JP5003139B2 - Porous filler for paper, its production method and porous filler slurry for paper and paper - Google Patents
Porous filler for paper, its production method and porous filler slurry for paper and paper Download PDFInfo
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- JP5003139B2 JP5003139B2 JP2006343028A JP2006343028A JP5003139B2 JP 5003139 B2 JP5003139 B2 JP 5003139B2 JP 2006343028 A JP2006343028 A JP 2006343028A JP 2006343028 A JP2006343028 A JP 2006343028A JP 5003139 B2 JP5003139 B2 JP 5003139B2
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- silicon oxide
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- 239000000945 filler Substances 0.000 title claims description 261
- 239000002002 slurry Substances 0.000 title claims description 107
- 238000004519 manufacturing process Methods 0.000 title claims description 29
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 116
- 239000011707 mineral Substances 0.000 claims description 116
- 239000002253 acid Substances 0.000 claims description 115
- 239000007771 core particle Substances 0.000 claims description 100
- 239000002245 particle Substances 0.000 claims description 97
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000002184 metal Substances 0.000 claims description 59
- -1 silicon oxide compound Chemical class 0.000 claims description 58
- 239000011148 porous material Substances 0.000 claims description 56
- 239000007864 aqueous solution Substances 0.000 claims description 54
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 53
- 239000003792 electrolyte Substances 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 42
- 150000003839 salts Chemical class 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 30
- 239000012266 salt solution Substances 0.000 claims description 23
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 22
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000000123 paper Substances 0.000 description 104
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 90
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 64
- 238000003756 stirring Methods 0.000 description 49
- 230000015572 biosynthetic process Effects 0.000 description 45
- 238000003786 synthesis reaction Methods 0.000 description 45
- 230000002093 peripheral effect Effects 0.000 description 37
- 238000006386 neutralization reaction Methods 0.000 description 36
- 229910000019 calcium carbonate Inorganic materials 0.000 description 32
- 239000007787 solid Substances 0.000 description 24
- 239000004576 sand Substances 0.000 description 22
- 238000000034 method Methods 0.000 description 21
- 239000006185 dispersion Substances 0.000 description 20
- 239000004115 Sodium Silicate Substances 0.000 description 19
- 238000009826 distribution Methods 0.000 description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 19
- 229910052911 sodium silicate Inorganic materials 0.000 description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 17
- 229910052938 sodium sulfate Inorganic materials 0.000 description 17
- 235000011152 sodium sulphate Nutrition 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 239000008399 tap water Substances 0.000 description 15
- 235000020679 tap water Nutrition 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 239000011362 coarse particle Substances 0.000 description 12
- 229920001131 Pulp (paper) Polymers 0.000 description 10
- 239000010419 fine particle Substances 0.000 description 9
- 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 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 7
- 238000010008 shearing Methods 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 238000004513 sizing Methods 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 239000011246 composite particle Substances 0.000 description 5
- 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 5
- 238000002156 mixing Methods 0.000 description 5
- 239000013055 pulp slurry Substances 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000003490 calendering Methods 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 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
- 238000009835 boiling Methods 0.000 description 2
- 239000004067 bulking agent Substances 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
- 239000002775 capsule Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007788 liquid 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
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000004111 Potassium silicate Substances 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
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base 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
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 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
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005517 mercerization Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 1
- 229910052913 potassium silicate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active 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
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paper (AREA)
Description
本発明は、紙の嵩高化に用いられる多孔性填料ならび多孔性填料スラリーに関する。また、多孔性填料が配合された紙に関する。 The present invention relates to a porous filler and a porous filler slurry used for increasing the bulk of paper. The present invention also relates to a paper containing a porous filler.
紙は省資源や物流費の削減といった観点、環境保護運動の高まりといった社会的要求等から軽量化が望まれている。しかし、紙を軽量化すると紙厚が減少し、不透明度が下がって裏側の印刷が透けてしまうため、読みにくくなるだけでなく紙の高級感も損なわれるという問題があった。そのため、紙の厚さを維持した上での軽量化、すなわち嵩高化が要求されている。 Paper is desired to be reduced in weight from the viewpoints of resource saving and logistics cost reduction, and social demands such as an increasing environmental protection movement. However, when the paper is lightened, the paper thickness is reduced, the opacity is lowered, and the printing on the back side is transparent. Thus, there is a problem that not only it is difficult to read but also the high quality of the paper is impaired. Therefore, it is required to reduce the weight while maintaining the thickness of the paper, that is, to increase the bulk.
紙の嵩高化方法としては、例えば、紙の主原料である木材パルプを適宜選択する方法、パルプを叩解、マーセル化処理や酵素処理する方法、抄紙時にかかるウェットプレス圧または平滑化処理の圧力を緩和する方法、界面活性剤などの嵩高剤をパルプに添加する方法などが知られている。
しかしながら、これらの方法では、紙を充分に嵩高にできない上に、嵩高剤を用いた場合には抄紙時に発泡するという問題があった。
Examples of methods for increasing the bulk of the paper include, for example, a method of appropriately selecting wood pulp, which is the main raw material of paper, a method of beating pulp, a mercerization treatment or an enzyme treatment, and a wet press pressure or a smoothing treatment pressure applied during papermaking. A method of relaxing, a method of adding a bulking agent such as a surfactant to the pulp, and the like are known.
However, in these methods, there is a problem that the paper cannot be made sufficiently bulky, and when a bulking agent is used, foaming occurs during paper making.
そこで、嵩比重が小さい填料を添加する方法が提案されている。例えば、針状、柱状、イガグリ状炭酸カルシウム等のアスペクト比の高い填料を配合する方法（特許文献１参照）、中空の合成有機物カプセルを配合する方法（特許文献２参照）、無定形シリカや無定形シリケート、ゼオライト等の多孔性填料を配合する方法（特許文献３参照）などが提案されている。
しかしながら、針状、柱状、イガグリ状炭酸カルシウム等の様にアスペクト比の高い填料は粒子径が大きくなるほど嵩比重は小さくなるが、このような填料を紙に配合した場合には、抄紙時のシェアや、ロールニップなどの機械的な負荷により多孔性填料の多孔性構造が破壊されてしまい、充分な嵩高化効果が得られないのが実情である。また、中空の合成有機物カプセルを配合する方法は優れた嵩高化効果を示すものの、高価であることから汎用性のある印刷用紙への適用は難しい。
Therefore, a method of adding a filler having a small bulk specific gravity has been proposed. For example, a method of blending a filler having a high aspect ratio such as needle-like, columnar, and tiger-like calcium carbonate (see Patent Document 1), a method of blending a hollow synthetic organic capsule (see Patent Document 2), amorphous silica, A method of blending a porous filler such as regular silicate and zeolite (see Patent Document 3) has been proposed.
However, fillers with a high aspect ratio, such as needle-like, columnar, and tiger-like calcium carbonate, have a lower bulk specific gravity as the particle size increases. However, when such fillers are added to paper, the share at the time of papermaking is reduced. In fact, the porous structure of the porous filler is destroyed by a mechanical load such as a roll nip, so that a sufficient bulking effect cannot be obtained. Moreover, the method of blending hollow synthetic organic capsules shows an excellent bulking effect, but is expensive and difficult to apply to versatile printing paper.
多孔性填料は、紙の嵩高化効果に優れる上に、印刷時のインキ成分を吸収する能力が他の填料よりも優れているが、炭酸カルシウムやタルクに比べて紙の不透明度を高める能力が低かった。また、粒度分布が広いため、表面強度が乏しく、粗大粒子に起因する印刷時のパイリングや粉落ちといった問題が生じると共に、微細粒子に起因する繊維間結合強度（内部結合強度）の低下といった問題が生じた。
そこで、紙の不透明度を高める方法として、二酸化チタンなどの高屈折率の填料を配合することが提案されている。しかし、二酸化チタンは粒子径が０．２〜０．３μｍと微小であり、歩留が低くなるため、特許文献４では、二酸化チタンと炭酸カルシウムやホワイトカーボンなどとを複合化した複合粒子が提案されている。また、特許文献５には、二酸化ケイ素またはケイ酸塩と軽質炭酸カルシウムとからなり、二酸化ケイ素またはケイ酸塩より軽質炭酸カルシウムが多い複合粒子が提案されている。
また、粗大粒子を除去する方法として、振動スクリーン等を用いた分級処理や、反応終了後のスラリーを湿式粉砕する方法（特許文献６参照）が提案されている。また、多孔性填料の製造工程中に徹底的に粉砕処理を施すことで、粗大粒子を減らして平均粒子径を小さくしつつ、１μｍ以下の微細粒子の生成を少なくする方法が開示されている（特許文献７参照）。
Therefore, as a method for increasing the opacity of paper, it has been proposed to blend a high refractive index filler such as titanium dioxide. However, since titanium dioxide has a small particle size of 0.2 to 0.3 μm and the yield is low, Patent Document 4 proposes composite particles in which titanium dioxide is combined with calcium carbonate, white carbon, or the like. Has been. Patent Document 5 proposes composite particles composed of silicon dioxide or silicate and light calcium carbonate, and containing light calcium carbonate more than silicon dioxide or silicate.
