかに粗粒の消石灰粒子が混在するものの、微細な針状の炭酸カルシウムが得られ、顔料評価紙品質において、本発明例１および６に次いで良好な結果が得られた。 Further, in Inventive Example 4 in which the classification of Inventive Example 1 was performed with a relatively coarse sieve, fine acicular calcium carbonate was obtained, although slightly coarse slaked lime particles were mixed, and pigment evaluation paper In terms of quality, good results were obtained after Invention Examples 1 and 6.
本発明例１の消和水をわずかに増やした本発明例２、分級を行わずに消石灰粒子の粉砕を行った本発明例３、および湿式消和法により生成した消石灰粒子を篩および遠心分離を用いて分級した本発明例７では、微細な消石灰粒子が比較的多く生成されるため、一部紡錘状の炭酸カルシウムが生じた。顔料評価紙品質において、本発明例１、４および６と比較してわずかに劣るものの、下記の比較例１および２よりは優れていた。 Invention Example 2 with a slight increase in slaked water of Invention Example 1, Invention Example 3 in which slaked lime particles were pulverized without classification, and slaked lime particles produced by the wet slaked method were sieved and centrifuged In Example 7 of the present invention, which was classified by using a relatively large amount of fine slaked lime particles, a part of spindle-shaped calcium carbonate was generated. Although the pigment evaluation paper quality was slightly inferior to Examples 1, 4 and 6 of the present invention, it was superior to Comparative Examples 1 and 2 below.
本発明例５では、消石灰粒子の原料として二酸化炭素含有率の高い生石灰を用いたため、一部紡錘状の炭酸カルシウムが生じた。本発明例２、３および７と同様に品質がわずかに劣るものの、下記の比較例１および２よりは優れていた。 In Example 5 of the present invention, quick lime having a high carbon dioxide content was used as a raw material for the slaked lime particles, so that partly spindle-shaped calcium carbonate was produced. Although the quality was slightly inferior like Examples 2, 3 and 7, it was superior to Comparative Examples 1 and 2 below.
一方、比較例１では、本発明例１の分級を行わず、粗粒の消石灰粒子が本発明の規定を超える量含まれるため、炭酸カルシウムが一部毬栗状を呈し、顔料評価紙品質の結果が著しく悪化した。 On the other hand, in Comparative Example 1, the classification of Inventive Example 1 is not performed, and the amount of coarse slaked lime particles exceeds the amount defined in the present invention. Was significantly worse.
また、比較例２では、湿式消和法により生成した消石灰粒子を破砕のみ行い、分級しなかったため細粒の消石灰粒子が本発明の規定を超える量含まれ、炭酸カルシウムが紡錘状を呈し、顔料評価紙品質の結果が悪化した。 In Comparative Example 2, the slaked lime particles produced by the wet slaked method were only crushed and not classified, so fine slaked lime particles were included in an amount exceeding the provisions of the present invention, the calcium carbonate had a spindle shape, and the pigment The result of evaluation paper quality deteriorated.
２．填料として使用した上質紙の作製
上記の本発明例および比較例で得られた軽質炭酸カルシウムを粉砕処理した後、填料として使用して、上質紙を作製した。
2. Preparation of high-quality paper used as a filler After the light calcium carbonate obtained in the above examples of the present invention and comparative examples was pulverized, it was used as a filler to prepare a high-quality paper.
（本発明例８）
本発明例８では、広葉樹パルプ（ＬＢＫＰ濾水度４５０ｍｌ）のスラリー（濃度２．５％）に、本発明例１の軽質炭酸カルシウムをパルプ絶乾重量当たり１５部、カチオン化澱粉（商品名：エースＫ１００、王子コーンスターチ社製）０．８部、硫酸バンド０．５部、アルキルケテンダイマー（商品名：Ｋ−２８７、荒川化学工業社製）０．１部をそれぞれ添加し、固形分濃度０．５％の紙料を調製した。調製した紙料をオントップのツインワイヤー抄紙機で抄紙、乾燥し、続いて、ゲートロールコーターで酸化澱粉の塗布量が乾燥重量で両面合計１．５ｇ／ｍ２となるように塗布、乾燥後、３ニップのマシンカレンダに通紙して、米坪７０ｇ／ｍ２の上質紙を得た。
(Invention Example 8)
In Inventive Example 8, 15 parts of light calcium carbonate of Inventive Example 1 per pulp dry weight of a hardwood pulp (LBKP freeness: 450 ml) (concentration: 2.5%), cationized starch (trade name: Ace K100 (manufactured by Oji Cornstarch Co., Ltd.) 0.8 part, sulfuric acid band 0.5 part, alkyl ketene dimer (trade name: K-287, Arakawa Chemical Industries Co., Ltd.) 0.1 part were added, and the solid content concentration was 0. A 5% paper stock was prepared. Paper is prepared and dried with an on-top twin-wire paper machine, and then coated and dried with a gate roll coater so that the coated amount of oxidized starch is 1.5 g / m 2 on both sides in terms of dry weight. The paper was passed through a 3-nip machine calendar to obtain a high-quality paper of 70 g / m 2 .