Further, as a method for removing coarse particles, a classification process using a vibrating screen or a method of wet pulverizing the slurry after the reaction has been proposed (see Patent Document 6). In addition, a method of reducing the generation of fine particles of 1 μm or less while reducing the average particle size by reducing coarse particles by thoroughly pulverizing during the manufacturing process of the porous filler is disclosed ( (See Patent Document 7).
しかしながら、特許文献４に記載の複合粒子では、二酸化チタンが他の填料に比べて高価であるため、汎用性の高い印刷用紙ではコスト面から二酸化チタンの使用量に限界があり、白紙の不透明度を充分に確保できなかった。特許文献５に記載の複合粒子では、紙の嵩高化効果が不充分であった。
また、分級処理では、粗大粒子を除去できるものの、嵩高化効果が不充分である他、分留まりが低くなってしまう。また、特許文献６に記載の湿式粉砕では、粉砕処理によって微細粒子が増加するため、得られた多孔性填料を紙に配合した場合に内部結合強度を確保できなかった。しかも、粉砕によって多孔性填料の多孔性構造が破壊され、多孔性填料の嵩高性が低下した。特許文献７に記載の方法によれば、嵩高化効果を保持したまま粗大粒子を少なくできるが、湿式粉砕ほどではないにしても、製造工程中の徹底的な粉砕処理により、微細粒子量が増加した。そのため、紙に配合した際の繊維間結合（内部結合強度）が低下した上に、多孔性填料を含む液の粘性が増加した。
本発明は、紙に配合した際の嵩高化効果および白紙不透明度が高く、しかも適切な平均粒子径および狭い粒度分布を有し、紙の表面強度および内部結合強度を高くできる多孔性填料とその製造方法、その多孔性填料を得るためのスラリーを提供するものである。また、嵩高であり、不透明度、表面強度および内部結合強度が高い紙を提供するものである。
However, in the composite particles described in Patent Document 4, since titanium dioxide is more expensive than other fillers, there is a limit to the amount of titanium dioxide used for printing paper with high versatility in terms of cost. Could not be secured sufficiently. In the composite particles described in Patent Document 5, the effect of increasing the bulk of the paper was insufficient.
In the classification treatment, coarse particles can be removed, but the bulking effect is insufficient and the yield is lowered. Further, in the wet pulverization described in Patent Document 6, since fine particles are increased by the pulverization treatment, the internal bond strength cannot be ensured when the obtained porous filler is blended with paper. Moreover, the porous structure of the porous filler was destroyed by pulverization, and the bulkiness of the porous filler was lowered. According to the method described in Patent Document 7, coarse particles can be reduced while maintaining the bulking effect, but the amount of fine particles is increased by thorough pulverization during the manufacturing process, even if not as much as wet pulverization. did. For this reason, the fiber-to-fiber bond (internal bond strength) when blended with paper was lowered, and the viscosity of the liquid containing the porous filler was increased.
The present invention relates to a porous filler that has a high bulking effect and white paper opacity when blended in paper, has an appropriate average particle size and narrow particle size distribution, and can increase the surface strength and internal bond strength of paper. A production method and a slurry for obtaining the porous filler are provided. It also provides a paper that is bulky and has high opacity, surface strength and internal bond strength.
本発明は、以下の構成を含む。
［１］ コア粒子と、該コア粒子の周囲に付着した酸化ケイ素化合物とを有する平均粒子径が１０〜４０μｍの紙用多孔性填料であって、
前記酸化ケイ素化合物は、二酸化ケイ素および／またはケイ酸塩であり、前記ケイ酸塩が、一般式ｘＭ ２ Ｏ・ｙＳｉＯ ２ 、ｘＭＯ・ｙＳｉＯ ２ 、ｘＭ ２ Ｏ ３ ・ｙＳｉＯ ２ （ＭはＡｌ，Ｆｅ，Ｃａ，Ｍｇ，Ｎａ，Ｋ，Ｔｉ，Ｚｎのいずれかであり、ｘ，ｙは任意の正の数値である。）のいずれかで表され、
コア粒子の質量割合が酸化ケイ素化合物１００質量部に対して１〜２４質量部であり、
比表面積が２０〜２００ｍ２／ｇ、かつ、細孔径が０．１０〜０．８０μｍであることを特徴とする紙用多孔性填料。
［２］ コア粒子と該コア粒子の周囲に付着した酸化ケイ素化合物とを有する平均粒子径が１０〜４０μｍの紙用多孔性填料を分散媒中に含む紙用多孔性填料スラリーであって、
前記酸化ケイ素化合物は、二酸化ケイ素および／またはケイ酸塩であり、前記ケイ酸塩が、一般式ｘＭ ２ Ｏ・ｙＳｉＯ ２ 、ｘＭＯ・ｙＳｉＯ ２ 、ｘＭ ２ Ｏ ３ ・ｙＳｉＯ ２ （ＭはＡｌ，Ｆｅ，Ｃａ，Ｍｇ，Ｎａ，Ｋ，Ｔｉ，Ｚｎのいずれかであり、ｘ，ｙは任意の正の数値である。）のいずれかで表されたものであり、
コア粒子の質量割合が酸化ケイ素化合物１００質量部に対して１〜２４質量部であり、
鉱酸、鉱酸の金属塩およびケイ酸アルカリに由来するイオンを含む電解質の濃度が３５〜８０ｇ／Ｌであることを特徴とする紙用多孔性填料スラリー。
［３］ ｐＨが６．６〜７．８である［２］に記載の紙用多孔性填料スラリー。
［４］ ケイ酸アルカリ水溶液にコア粒子を添加した後、鉱酸溶液および/または鉱酸の金属塩溶液を添加し、中和して、コア粒子の周囲に酸化ケイ素化合物を析出させて平均粒子径が１０〜４０μｍの紙用多孔性填料を含む紙用多孔性填料スラリーを調製する工程と、該紙用多孔性填料スラリーから紙用多孔性填料を回収する工程とを有する紙用多孔性填料の製造方法であって、
コア粒子の添加量が、生成する酸化ケイ素化合物１００質量部に対して１〜２４質量部になるように、紙用多孔性填料スラリー中の、鉱酸、鉱酸の金属塩およびケイ酸アルカリに由来するイオンを含む電解質の濃度を３５〜８０ｇ／Ｌにし、
前記酸化ケイ素化合物は、二酸化ケイ素および／またはケイ酸塩であり、前記ケイ酸塩が、一般式ｘＭ ２ Ｏ・ｙＳｉＯ ２ 、ｘＭＯ・ｙＳｉＯ ２ 、ｘＭ ２ Ｏ ３ ・ｙＳｉＯ ２ （ＭはＡｌ，Ｆｅ，Ｃａ，Ｍｇ，Ｎａ，Ｋ，Ｔｉ，Ｚｎのいずれかであり、ｘ，ｙは任意の正の数値である。）のいずれかで表されたものであることを特徴とする紙用多孔性填料の製造方法。
［５］紙用多孔性填料スラリーのｐＨを６．６〜７．８にする［４］に記載の紙用多孔性填料の製造方法。
「６」［１］に記載の紙用多孔性填料を含有することを特徴とする紙。
The present invention includes the following configurations.
[1] A porous filler for paper having an average particle size of 10 to 40 μm having core particles and a silicon oxide compound attached around the core particles,
The silicon oxide compound is silicon dioxide and / or silicate, and the silicate has a general formula xM 2 O · ySiO 2 , xMO · ySiO 2 , xM 2 O 3 · ySiO 2 (M is Al, Fe , Ca, Mg, Na, K, Ti, Zn, and x and y are arbitrary positive numerical values).
The mass ratio of the core particles is 1 to 24 parts by mass with respect to 100 parts by mass of the silicon oxide compound,
A porous filler for paper , which has a specific surface area of 20 to 200 m 2 / g and a pore diameter of 0.10 to 0.80 μm.
[2] A porous filler slurry for paper containing a core filler and a porous filler for paper having an average particle size of 10 to 40 μm having a core particle and a silicon oxide compound attached around the core particle,
The silicon oxide compound is silicon dioxide and / or silicate, and the silicate has a general formula xM 2 O · ySiO 2 , xMO · ySiO 2 , xM 2 O 3 · ySiO 2 (M is Al, Fe , Ca, Mg, Na, K, Ti, and Zn, and x and y are arbitrary positive numerical values).
The mass ratio of the core particles is 1 to 24 parts by mass with respect to 100 parts by mass of the silicon oxide compound,
A porous filler slurry for paper , wherein the concentration of the electrolyte containing mineral acid, metal salt of mineral acid and ions derived from alkali silicate is 35 to 80 g / L.
[3] The porous filler slurry for paper according to [ 2 ], wherein the pH is 6.6 to 7.8.
[4] After the core particles are added to the alkali silicate aqueous solution, the mineral acid solution and / or the metal salt solution of the mineral acid is added and neutralized, and the silicon oxide compound is precipitated around the core particles to obtain an average particle. the porous filler for papers with preparing a porous filler slurries for paper, and recovering the porous filler for paper from a porous filler slurry the paper containing the size paper for porous fillers 10~40μm A manufacturing method of
The mineral acid, the metal salt of the mineral acid, and the alkali silicate in the porous filler slurry for paper so that the amount of the core particles added is 1 to 24 parts by mass with respect to 100 parts by mass of the silicon oxide compound to be produced. The concentration of the electrolyte containing the ions derived from 35 to 80 g / L ,
The silicon oxide compound is silicon dioxide and / or silicate, and the silicate has a general formula xM 2 O · ySiO 2 , xMO · ySiO 2 , xM 2 O 3 · ySiO 2 (M is Al, Fe , Ca, Mg, Na, K , Ti, is any of Zn, x, y is any positive number.) for paper porosity, characterized in der Rukoto those represented by any one of A method for producing sex fillers.
[ 5 ] The method for producing a porous filler for paper according to [ 4 ], wherein the pH of the porous filler slurry for paper is set to 6.6 to 7.8.
A paper comprising the porous filler for paper described in “6” [1 ] .
本発明の多孔性填料は、紙に配合した際の嵩高化効果および白紙不透明度が高く、しかも適切な平均粒子径および狭い粒度分布を有し、紙の表面強度および内部結合強度を高くできる。
本発明の多孔性填料スラリーおよび多孔性填料の製造方法によれば、紙に配合した際の嵩高化効果および白紙不透明度が高く、しかも適切な平均粒子径および狭い粒度分布を有し、紙の表面強度および内部結合強度を高い多孔性填料が得られる。
本発明の紙は、嵩高であり、不透明度、表面強度および内部結合強度が高い。
The porous filler of the present invention has a high bulking effect and white paper opacity when blended with paper, has an appropriate average particle size and narrow particle size distribution, and can increase the surface strength and internal bond strength of the paper.
According to the porous filler slurry and the method for producing a porous filler of the present invention, the bulking effect and white paper opacity when blended in paper are high, and it has an appropriate average particle diameter and narrow particle size distribution, A porous filler having high surface strength and high internal bond strength can be obtained.
The paper of the present invention is bulky and has high opacity, surface strength and internal bond strength.
（多孔性填料）
本発明の多孔性填料は、コア粒子と、該コア粒子の周囲に付着した酸化ケイ素化合物とを有する複合粒子である。
(Porous filler)
The porous filler of the present invention is a composite particle having core particles and a silicon oxide compound attached around the core particles.
コア粒子の材質としては、例えば、カオリン、焼成カオリン、炭酸カルシウム、硫酸バリウム、二酸化チタン、タルク、アルミナ、炭酸マグネシウム、酸化マグネシウム、水酸化マグネシウムなどが挙げられる。これらの中でも、コスト的にも優位であることから、炭酸カルシウム、カオリン、タルクが好ましい。さらに、炭酸カルシウムとしては、軽質炭酸カルシウム、重質炭酸カルシウムなどが挙げられる。
また、コア粒子の形状としては、紡錘状、立方状、柱状、花飾り状、針状、扁平状（板状）、球状、不定形状などが挙げられる。
Examples of the material for the core particles include kaolin, calcined kaolin, calcium carbonate, barium sulfate, titanium dioxide, talc, alumina, magnesium carbonate, magnesium oxide, and magnesium hydroxide. Among these, calcium carbonate, kaolin, and talc are preferable because of cost advantage. Further, examples of calcium carbonate include light calcium carbonate and heavy calcium carbonate.
Examples of the shape of the core particle include a spindle shape, a cubic shape, a column shape, a flower decoration shape, a needle shape, a flat shape (plate shape), a spherical shape, and an indefinite shape.
コア粒子の質量割合は、酸化ケイ素化合物１００質量部に対して０．１〜４０質量部であり、好ましくは０．５〜３０質量部であり、さらに好ましくは１〜２４質量部である。本発明者らが調べたところ、コア粒子の質量割合が０．１質量部以上では、多孔性填料の粒度分布を狭くでき、紙の表面強度および内部結合強度を高くできることが判明した。また、コア粒子の質量割合が４０質量部以下では、多孔性填料の粒度分布を狭くできる上に、嵩高化効果を充分に発揮できることが判明した。さらに、多孔性填料の透明性が低くなり、紙に配合した際の不透明度が向上することが判明した。
なお、コア粒子の質量割合は、多孔性填料の粉末サンプルを錠剤化した後、蛍光Ｘ線分析により各元素の酸化物量として測定することにより求められる。
The mass ratio of the core particles is 0.1 to 40 parts by mass with respect to 100 parts by mass of the silicon oxide compound, preferably 0.5 to 30 parts by mass, and more preferably 1 to 24 parts by mass. As a result of investigations by the present inventors, it was found that when the mass ratio of the core particles is 0.1 parts by mass or more, the particle size distribution of the porous filler can be narrowed, and the surface strength and internal bond strength of the paper can be increased. Further, it was found that when the mass ratio of the core particles is 40 parts by mass or less, the particle size distribution of the porous filler can be narrowed and the effect of increasing the bulk can be sufficiently exhibited. Furthermore, it has been found that the transparency of the porous filler is lowered and the opacity when blended into paper is improved.
The mass ratio of the core particles is determined by tableting a porous filler powder sample and then measuring the amount of oxide of each element by fluorescent X-ray analysis.
コア粒子の平均粒子径は０．２〜７．０μｍであることが好ましい。コア粒子の平均粒子径は、サンドグラインダ等の粉砕設備を用いることにより調整できる。その際、ポリアクリル酸塩、ポリカルボン酸塩、ヘキサメタリン酸塩、ピロリン酸塩などの分散剤を用いることができる。
本発明における平均粒子径とは、レーザー回折法により測定した体積積算で５０％となる値のことである。
The average particle diameter of the core particles is preferably 0.2 to 7.0 μm. The average particle diameter of the core particles can be adjusted by using a grinding facility such as a sand grinder. At that time, a dispersant such as polyacrylate, polycarboxylate, hexametaphosphate, pyrophosphate can be used.
The average particle diameter in the present invention is a value that is 50% in volume integration measured by a laser diffraction method.
多孔性填料を構成する酸化ケイ素化合物は、具体的には、二酸化ケイ素および／またはケイ酸塩である。ケイ酸塩とは、一般式ｘＭ２Ｏ・ｙＳｉＯ２、ｘＭＯ・ｙＳｉＯ２、ｘＭ２Ｏ３・ｙＳｉＯ２のいずれかで表される化合物であって、ＭがＡｌ，Ｆｅ，Ｃａ，Ｍｇ，Ｎａ，Ｋ，Ｔｉ，Ｚｎのいずれかのものである（ｘ，ｙは任意の正の数値である。）。 Specifically, the silicon oxide compound constituting the porous filler is silicon dioxide and / or silicate. Silicate is a compound represented by any of the general formulas xM 2 O · ySiO 2 , xMO · ySiO 2 , xM 2 O 3 · ySiO 2 , where M is Al, Fe, Ca, Mg, Na , K, Ti, Zn (x and y are arbitrary positive numerical values).
本発明の多孔性填料は、比表面積が２０〜２００ｍ２／ｇであり、好ましくは２０〜１５０ｍ２／ｇである。本発明者らが調べたところ、多孔性填料の比表面積が２０ｍ２／ｇ以上では、多孔性填料の粒度分布が狭くなり、微細粒子と粗大粒子が少なくなるため、内部結合強度および表面強度が向上することが判明した。また、比表面積が２００ｍ２／ｇ以下では、多孔性填料の強度が向上し、パルプスラリー調製時の剪断力およびプレス圧、キャレンダー処理圧力で潰れにくくなり、紙に配合した際の嵩高性が高くなることが判明した。また、多孔性填料の不透明度が向上し、紙に抄き込んだ際の不透明度が向上する。
本発明における比表面積は、水銀圧入法により測定した値であって、細孔形状が幾何学的な円筒であると仮定した全細孔の表面積で、測定範囲内における圧力と圧入された水銀量の関係から求めた値である。
The porous filler of the present invention has a specific surface area of 20 to 200 m 2 / g, preferably from 20~150m 2 / g. As a result of investigations by the present inventors, when the specific surface area of the porous filler is 20 m 2 / g or more, the particle size distribution of the porous filler becomes narrow and the number of fine particles and coarse particles decreases, so that the internal bond strength and the surface strength are low. It turned out to improve. In addition, when the specific surface area is 200 m 2 / g or less, the strength of the porous filler is improved, it becomes difficult to be crushed by the shearing force, the pressing pressure, and the calendering pressure at the time of pulp slurry preparation, and the bulkiness when blended with paper is increased. It turned out to be high. In addition, the opacity of the porous filler is improved, and the opacity when it is incorporated into paper is improved.
The specific surface area in the present invention is a value measured by a mercury intrusion method, and is the surface area of all pores assuming that the pore shape is a geometric cylinder. The pressure in the measurement range and the amount of mercury injected The value obtained from the relationship.