（本発明例９）
本発明例９では、填料の軽質炭酸カルシウムを本発明例２の軽質炭酸カルシウムとした以外は、本発明例８と同様にして上質紙を得た。
（本発明例１０）
本発明例１０では、填料の軽質炭酸カルシウムを本発明例３の軽質炭酸カルシウムとした以外は、本発明例８と同様にして上質紙を得た。
（比較例３）
比較例３では、填料の軽質炭酸カルシウムを比較例１の軽質炭酸カルシウムとした以外は、本発明例８と同様にして上質紙を得た。
（比較例４）
比較例４では、填料の軽質炭酸カルシウムを比較例２の軽質炭酸カルシウムとした以外は、本発明例８と同様にして上質紙を得た。
(Invention Example 9)
In Inventive Example 9, fine paper was obtained in the same manner as in Inventive Example 8, except that the light calcium carbonate used as the filler was changed to the light calcium carbonate of Inventive Example 2.
(Invention Example 10)
In Inventive Example 10, fine paper was obtained in the same manner as in Inventive Example 8, except that the light calcium carbonate used as the filler was changed to the light calcium carbonate of Inventive Example 3.
(Comparative Example 3)
In Comparative Example 3, fine paper was obtained in the same manner as in Example 8 except that the light calcium carbonate used as the filler was changed to the light calcium carbonate of Comparative Example 1.
(Comparative Example 4)
In Comparative Example 4, a fine paper was obtained in the same manner as in Example 8 except that the light calcium carbonate used as the filler was changed to the light calcium carbonate of Comparative Example 2.
上記で得た上質紙の品質を、下記の項目の評価を行い、結果を表２に示した。評価は、特に記載ない限り、２３℃、５０ＲＨ％の環境下で行った。 The quality of the quality paper obtained above was evaluated for the following items, and the results are shown in Table 2. Evaluation was performed in an environment of 23 ° C. and 50 RH% unless otherwise specified.
（ＰＰＳ平滑度の測定）
パーカープリントサーフ（ＰＰＳ）表面平滑度試験機（機種名：ＭＯＤＥＬ Ｍ−５６９型、ＭＥＳＳＭＥＲ ＢＵＣＨＥＬ社製、英国）を用い、バッキングディスク：ソフトラバー、クランプ圧力：０．９８ＭＰａで５回平滑度測定を行ない、その平均を求めた。
(Measurement of PPS smoothness)
Using a Parker Print Surf (PPS) surface smoothness tester (model name: MODEL M-569, manufactured by MESSMER BUCHEL, UK), backing disk: soft rubber, clamp pressure: 0.98 MPa, 5 times smoothness measurement The average was calculated.
（層間強度の測定）
インターナルボンドテスタを使用し、ＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．１８−２に準拠して測定した。
(Measurement of interlayer strength)
Using an internal bond tester, JAPAN TAPPI No. It measured based on 18-2.
表２より、本発明の軽質炭酸カルシウムを填料として用いた本発明例８〜１０の上質紙は、比較例３および４で得られた上質紙と比較して、平滑度および層間強度において優れる結果となった。 From Table 2, the high-quality papers of Examples 8 to 10 of the present invention using the light calcium carbonate of the present invention as a filler are superior in smoothness and interlayer strength as compared with the high-quality paper obtained in Comparative Examples 3 and 4. It became.
さらに詳細を見ると、上記で評価した炭酸カルシウムの品質が優れる程、それを填料として用いた上質紙の品質が優れる傾向が明瞭に認められる。 When the details are further seen, the tendency that the quality of the quality paper using the filler as the filler is superior as the quality of the calcium carbonate evaluated as described above is excellent is clearly recognized.
３．顔料として使用した塗被紙の作製
上記本発明例および比較例で得られた軽質炭酸カルシウムを粉砕処理した後、顔料として配合して、下記の要領において塗被紙を作製した。
3. Preparation of coated paper used as pigment After the light calcium carbonate obtained in the above invention examples and comparative examples was pulverized, it was blended as a pigment and coated paper was prepared in the following manner.
（i）２層両面塗被紙の作製
（本発明例１１）
本発明例１１では、以下に示す通りに下塗り塗被液および上塗り塗被液の調製を行った。
(I) Preparation of double-layer coated paper (Invention Example 11)
In Invention Example 11, an undercoat coating solution and an overcoat coating solution were prepared as shown below.
平均粒径１．３μｍの重質炭酸カルシウム（商品名：ハイドロカーブＫ−９、備北粉化工業社製）１００質量％からなる顔料スラリーに、顔料１００部に対して、酸化澱粉（商品名：エースＢ、前出）４部、スチレン−ブタジエン共重合体ラテックス（商品名：Ｔ２６２８Ｇ、前出）６部（いずれも固形分換算）、さらに、助剤として消泡剤及び染料を添加し、最終的に固形分濃度６２％の下塗り塗被液を調製した。 Heavy pigmented calcium carbonate having an average particle size of 1.3 μm (trade name: Hydrocurve K-9, manufactured by Bihoku Flour & Chemical Co., Ltd.), 100 parts by mass of pigment starch, 100 parts of pigment, oxidized starch (trade name: Ace B, supra) 4 parts, styrene-butadiene copolymer latex (trade name: T2628G, supra) 6 parts (all in terms of solid content), and further, an antifoaming agent and a dye are added as auxiliary agents. Specifically, an undercoat coating solution having a solid content concentration of 62% was prepared.
本発明例６の粉砕処理で得た軽質炭酸カルシウム７５％、平均粒径１．３μｍの重質炭酸カルシウム（商品名：ハイドロカーブＫ−９、前出）２５％からなる顔料スラリーに、顔料１００部に対して、酸化澱粉（商品名：エースＢ、前出）２部、スチレン−ブタジエン共重合体ラテックス（商品名：Ｔ２６２８Ｇ、前出）１０部（いずれも固形分換算）、さらに、助剤として消泡剤及び染料を添加し、最終的に固形分濃度６５％の上塗り塗被液を調製した。 Pigment 100 was added to a pigment slurry consisting of 75% light calcium carbonate obtained by the pulverization treatment of Invention Example 6 and 25% heavy calcium carbonate having an average particle size of 1.3 μm (trade name: Hydrocurve K-9, supra). Parts, oxidized starch (trade name: Ace B, supra) 2 parts, styrene-butadiene copolymer latex (trade name: T2628G, supra) 10 parts (all in terms of solid content), auxiliary agent Were added as an antifoaming agent and a dye, and finally an overcoating solution with a solid content of 65% was prepared.
（比較例５）
比較例５では、本発明例１１の上塗り塗被液の顔料を、比較例２の粉砕処理で得た軽質炭酸カルシウム７５％、平均粒径１．３μｍの重質炭酸カルシウム（商品名：ハイドロカーブＫ−９、前出）２５％とした以外は、本発明例１１と同様にして塗被液を調製した。
(Comparative Example 5)
In Comparative Example 5, the pigment of the top coat liquid of Invention Example 11 was obtained by using 75% light calcium carbonate obtained by the pulverization treatment of Comparative Example 2 and heavy calcium carbonate having an average particle size of 1.3 μm (trade name: Hydrocurve). K-9, ibid.) A coating solution was prepared in the same manner as in Example 11 except that 25%.
（比較例６）
比較例６では、本発明例１１の上塗り塗被液の顔料を、微粒カオリン（商品名：ミラグロスＪ、ＢＡＳＦ社製）５０％、平均粒径１．３μｍの重質炭酸カルシウム（商品名：ハイドロカーブＫ−９、前出）５０％とした以外は、本発明例１１と同様にして塗被液を調製した。
(Comparative Example 6)
In Comparative Example 6, the pigment of the top coat liquid of Invention Example 11 was obtained by using heavy calcium carbonate (trade name: Hydro A coating solution was prepared in the same manner as in Example 11 except that the curve K-9, ibid.) Was 50%.
(塗被紙の作製)
上記の本発明例および比較例で得られた塗被液を用いて塗被紙を作製した。
(Preparation of coated paper)
A coated paper was prepared using the coating solutions obtained in the above-described inventive examples and comparative examples.