本発明の多孔性填料は、細孔径が０．１０〜０．８０μｍであり、好ましくは０．１５〜０．８０μｍである。多孔性填料の細孔径が０．１０μｍ以上であることにより、多孔性填料の凝集結合力が高くなり、多孔性填料の強度が向上し、パルプスラリー調製時の剪断力およびプレス圧力、キャレンダー処理圧力で潰れにくくなり、紙に配合した際の嵩高性が高くなる。また、本発明者らが調べたところ、多孔性填料の細孔径が０．８０μｍ以下では、多孔性填料の粒度分布が狭くなることが判明した。その結果、微細粒子と粗大粒子が少なくなり、内部結合強度および表面強度が向上することがわかった。
本発明における細孔径は、水銀圧入法により測定した値であって、積分比表面積曲線から得られるメジアン細孔直径のことである。
The porous filler of the present invention has a pore diameter of 0.10 to 0.80 μm, preferably 0.15 to 0.80 μm. When the pore size of the porous filler is 0.10 μm or more, the cohesive bond strength of the porous filler is increased, the strength of the porous filler is improved, the shearing force and press pressure during the preparation of the pulp slurry, and the calendar treatment. It becomes difficult to be crushed by pressure, and the bulkiness when blended with paper is increased. Further, when the present inventors investigated, it was found that the particle size distribution of the porous filler becomes narrow when the pore diameter of the porous filler is 0.80 μm or less. As a result, it was found that the fine particles and coarse particles are reduced, and the internal bond strength and the surface strength are improved.
The pore diameter in the present invention is a value measured by a mercury intrusion method and is a median pore diameter obtained from an integral specific surface area curve.
本発明の多孔性填料は平均粒子径が１０〜４０μｍであることが好ましく、１５〜３０μｍであることがより好ましい。多孔性填料の平均粒子径が１０μｍ以上であれば、紙に配合した際の嵩高化効果がより高くなり、平均粒子径が４０μｍ以下であれば、紙面に存在する粗大粒子が少なくなり、粗大粒子の脱落に起因する表面強度の低下を防止できる。
また、多孔性填料の粒度分布としては、標準偏差（σ）が０．３５０以下であることが好ましく、さらには０．３００以下であることが好ましい。このような粒度分布であれば、粗大粒子および微細粒子が共により少なくなり、紙に配合した際に、より優れた表面強度および内部結合強度が得られる。
The porous filler of the present invention preferably has an average particle size of 10 to 40 μm, and more preferably 15 to 30 μm. If the average particle diameter of the porous filler is 10 μm or more, the effect of increasing the bulk when blended in paper becomes higher, and if the average particle diameter is 40 μm or less, the coarse particles present on the paper surface are reduced, and the coarse particles It is possible to prevent the surface strength from being lowered due to the falling off.
As the particle size distribution of the porous filler, the standard deviation (σ) is preferably 0.350 or less, and more preferably 0.300 or less. With such a particle size distribution, both coarse particles and fine particles are reduced, and when blended in paper, better surface strength and internal bond strength can be obtained.
上記多孔性填料は、コア粒子とコア粒子の周囲に配置された酸化ケイ素化合物とを特定量を含有している上に、特定範囲の比表面積と細孔径を有している。比表面積と細孔径とが前記特定の範囲にあることにより、多孔性填料の嵩高性を確保できる上に、不透明度を高くできる。このような多孔性填料は、充分な嵩高性を有しつつ強度を有しているため、紙を製造する際のパルプスラリー調製時に剪断力がかかっても、あるいは抄紙時のプレス処理およびキャレンダー処理時に圧力がかかっても多孔性構造が破壊されにくい。したがって、多孔性を保ったまま紙中に含まれるため、得られる紙を充分に嵩高にできる。
また、上記多孔性填料は、酸化ケイ素化合物と酸化ケイ素化合物より少ない特定量のコア粒子とを含有していることにより、微細粒子と粗大粒子とが共に少ない狭い粒度分布を有し、紙に配合した際に紙の表面強度および内部結合強度を高くできる。
さらに、上記多孔性填料が紙に配合された際には白紙の不透明度を高くすることができるほか、紙に抄き込んだ際に充分に嵩高にできる。
The porous filler contains a specific amount of core particles and a silicon oxide compound arranged around the core particles, and has a specific surface area and a pore diameter in a specific range. When the specific surface area and the pore diameter are in the specific range, the bulkiness of the porous filler can be secured and the opacity can be increased. Since such a porous filler has sufficient bulkiness and strength, even if a shearing force is applied when preparing a pulp slurry when manufacturing paper, or press processing and calendaring during papermaking Even if pressure is applied during processing, the porous structure is not easily destroyed. Therefore, since it is contained in the paper while maintaining the porosity, the resulting paper can be made sufficiently bulky.
The porous filler contains a silicon oxide compound and a specific amount of core particles smaller than that of the silicon oxide compound, so that both fine particles and coarse particles have a narrow particle size distribution and are incorporated into paper. When this is done, the surface strength and internal bond strength of the paper can be increased.
Further, when the porous filler is incorporated into the paper, the opacity of the white paper can be increased, and the paper can be sufficiently bulky when it is incorporated into the paper.
（多孔性填料スラリー）
本発明の多孔性填料スラリーは、上記多孔性填料を得るためのものであって、コア粒子と該コア粒子の周囲に付着した酸化ケイ素化合物とを有する多孔性填料を分散媒中に含むものである。分散媒としては、水、各種有機溶媒が挙げられる。
この多孔性填料におけるコア粒子の質量割合は、酸化ケイ素化合物１００質量部に対して０．１〜４０質量部、好ましくは０．５〜３０質量部であり、さらに好ましくは１〜２４質量部である。
(Porous filler slurry)
The porous filler slurry of the present invention is for obtaining the above porous filler, and contains in the dispersion medium a porous filler having core particles and a silicon oxide compound attached around the core particles. Examples of the dispersion medium include water and various organic solvents.
The mass ratio of the core particles in this porous filler is 0.1 to 40 parts by mass, preferably 0.5 to 30 parts by mass, and more preferably 1 to 24 parts by mass with respect to 100 parts by mass of the silicon oxide compound. is there.
本発明の多孔性填料スラリーの電解質濃度は３５〜８０ｇ／Ｌ、好ましくは４５〜８０ｇ／Ｌ、より好ましくは５５〜８０ｇ／Ｌである。本発明者らが調べたところ、電解質濃度が３５ｇ／Ｌ以上では、粒子の過度の凝集を抑制でき、多孔性填料の比表面積を２００ｍ２／ｇ以下、かつ、細孔径を０．１０μｍ以上にできることが判明した。そして、多孔性填料の比表面積および細孔径が前記範囲になった結果、得られる多孔性填料は、パルプスラリーに添加した後の攪拌で生ずる剪断力や、紙に配合された後のプレス圧およびキャレンダー処理圧によっても、多孔性構造が破壊されにくくなることが判明した。
一方、電解質濃度が８０ｇ／Ｌ以下では、多孔性填料の比表面積を２０ｍ２／ｇ以上、かつ、細孔径を０．８０μｍ以下にできることが判明した。また、多孔性填料の粒度分布を狭くでき、微細粒子および粗大粒子を共に少なくできるため、多孔性填料を紙に配合した際に、紙の内部結合強度および表面強度を高くすることができることが判明した。
The electrolyte concentration of the porous filler slurry of the present invention is 35 to 80 g / L, preferably 45 to 80 g / L, and more preferably 55 to 80 g / L. As a result of investigation by the present inventors, when the electrolyte concentration is 35 g / L or more, excessive aggregation of particles can be suppressed, the specific surface area of the porous filler is 200 m 2 / g or less, and the pore diameter is 0.10 μm or more. It turns out that you can. And as a result of the specific surface area and pore diameter of the porous filler being in the above range, the resulting porous filler is shear force generated by stirring after being added to the pulp slurry, press pressure after being mixed with paper and It was found that the porous structure is not easily destroyed even by the calendering pressure.
On the other hand, it has been found that when the electrolyte concentration is 80 g / L or less, the specific surface area of the porous filler can be 20 m 2 / g or more and the pore diameter can be 0.80 μm or less. In addition, the particle size distribution of the porous filler can be narrowed, and both fine particles and coarse particles can be reduced, so it was found that the internal bond strength and surface strength of the paper can be increased when the porous filler is added to the paper. did.
ここで、電解質とは、水に溶解した際に陽イオンと陰イオンを生じる物質のことであり、具体的には、ＮａＨＳＯ4、ＮａＨＣＯ３、ＮａＣｌ、Ｎａ２ＳＯ４、Ｎａ２ＣＯ３、ＮａＨ２ＰＯ４、Ｎａ２ＨＰＯ４、Ｎａ３ＰＯ４、ＫＣｌ、Ｋ２ＳＯ４、Ｋ２ＣＯ３、Ｃａ（ＨＣＯ３）２、ＣＨ３ＣＯＯＮａ、ＣｕＳＯ４、ＦｅＣｌ３、ＣＨ３ＣＯＯＮＨ４、ＭｇＣｌ、Ｍｇ（ＯＨ）、ＭｇＣｌ２・Ｍｇ（ＯＨ）２、ＮａＣｌ、ＮＨ４Ｃｌ、ＣａＣｌ２、ＡｌＣｌ３、ＮａＮＯ３、ＮＨ４ＮＯ３、Ｃａ（ＮＯ３）２、Ａｌ（ＮＯ３）３、（ＮＨ４）２ＳＯ４、ＣａＳＯ４、Ａｌ２（ＳＯ４）３などが挙げられる。 Here, the electrolyte is a substance that generates a cation and an anion when dissolved in water. Specifically, NaHSO 4 , NaHCO 3 , NaCl, Na 2 SO 4 , Na 2 CO 3, NaH 2 PO 4 , Na 2 HPO 4 , Na 3 PO 4 , KCl, K 2 SO 4 , K 2 CO 3 , Ca (HCO 3 ) 2 , CH 3 COONa, CuSO 4 , FeCl 3 , CH 3 COONH 4 , MgCl, Mg (OH), MgCl 2 .Mg (OH) 2 , NaCl, NH 4 Cl, CaCl 2 , AlCl 3 , NaNO 3 , NH 4 NO 3 , Ca (NO 3 ) 2 , Al (NO 3 ) 3 , (NH 4 ) 2 SO 4 , CaSO 4 , Al 2 (SO 4 ) 3 and the like.
多孔性填料スラリーのｐＨは２．５超１０以下であることが好ましく、６．６〜７．８であることがより好ましい。多孔性填料スラリーのｐＨが２．５以下であると、腐食性が高くなり、１０を超えると、粘度が高くなり、紙の製造に不具合を生じやすくなる。 The pH of the porous filler slurry is preferably more than 2.5 and 10 or less, and more preferably 6.6 to 7.8. When the pH of the porous filler slurry is 2.5 or less, the corrosiveness is high, and when it exceeds 10, the viscosity becomes high and troubles are likely to occur in the production of paper.
多孔性填料スラリーの電解質濃度を求めるためには、まず、多孔性填料スラリーをろ紙（５Ｃ、例えば、アドバンテック社製ろ紙）でろ過して固形分を除去した後、得られたろ液の体積を測定する。そして、このろ液を乾燥し、電解質からなる乾固物の質量を測定し、（乾固物の質量）／（ろ液体積）により求められる。
なお、多孔性填料スラリー中の電解質は、後述する製造方法で使用する鉱酸の金属塩のみに由来するものではなく、ケイ酸ナトリウム水溶液および鉱酸溶液中のイオンなどにも由来する。そのため、必ずしも鉱酸の金属塩の添加量のみによって電解質濃度が決まるものではない。
In order to determine the electrolyte concentration of the porous filler slurry, first, the porous filler slurry is filtered through a filter paper (5C, for example, filter paper manufactured by Advantech) to remove solids, and then the volume of the obtained filtrate is measured. To do. And this filtrate is dried, the mass of the dried product which consists of electrolyte is measured, and it calculates | requires by (mass of dried product) / (filtrate volume).
The electrolyte in the porous filler slurry is not only derived from the metal salt of the mineral acid used in the production method described later, but also derived from ions in the sodium silicate aqueous solution and the mineral acid solution. Therefore, the electrolyte concentration is not necessarily determined only by the amount of mineral acid metal salt added.
多孔性填料スラリーは、ケイ酸アルカリ水溶液中にコア粒子を添加した後、鉱酸溶液および／または鉱酸の金属塩溶液を添加し、コア粒子の周囲に酸化ケイ素化合物を析出させることにより得られる。
ここで、ケイ酸アルカリ水溶液としては特に制限されないが、ケイ酸ナトリウム水溶液またはケイ酸カリウム水溶液が好ましい。ケイ酸アルカリ水溶液の濃度は、多孔性填料が効率的に製造できることから、３〜１５質量％であることが好ましく、ケイ酸アルカリ水溶液がケイ酸ナトリウム水溶液の場合には、ＳｉＯ２／Ｎａ２Ｏモル比が２．０〜３．４であることが好ましい。
コア粒子の添加量は、生成する酸化ケイ素化合物１００質量部に対して０．１〜４０質量部、好ましくは０．５〜３０質量部、さらに好ましくは１〜２４質量部になる量である。
The porous filler slurry is obtained by adding the core particles to the alkali silicate aqueous solution and then adding the mineral acid solution and / or the metal salt solution of the mineral acid to precipitate the silicon oxide compound around the core particles. .
Here, the alkali silicate aqueous solution is not particularly limited, but a sodium silicate aqueous solution or a potassium silicate aqueous solution is preferable. The concentration of the alkali silicate aqueous solution is preferably 3 to 15% by mass because the porous filler can be efficiently produced. When the alkali silicate aqueous solution is a sodium silicate aqueous solution, SiO 2 / Na 2 O It is preferable that the molar ratio is 2.0 to 3.4.
The addition amount of the core particles is 0.1 to 40 parts by mass, preferably 0.5 to 30 parts by mass, and more preferably 1 to 24 parts by mass with respect to 100 parts by mass of the silicon oxide compound to be generated.
コア粒子のケイ酸アルカリ水溶液への添加は、ケイ酸アルカリ水溶液を攪拌しながら、その中にコア粒子を添加することが好ましいが、コア粒子の水性スラリーに、ケイ酸アルカリ水溶液を添加しても差しつかえない。
また、コア粒子は、鉱酸溶液および／または鉱酸の金属塩溶液の添加前に全部を一括してケイ酸アルカリ水溶液中に添加してもよいし、複数に分けて添加してもよい。
The core particles are preferably added to the alkali silicate aqueous solution while stirring the alkali silicate aqueous solution while the core particles are added to the aqueous solution of the core particles. I don't mind.
Further, the core particles may be added all at once to the alkali silicate aqueous solution before the addition of the mineral acid solution and / or the metal salt solution of the mineral acid, or may be added in a plurality of portions.
本発明で用いる鉱酸溶液および／または鉱酸の金属塩溶液において、鉱酸としては、例えば、塩酸、硫酸、硝酸などが挙げられ、価格、ハンドリングの点で、硫酸が好ましい。
鉱酸の金属塩としては、前記鉱酸のナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩、アルミニウム塩などが挙げられる。これらの中でも、価格、ハンドリングの点で、硫酸アルミニウム（硫酸バンド）が好ましい。
また、鉱酸溶液、鉱酸の金属塩溶液は、水溶液であることが好ましい。
In the mineral acid solution and / or the metal salt solution of the mineral acid used in the present invention, examples of the mineral acid include hydrochloric acid, sulfuric acid, nitric acid and the like, and sulfuric acid is preferable in terms of cost and handling.
Examples of the metal salt of the mineral acid include sodium salt, potassium salt, calcium salt, magnesium salt and aluminum salt of the mineral acid. Among these, aluminum sulfate (sulfate band) is preferable in terms of price and handling.
The mineral acid solution and the mineral acid metal salt solution are preferably aqueous solutions.
鉱酸溶液および／または鉱酸の金属塩溶液の添加量は、中和率が９５〜１５０％の範囲になる量であり、酸化ケイ素化合物析出後の多孔性填料スラリーのｐＨが２．５超１０以下、好ましくは６．６〜７．８の範囲になる量であることが好ましい。鉱酸溶液および／または鉱酸の金属塩溶液の添加量が、中和率が９５％未満になる量あるいは得られる多孔性填料スラリーのｐＨが１０を超える量である場合には、原料であるケイ酸アルカリ水溶液の無駄が多くなる。一方、中和率が１５０％超になる量あるいは得られるスラリーのｐＨが２．５以下になる量である場合には多孔性填料を濃縮する際に発生するろ液ｐＨが低くなり過ぎて、取り扱いにくくなる。
ここで、中和率とは、［（鉱酸溶液および／または鉱酸の金属塩溶液の添加量（ｇ））／（理論必要中和量（ｇ））］×１００で求められる値である。
The addition amount of the mineral acid solution and / or the metal salt solution of the mineral acid is such that the neutralization rate is in the range of 95 to 150%, and the pH of the porous filler slurry after precipitation of the silicon oxide compound exceeds 2.5. The amount is preferably 10 or less, and preferably in the range of 6.6 to 7.8. When the amount of the mineral acid solution and / or metal salt solution of the mineral acid is such that the neutralization rate is less than 95% or the pH of the resulting porous filler slurry is more than 10, it is a raw material Waste of alkali silicate aqueous solution increases. On the other hand, when the neutralization rate exceeds 150% or the pH of the resulting slurry is 2.5 or less, the filtrate pH generated when the porous filler is concentrated becomes too low, It becomes difficult to handle.
Here, the neutralization rate is a value obtained by [(addition amount of mineral acid solution and / or metal salt solution of mineral acid (g)) / (theoretical necessary neutralization amount (g))] × 100. .
酸化ケイ素化合物の析出時には、攪拌装置により、周速として５〜１５ｍ／秒で攪拌することが好ましい。ここで、周速は剪断力の指標となり、周速が速ければ剪断力が大きくなる。周速が５ｍ／秒未満である場合は、剪断力が小さすぎて、コア粒子の周囲に酸化ケイ素化合物を析出させても、適切な平均粒子径および狭い粒度分布を得ることが困難になることがある。
一方、析出時の周速が１５ｍ／秒を超える場合には、剪断力が大きくなりすぎて、多孔性填料の粒子径が小さくなり、紙に配合した際に内部結合強度が低くなることがある上に、負荷電力の増加、設備費の高額化を招く。
攪拌装置としては、アジテータ、ホモミキサ、パイプラインミキサなどの装置が好ましい。なお、ボールミルやサンドグラインダ等の粉砕機を用いることも可能ではある。
また、ポンプなどの装置を用いて液循環を高めることが好ましい。
When depositing the silicon oxide compound, it is preferable to stir at a peripheral speed of 5 to 15 m / sec with a stirring device. Here, the peripheral speed is an index of the shearing force, and the shearing force increases as the peripheral speed increases. When the peripheral speed is less than 5 m / sec, the shear force is too small, and it becomes difficult to obtain an appropriate average particle size and narrow particle size distribution even if the silicon oxide compound is precipitated around the core particles. There is.