米坪７０．０ｇ／ｍ２の上質原紙（緊度０．７５ｇ／ｃｍ３）に、下塗り塗被液を片面当たりの乾燥重量が７ｇ／ｍ２となるようにブレードコーターを使用して両面塗被、乾燥を行い、下塗り塗被層を設けた。次いで、上塗り塗被液を片面当たりの乾燥重量が９ｇ／ｍ２となるようにブレードコーターを使用して両面塗被、乾燥を行い、上塗り塗被層を設けた。このようにして得られた塗被紙を、温度７０℃、線圧２００ｋＮ／ｍでスーパーカレンダに通紙して、塗被紙を得た。 A basis weight 70.0 g / m 2 fine sheet (bulk density 0.75g / cm 3), both surfaces coated with a subbing coated liquid dry weight per one side using a blade coater so that 7 g / m 2 Covering and drying were performed to provide an undercoat coating layer. Next, the top coat liquid was coated on both sides using a blade coater and dried so that the dry weight per side was 9 g / m 2 , thereby providing a top coat layer. The coated paper thus obtained was passed through a super calendar at a temperature of 70 ° C. and a linear pressure of 200 kN / m to obtain a coated paper.
（ii）１層両面塗被紙の作製
（本発明例１２）
本発明例１２では、以下に示す通りに塗被液の調製を行った。
(Ii) Production of single-layer double-sided coated paper (Invention Example 12)
In Invention Example 12, a coating solution was prepared as described below.
本発明例６の粉砕処理で得た軽質炭酸カルシウム６５％、平均粒径１．３μｍの重質炭酸カルシウム（商品名：ハイドロカーブＫ−９、前出）３５％からなる顔料スラリーに、顔料１００部に対して、酸化澱粉（商品名：エースＢ、前出）４部、スチレン−ブタジエン共重合体ラテックス（商品名：Ｔ２６２８Ｇ、前出）７部（いずれも固形分換算）、さらに、助剤として消泡剤及び染料を添加し、最終的に固形分濃度６２％の塗被液を調製した。 Pigment 100 was added to a pigment slurry consisting of 65% light calcium carbonate obtained by the pulverization treatment of Invention Example 6 and 35% heavy calcium carbonate having an average particle size of 1.3 μm (trade name: Hydrocurve K-9, supra). Parts, oxidized starch (trade name: Ace B, supra) 4 parts, styrene-butadiene copolymer latex (trade name: T2628G, supra) 7 parts (all in terms of solid content), auxiliary agent As a defoaming agent and a dye, a coating solution having a solid concentration of 62% was finally prepared.
（比較例７）
比較例７では、本発明例１２の塗被液の顔料を、比較例２の粉砕処理で得た軽質炭酸カルシウム６５％、平均粒径１．３μｍの重質炭酸カルシウム（商品名：ハイドロカーブＫ−９、前出）３５％とした以外は、本発明例１２と同様にして塗被液を調製した。
(Comparative Example 7)
In Comparative Example 7, the pigment of the coating liquid of Inventive Example 12 was obtained by using 65% light calcium carbonate obtained by the pulverization treatment of Comparative Example 2 and heavy calcium carbonate having an average particle size of 1.3 μm (trade name: Hydrocurve K). -9, supra) A coating solution was prepared in the same manner as in Example 12 except that the content was 35%.
（比較例８）
比較例８では、本発明例１２の上塗り塗被液の軽質炭酸カルシウムを、微粒カオリン（ミラグロスＪ、前出）３０％、平均粒径１．３μｍの重質炭酸カルシウム（商品名：ハイドロカーブＫ−９、前出）７０％とした以外は、本発明例１２と同様にして塗被液を調製した。
(Comparative Example 8)
In Comparative Example 8, light calcium carbonate of the top coat liquid of Invention Example 12 was used as heavy calcium carbonate (trade name: Hydrocurve K) with 30% fine kaolin (Miragros J, supra) and an average particle size of 1.3 μm. -9, supra) A coating solution was prepared in the same manner as in Example 12 except that the content was 70%.
(塗被紙の作製)
上記の本発明例および比較例で得られた塗被液を用いて塗被紙を作製した。
(Preparation of coated paper)
A coated paper was prepared using the coating solutions obtained in the above-described inventive examples and comparative examples.
米坪７０．０ｇ／ｍ２の上質原紙（緊度０．７５ｇ／ｃｍ３）に、塗被層用塗被液を片面当たりの乾燥重量が８ｇ／ｍ２となるようにブレードコーターを使用して両面塗被、乾燥を行い、塗被層を設けた。このようにして得られた塗被紙を、温度７０℃、線圧２００ｋＮ／ｍでスーパーカレンダに通紙して、塗被紙を得た。 Use a blade coater on a fine base paper of 70.0 g / m 2 in weight (tension of 0.75 g / cm 3 ) so that the dry weight per side of the coating liquid is 8 g / m 2. Then, both sides were coated and dried to provide a coating layer. The coated paper thus obtained was passed through a super calendar at a temperature of 70 ° C. and a linear pressure of 200 kN / m to obtain a coated paper.