On the other hand, when the peripheral speed at the time of precipitation exceeds 15 m / sec, the shearing force becomes too large, the particle size of the porous filler becomes small, and the internal bond strength may be lowered when blended in paper. In addition, the load power increases and the equipment costs increase.
As the stirring device, an agitator, a homomixer, a pipeline mixer or the like is preferable. It is also possible to use a pulverizer such as a ball mill or a sand grinder.
Further, it is preferable to enhance the liquid circulation using a device such as a pump.
鉱酸溶液および／または鉱酸の金属塩溶液は１段で一括してケイ酸アルカリ水溶液中に添加してもよいが、より良好な粒径分布になることから、２段以上に分割して添加することが好ましい。
鉱酸溶液および／または鉱酸の金属塩溶液を２段以上で添加する場合には、特に良好な粒度分布になることから、１段目のケイ酸アルカリ水溶液の温度を２０〜７０℃にし、２段目以降では７０℃以上にすることが好ましい。また、１段目では、鉱酸溶液および／または鉱酸の金属塩溶液の添加量を、中和率が１０〜５０％の範囲になる量とすることが好ましい。
２段以上で添加する場合には、２段目以降で鉱酸の金属塩溶液を添加することが好ましい。２段目以降で鉱酸の金属塩溶液を添加すれば、多孔性填料スラリーの粘度をより低くでき、また、得られる多孔性填料を紙に配合した際の嵩高性および不透明度をより高くできる。２段目以降に添加する鉱酸の金属塩溶液としては、価格、ハンドリングの点で、硫酸アルミニウムが好ましい。
The mineral acid solution and / or the metal salt solution of the mineral acid may be added to the alkali silicate aqueous solution all at once, but since it has a better particle size distribution, it is divided into two or more stages. It is preferable to add.
When adding the mineral acid solution and / or the metal salt solution of the mineral acid in two or more stages, since the particle size distribution is particularly good, the temperature of the first stage alkali silicate aqueous solution is set to 20 to 70 ° C., It is preferable to set it to 70 degreeC or more after the 2nd step | paragraph. In the first stage, the addition amount of the mineral acid solution and / or the metal salt solution of the mineral acid is preferably set so that the neutralization rate is in the range of 10 to 50%.
When adding in two or more stages, it is preferable to add a metal salt solution of a mineral acid in the second and subsequent stages. If the metal salt solution of the mineral acid is added in the second and subsequent stages, the viscosity of the porous filler slurry can be lowered, and the bulkiness and opacity when the resulting porous filler is blended with paper can be further increased. . As the metal salt solution of the mineral acid added after the second stage, aluminum sulfate is preferable from the viewpoint of cost and handling.
１段目および２段目以降共に、鉱酸溶液および／または鉱酸の金属塩溶液の添加は、ケイ酸アルカリ水溶液に一括してまたは連続的に添加することができる。
鉱酸溶液および／または鉱酸の金属塩溶液の添加が終了した後には、必要に応じて、添加時の温度を維持したまま攪拌する熟成工程を有してもよい。
In both the first and second stages, the mineral acid solution and / or the metal salt solution of the mineral acid can be added all at once or continuously to the alkali silicate aqueous solution.
After completion of the addition of the mineral acid solution and / or the metal salt solution of the mineral acid, an aging step of stirring while maintaining the temperature at the time of addition may be included as necessary.
鉱酸溶液および／または鉱酸の金属塩溶液を１段で添加する場合には、ケイ酸アルカリ水溶液の温度を６０℃〜当該溶液の沸点にすることが好ましく、７５℃〜当該溶液の沸点にすることがより好ましい。鉱酸溶液および／または鉱酸の金属塩溶液の添加は、ケイ酸アルカリ水溶液に一括してまたは連続的に添加することができる。
１段で鉱酸溶液および鉱酸の金属塩溶液の両方を添加する場合には、鉱酸溶液を最初に添加することが好ましい。
When adding the mineral acid solution and / or the metal salt solution of the mineral acid in one stage, the temperature of the alkali silicate aqueous solution is preferably 60 ° C. to the boiling point of the solution, and 75 ° C. to the boiling point of the solution. More preferably. The mineral acid solution and / or the metal salt solution of the mineral acid can be added to the alkali silicate aqueous solution all at once or continuously.
If both the mineral acid solution and the mineral acid metal salt solution are added in one stage, it is preferred to add the mineral acid solution first.
多孔性填料スラリーの電解質濃度を前記範囲に調整するためには、上記製造方法におけるケイ酸アルカリ水溶液の濃度、鉱酸溶液および／または鉱酸の金属塩溶液の添加量を適宜選択すればよい。電解質濃度を高くするためには、ケイ酸アルカリ水溶液の濃度を高く、鉱酸溶液および／または鉱酸の金属塩溶液の添加量を多くすればよく、さらには、電解質溶液および／または粉末を必要に応じて一括又は複数回に分けて添加してもよい。電解質濃度を低くするためには、ケイ酸アルカリ水溶液の濃度を低く、鉱酸溶液および／または鉱酸の金属塩溶液の添加量を少なくすればよい。 In order to adjust the electrolyte concentration of the porous filler slurry to the above range, the concentration of the alkali silicate aqueous solution and the addition amount of the mineral acid solution and / or the metal salt solution of the mineral acid in the above production method may be appropriately selected. In order to increase the electrolyte concentration, the concentration of the alkali silicate aqueous solution should be increased, the amount of the mineral acid solution and / or the metal salt solution of the mineral acid added should be increased, and further, the electrolyte solution and / or powder is required. Depending on the case, it may be added in one batch or in several batches. In order to lower the electrolyte concentration, the concentration of the alkali silicate aqueous solution may be lowered and the amount of the mineral acid solution and / or the metal salt solution of the mineral acid may be reduced.
本発明の多孔性填料スラリーでは、特定量のコア粒子の周囲に酸化ケイ素化合物が付着した多孔性填料を含有し、電解質濃度が特定量になっている。このような多孔性填料スラリーから、ベルトフィルター、フィルタープレス、スクリュープレス等のろ過等により回収され、水等で洗浄された多孔性填料は、比表面積が２０〜２００ｍ２／ｇ、かつ細孔径が０．１０〜０．８０μｍになる。上述したように、このような多孔性填料によれば、紙に配合した際の嵩高化効果および白紙不透明度が高く、しかも適切な平均粒子径および狭い粒度分布を有し、紙の表面強度および内部結合強度を高くできる。
また、この多孔性填料スラリーによれば、平均粒子径が１０〜４０μｍで紙に配合した際に嵩高性に優れる多孔性填料を得ることができる。
さらに、上記多孔性填料スラリーから得られた多孔性填料を紙に配合した際には、白紙の不透明度を高くできる。
The porous filler slurry of the present invention contains a porous filler having a silicon oxide compound attached around a specific amount of core particles, and the electrolyte concentration is a specific amount. A porous filler recovered from such a porous filler slurry by filtration using a belt filter, filter press, screw press or the like and washed with water or the like has a specific surface area of 20 to 200 m 2 / g and a pore diameter. 0.10 to 0.80 μm. As described above, according to such a porous filler, the bulking effect and white paper opacity when blended in paper are high, and it has an appropriate average particle diameter and narrow particle size distribution, and the surface strength of the paper and The internal bond strength can be increased.
In addition, according to this porous filler slurry, it is possible to obtain a porous filler having an average particle size of 10 to 40 μm and excellent in bulkiness when blended with paper.
Furthermore, when the porous filler obtained from the porous filler slurry is blended with paper, the opacity of the white paper can be increased.
上記多孔性填料スラリーは、ろ過し、洗浄した後、水で再分散させ、多孔性填料１００質量部に対して硫酸アルミニウムを０．５〜１０質量部添加し、混合・攪拌することが好ましい。硫酸アルミニウム添加量は１〜５質量部であれば、さらに好ましい。このようにして新たに調製された多孔性填料スラリーは粘度がより低くなり、取り扱い性および操業性が高くなる。 The porous filler slurry is preferably filtered, washed, and redispersed with water, and 0.5 to 10 parts by mass of aluminum sulfate is added to 100 parts by mass of the porous filler, followed by mixing and stirring. The amount of aluminum sulfate added is more preferably 1 to 5 parts by mass. The newly prepared porous filler slurry has a lower viscosity and a higher handleability and operability.
（紙）
本発明の紙は、上記多孔性填料が含まれるものである。また、上記多孔性填料の他にも、必要に応じて、一般に紙に用いられる各種の顔料、例えば、カオリン、焼成カオリン、炭酸カルシウム、硫酸カルシウム、硫酸バリウム、二酸化チタン、タルク、酸化亜鉛、アルミナ、炭酸マグネシウム、酸化マグネシウム、無定形シリケート、ベントナイト、ゼオライト、セリサイト、スメクタイト等の鉱物質顔料や、スチレン系樹脂、尿素系樹脂、メラミン系樹脂、アクリル系樹脂、塩化ビニリデン系樹脂並びにそれらの微小中空粒子等の有機顔料が含まれていてもよい。
(paper)
The paper of the present invention contains the above porous filler. In addition to the above porous filler, various pigments generally used for paper as required, such as kaolin, calcined kaolin, calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, zinc oxide, alumina , Magnesium carbonate, magnesium oxide, amorphous silicate, bentonite, zeolite, sericite, smectite and other mineral pigments, styrene resins, urea resins, melamine resins, acrylic resins, vinylidene chloride resins and their fine Organic pigments such as hollow particles may be included.
紙を形成するセルロース繊維原料としては、例えば、クラフトパルプ（ＫＰ）、サルファイトパルプ（ＳＰ）、ソーダパルプ（ＡＰ）等の化学パルプ、セミケミカルパルプ（ＳＣＰ）、ケミグラウンドウッドパルプ（ＣＧＰ）等の半化学パルプ、砕木パルプ（ＧＰ）、サーモメカニカルパルプ（ＴＭＰ、ＢＣＴＭＰ）等の機械パルプ、あるいは、楮、三椏、麻、ケナフ等を原料とする非木材パルプ、古紙を原料とする脱墨パルプ（ＤＩＰ）が挙げられる。
これら単独で用いてもよいし、２種以上混合して用いてもよい。
Examples of cellulose fiber raw materials for forming paper include chemical pulps such as kraft pulp (KP), sulfite pulp (SP) and soda pulp (AP), semi-chemical pulp (SCP), and chemiground wood pulp (CGP). Semi-chemical pulp, mechanical pulp such as groundwood pulp (GP), thermomechanical pulp (TMP, BCTMP), etc., non-wood pulp made from straw, mitsumi, hemp, kenaf, etc., deinked pulp made from waste paper (DIP).
These may be used alone or in combination of two or more.
本発明の紙は、セルロース繊維原料および上記多孔性填料を含む紙料を調製し、その紙料を抄紙することにより得られる。その際に使用される抄紙機としては、例えば、長網式、円網式、短網式、ツインワイヤー式抄紙機などが挙げられる。
紙料中には、必要に応じて、各種のアニオン性、ノニオン性、カチオン性あるいは両性の歩留向上剤、濾水性向上剤、紙力増強剤や内添サイズ剤等の各種抄紙用内添助剤、染料、蛍光増白剤、ｐＨ調整剤、消泡剤、ピッチコントロール剤、スライムコントロール剤等の抄紙用内添助剤を適宜添加できる。
The paper of the present invention is obtained by preparing a stock containing a cellulose fiber raw material and the above porous filler, and papermaking the stock. Examples of the paper machine used at that time include a long net type, a circular net type, a short net type, and a twin wire type paper machine.
In the paper stock, various anionic, nonionic, cationic or amphoteric retention improvers, freeness improvers, paper strength enhancers, internal sizing agents, and other various internal additives for papermaking, as required. Auxiliary additives for paper making such as auxiliary agents, dyes, fluorescent brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be appropriately added.
本発明の紙には、澱粉、ポリビニルアルコール、ポリアクリルアマイド等の各種表面バインダーや、ロジン系サイズ剤、合成サイズ剤、石油樹脂系サイズ剤、中性サイズ剤等の表面サイズ剤、塩化ナトリウムや硫酸ナトリウム等の導電剤が塗布または含浸されていてもよい。 The paper of the present invention includes various surface binders such as starch, polyvinyl alcohol, and polyacrylamide, surface sizing agents such as rosin sizing agents, synthetic sizing agents, petroleum resin sizing agents, neutral sizing agents, sodium chloride, A conductive agent such as sodium sulfate may be applied or impregnated.
上述した本発明の紙は、上記多孔性填料が含まれるものであるから、嵩高であり、不透明度、表面強度および内部結合強度が高い。このような紙は印刷用紙、上質系塗工紙、中質系塗工紙、新聞用紙、各種原紙に好適に用いられる。 Since the paper of the present invention described above contains the porous filler, it is bulky and has high opacity, surface strength and internal bond strength. Such paper is suitably used for printing paper, high-quality coated paper, medium-sized coated paper, newsprint, and various base papers.
以下に実施例を挙げて、本発明を具体的に説明するが、本発明はそれらの実施例に限定されるものではない。なお、例中の「部」及び「％」は特に断らない限り、「質量部」及び「質量％」のことである。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.
以下の例において、平均粒子径は、レーザー回折式粒度分布計（ＳＡＬＤ２０００Ｊ（（株）島津製作所製）を用いて測定された５０％体積積算値の粒子径である。また、粒子径の標準偏差はレーザー回折式粒度分布計により求めた粒子径から算出した値である。
比表面積は、ポロシメーターであるポアサイザ９３２０（（株）島津製作所製））を用いて、細孔形状が幾何学的な円筒であると仮定した場合の全細孔の表面積であり、測定範囲内における圧力と圧入された水銀量の関係から求めた値である。
細孔径は、ポアサイザ９３２０（（株）島津製作所製））を用いて測定されたメジアン細孔直径である。
多孔性填料中のコア粒子の質量割合は、蛍光Ｘ線分析装置（スペクトリス社製ＰＷ２４０４）を用いて測定した値である。
配管腐食性は、１５％に調製した多孔性填料スラリー１ｋｇ中にＳＵＳ３０６Ｌ板（５０×１００×２ｍｍ）を浸漬させ、６０℃で７２時間放置し、スラリーの変色度合いを目視で評価した（ＳＵＳ板の腐食が進むとスラリー中へ溶出し、スラリーが変色する）。
５（優）：配管への腐食性が低い−１（劣）：配管への腐食性が高い
なお、評価が２未満のものは、実用上問題がある。
In the following examples, the average particle size is a particle size of a 50% volume integrated value measured using a laser diffraction particle size distribution analyzer (SALD2000J (manufactured by Shimadzu Corporation)), and the standard deviation of the particle size. Is a value calculated from the particle size obtained by a laser diffraction particle size distribution meter.
The specific surface area is the surface area of all pores when the pore shape is assumed to be a geometric cylinder using a pore sizer 9320 (manufactured by Shimadzu Corporation), which is a porosimeter. It is a value obtained from the relationship between pressure and the amount of mercury injected.
The pore diameter is a median pore diameter measured using a pore sizer 9320 (manufactured by Shimadzu Corporation).
The mass ratio of the core particles in the porous filler is a value measured using a fluorescent X-ray analyzer (Spectras PW2404).
The pipe corrosiveness was determined by immersing a SUS306L plate (50 × 100 × 2 mm) in 1 kg of a porous filler slurry adjusted to 15% and leaving it at 60 ° C. for 72 hours, and visually evaluating the degree of discoloration of the slurry (SUS plate). As the corrosion of the water advances, it elutes into the slurry and the slurry discolors).
5 (excellent): low corrosiveness to pipes -1 (poor): high corrosiveness to pipes Note that those having an evaluation of less than 2 have practical problems.
合成例１
水道水２６３ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａ（ＴＰ−１２１「紡錘状」、奥多摩工業製、固形分濃度９．５％、表中では「炭カルＡ」と表記する。）１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）７４ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸２２０ｇを４０分かけて添加し、２段目の中和を行って、多孔性填料を含むスラリー（多孔性填料スラリー）を得た。その際の全鉱酸および鉱酸の金属塩添加量（中和率で表す。）、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差を表１に示す。
多孔性填料スラリーはろ過・洗浄した後、水に再分散させ、手抄き評価に用いた。また、ろ過・洗浄後のケーキの一部を１０５℃にて乾燥し、比表面積および細孔径を測定し、また、蛍光Ｘ線分析装置によるコア粒子質量割合の測定に供した。多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis example 1
After adding 754 g of 5% sodium sulfate aqueous solution to 263 g of tap water, 330 g of commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Furthermore, as a core particle, a dispersion A of calcium carbonate (TP-121 “spindle”, manufactured by Okutama Kogyo Co., Ltd., solid content concentration of 9.5%, adjusted to an average particle size of 0.6 μm with a sand grinder) In the table, it is expressed as “charcoal cal A.”) 100 g (10 parts with respect to 100 parts of silicon oxide compound) was added at a temperature of 50 ° C. while stirring with a three-one motor. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 74 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Next, 220 g of sulfuric acid was added over 40 minutes at the same temperature, and the second stage neutralization was performed to obtain a slurry containing a porous filler (porous filler slurry). Table 1 shows the total mineral acid and metal salt addition amount (expressed by neutralization rate), the pH of the porous filler slurry, the electrolyte concentration, the average particle diameter of the porous filler, and the standard deviation.
The porous filler slurry was filtered and washed, then redispersed in water, and used for handsheet evaluation. In addition, a part of the cake after filtration and washing was dried at 105 ° C., the specific surface area and the pore diameter were measured, and the core particle mass ratio was measured with a fluorescent X-ray analyzer. Table 1 shows the specific surface area, the pore diameter, and the mass ratio of the core particles of the porous filler.