上記で得られた各塗被紙について、前記の評価および下記の評価を追加して行った。その結果を表３および表４に示した。 About each coated paper obtained above, the said evaluation and the following evaluation were added and performed. The results are shown in Tables 3 and 4.
（印刷光沢度）
ＲＩ印刷機で、印刷インキ（商品名：ＦＵＳＩＯＮ−Ｇ 墨、Ｓタイプ、大日本インキ化学工業社製）０．４ｃｃ使用して印刷を行い、光沢度計（ＧＭ−２６Ｄ、村上色彩研究所製）を用いて６０度光沢度を測定した。
(Print gloss)
Using an RI printer, printing was performed using 0.4 cc of printing ink (trade name: FUSION-G black, S type, manufactured by Dainippon Ink & Chemicals, Inc.), and a gloss meter (GM-26D, manufactured by Murakami Color Research Laboratory). ) Was used to measure 60 degree glossiness.
（インキセット評価）
ＲＩ印刷機で、印刷インキ（商品名：ＦＵＳＩＯＮ−Ｇ 墨、Ｓタイプ、既述）を０．６ｃｃ使用して印刷を行い、３分後に白紙と印刷面を重ねて、再度ＲＩ印刷機にニップし、白紙に転写したインキ濃度を目視評価した。
○：インキセットが早く、優れる。
△：インキセットはやや遅いが、実用上問題ない。
×：インキセットが遅く、実用上問題がある。
(Ink set evaluation)
Print using 0.6 cc of printing ink (trade name: FUSION-G black, S type, as described above) on the RI printer, and after 3 minutes, the blank paper and the printing surface are overlapped, and the RI printer is again nipped. The ink density transferred onto the white paper was visually evaluated.
○: The ink set is fast and excellent.
Δ: The ink set is a little slow, but there is no practical problem.
X: Ink setting is slow and there is a problem in practical use.
表３および表４より、２層両面塗被紙および１面両面塗被紙の双方において、本発明の軽質炭酸カルシウムを顔料として用いた本発明例１１および１２で得られた塗被紙が、比較例５および７と比べて優れる品質を示している。 From Table 3 and Table 4, the coated paper obtained in Invention Examples 11 and 12 using the light calcium carbonate of the present invention as a pigment in both the two-layer double-sided coated paper and the single-sided double-sided coated paper, Excellent quality compared to Comparative Examples 5 and 7.
また、本発明の軽質炭酸カルシウムを顔料として用いた塗被紙は、顔料としてカオリンを用いた塗被紙に匹敵する品質を有することが明らかになった。本発明の軽質炭酸カルシウムはカオリンと比較して安価であるため、高品質の塗被紙をより低コストで製造することが可能となる。 Moreover, it became clear that the coated paper using the light calcium carbonate of the present invention as a pigment has a quality comparable to a coated paper using kaolin as a pigment. Since the light calcium carbonate of the present invention is less expensive than kaolin, a high-quality coated paper can be produced at a lower cost.
以上の結果から、本発明により得られた軽質炭酸カルシウムは、いずれも白紙および印刷品質共に高品質であることが明らかになった。 From the above results, it has been clarified that the light calcium carbonate obtained by the present invention is of high quality in both blank paper and print quality.
本発明は、高品質な軽質炭酸カルシウム、粒径が揃った微細な軽質炭酸カルシウムを極めて容易かつ安定的に製造することができ、本発明の方法で得られた軽質炭酸カルシウムを填料ないし顔料として使用した紙は、白紙光沢度、平滑性、印刷表面強度等に優れる。 The present invention can produce high-quality light calcium carbonate and fine light calcium carbonate having a uniform particle size very easily and stably. The light calcium carbonate obtained by the method of the present invention can be used as a filler or pigment. The used paper is excellent in white paper glossiness, smoothness, printing surface strength, and the like.
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| JP2011027486A JP5673176B2 (en) | 2010-06-28 | 2011-02-10 | Slaked lime particles, method for producing light calcium carbonate, and paper and coated paper using light calcium carbonate obtained thereby |
| CN201180032703.7A CN102958843B (en) | 2010-06-28 | 2011-06-27 | The manufacture method of white lime particle, light calcium carbonate, the paper using it and White Board and light calcium carbonate |
| PCT/JP2011/064688 WO2012002324A1 (en) | 2010-06-28 | 2011-06-27 | Slaked lime particles, light calcium carbonate, paper and coated paper using same, and method for producing light calcium carbonate |
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