合成例２
９０℃まで昇温し、次いで、このままの温度で硫酸２００ｇを４０分かけて添加し、２段目の中和を行った以外は合成例１と同様にして、多孔性填料スラリーを得た。その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis example 2
The porous filler slurry was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 90 ° C. and 200 g of sulfuric acid was added at this temperature over 40 minutes to neutralize the second stage. Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 1.
合成例３
９０℃まで昇温し、次いで、このままの温度で硫酸１７０ｇを４０分かけて添加し、２段目の中和を行った以外は合成例１と同様にして、多孔性填料スラリーを得た。その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis example 3
The porous filler slurry was obtained in the same manner as in Synthesis Example 1 except that the temperature was raised to 90 ° C., and 170 g of sulfuric acid was added at this temperature over 40 minutes to neutralize the second stage. Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 1.
合成例４
水道水３５３ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの１．５ｇ（酸化ケイ素化合物１００部に対し０．１５部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）７４ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸１７４ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis example 4
After adding 754 g of 5% sodium sulfate aqueous solution to 353 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, 1.5 g of calcium carbonate dispersion A adjusted to have an average particle diameter of 0.6 μm by a sand grinder (0.15 parts with respect to 100 parts of silicon oxide compound) was used as a core particle with a three-one motor. It was added at a temperature of 50 ° C. with stirring. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 74 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 174 g of sulfuric acid was added over 40 minutes at this temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 1.
合成例５
水道水１２４ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ｂ（ＴＰ−１２１「紡錘状」、奥多摩工業製、固形分濃度１５．０％、表中では「炭カルＢ」と表記する。）２５３．３ｇ（酸化ケイ素化合物１００部に対し４０部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）７４ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸（濃度２０％）２８１ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis example 5
After adding 754 g of 5% sodium sulfate aqueous solution to 124 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, as a core particle, a dispersion B of calcium carbonate (TP-121 “spindle”, manufactured by Okutama Kogyo Co., Ltd., solid content concentration of 15.0%, adjusted to have an average particle size of 0.6 μm with a sand grinder, In the table, it is expressed as “charcoal cal B”.) 253.3 g (40 parts with respect to 100 parts of the silicon oxide compound) was added at a temperature of 50 ° C. while stirring with a three-one motor. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 74 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 281 g of sulfuric acid (concentration 20%) was added over 40 minutes at the same temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 1.
合成例６
水道水３４７ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの８．０ｇ（酸化ケイ素化合物１００部に対し０．８部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）７４ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸１７６ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis Example 6
After adding 754 g of 5% sodium sulfate aqueous solution to 347 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Furthermore, 8.0 g (0.8 parts with respect to 100 parts of the silicon oxide compound) of calcium carbonate dispersion A adjusted to have an average particle diameter of 0.6 μm with a sand grinder was used as a core particle with a three-one motor. It was added at a temperature of 50 ° C. with stirring. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 74 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 176 g of sulfuric acid was added over 40 minutes at this temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 1.
合成例７
水道水１００ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの２８０ｇ（酸化ケイ素化合物１００部に対し２８部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）７４ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸（濃度２０％）２４９ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis example 7
After adding 754 g of 5% sodium sulfate aqueous solution to 100 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, 280 g of calcium carbonate dispersion A (28 parts per 100 parts of silicon oxide compound) prepared as a core particle with a sand grinder so as to have an average particle diameter of 0.6 μm was stirred with a three-one motor. Added at 50 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 74 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 249 g of sulfuric acid (concentration 20%) was added over 40 minutes at the same temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 1.
合成例８
水道水２９８ｇに５％硫酸ナトリウム水溶液７１０ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）８２ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸１９３ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis Example 8
After adding 710 g of 5% sodium sulfate aqueous solution to 298 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, as core particles, 100 g of calcium carbonate dispersion A adjusted to have an average particle size of 0.6 μm with a sand grinder (10 parts with respect to 100 parts of the silicon oxide compound) was stirred with a three-one motor. Added at 50 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / sec, 82 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the above peripheral speed. Warm up. Next, 193 g of sulfuric acid was added over 40 minutes at the same temperature, and neutralization in the second stage was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 1.
合成例９
水道水２３３ｇに５％硫酸ナトリウム水溶液７４９ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５５℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）６９ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸２０５ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表１に示す。
Synthesis Example 9
After adding 749 g of 5% aqueous sodium sulfate solution to 233 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration: 38%) was added while stirring with a three-one motor. Further, as core particles, 100 g of calcium carbonate dispersion A adjusted to have an average particle size of 0.6 μm with a sand grinder (10 parts with respect to 100 parts of the silicon oxide compound) was stirred with a three-one motor. Added at 55 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 69 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 205 g of sulfuric acid was added over 40 minutes at this temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 1.
合成例１０
水道水２６３ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ｃ（ＴＰ−２２２ＨＳ「立方状」、奥多摩工業製、固形分濃度９．５％、表中では「炭カルＣ」と表記する。）１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加した。
その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）７４ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸２００ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表２に示す。
Synthesis Example 10
After adding 754 g of 5% sodium sulfate aqueous solution to 263 g of tap water, 330 g of commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, as a core particle, calcium carbonate dispersion C (TP-222HS “cubic”, manufactured by Okutama Kogyo Co., Ltd., solid content concentration 9.5%, adjusted to have an average particle size of 0.6 μm by a sand grinder In the table, it is expressed as “charcoal cal C”.) 100 g (10 parts with respect to 100 parts of silicon oxide compound) was added at a temperature of 50 ° C. while stirring with a three-one motor.
Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 74 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 200 g of sulfuric acid was added over 40 minutes at this temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 2.
合成例１１
コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ｄ（ＴＰ−１２３ＣＳ「針状」、奥多摩工業製、固形分濃度９．５％、表中では「炭カルＤ」と表記する。）１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加した以外は合成例２と同様にして多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表２に示す。
Synthesis Example 11
As a core particle, calcium carbonate dispersion D (TP-123CS “needle”, manufactured by Okutama Kogyo Co., Ltd., solid content concentration 9.5%, adjusted to have an average particle size of 0.6 μm with a sand grinder, in the table In this case, the porous filler slurry is prepared in the same manner as in Synthesis Example 2 except that 100 g (10 parts per 100 parts of the silicon oxide compound) is added at a temperature of 50 ° C. while stirring with a three-one motor. Obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 2.
合成例１２
コア粒子として、サンドグラインダにて平均粒子径が３．３μｍになるように調整した炭酸カルシウムの分散液Ｅ（カルライトＳＡ「花飾り状」、白石工業製、固形分濃度９．５％、表中では「炭カルＥ」と表記する。）１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加した以外は合成例２と同様にして多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表２に示す。
Synthesis Example 12
As a core particle, a dispersion E of calcium carbonate adjusted to an average particle size of 3.3 μm with a sand grinder (Callite SA “Flower decoration”, manufactured by Shiraishi Kogyo Co., Ltd., solid content concentration 9.5%, in the table) In this case, the porous filler slurry is prepared in the same manner as in Synthesis Example 2 except that 100 g (10 parts with respect to 100 parts of the silicon oxide compound) is added at a temperature of 50 ° C. while stirring with a three-one motor. Obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 2.
合成例１３
コア粒子として、サンドグラインダにて平均粒子径が４．０μｍになるように調整した炭酸カルシウムの分散液Ｆ（ＰＣ、白石工業製「紡錘状」、固形分濃度９．５％、表中では「炭カルＦ」と表記する。）１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加し、９０℃に昇温した後に硫酸１１７ｇを添加し、次いで、硫酸アルミニウム（表中では、「硫酸Ａｌ」と表記する。）水溶液（濃度２０％）５８ｇを添加した以外は合成例２と同様にして多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表２に示す。
Synthesis Example 13
As a core particle, a dispersion F of calcium carbonate (PC, “Spindle” manufactured by Shiraishi Kogyo Co., Ltd., solid content concentration of 9.5%, adjusted in a table with a sand grinder to have an average particle size of 4.0 μm, “ Charcoal Cal F ”)) 100 g (10 parts with respect to 100 parts of silicon oxide compound) was added at a temperature of 50 ° C. while stirring with a three-one motor, heated to 90 ° C., and then 117 g of sulfuric acid was added. A porous filler slurry was obtained in the same manner as in Synthesis Example 2 except that 58 g of an aqueous solution of aluminum sulfate (expressed as “Al sulfate” in the table) (concentration 20%) was added.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 2.
合成例１６
コア粒子として、サンドグラインダにて平均粒子径が１．２μｍになるように調整した重質炭酸カルシウムの分散液Ｉ（ＦＭＴ−９０、ファイマテック製、固形分濃度９．５％、表中では「炭カルＩ」と表記する。）１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加した以外は合成例２と同様にして多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表２に示す。
Synthesis Example 16
As a core particle, a dispersion I of heavy calcium carbonate adjusted to have an average particle size of 1.2 μm with a sand grinder (FMT-90, manufactured by PMMA Tech, solid content concentration 9.5%, in the table, “ Porous filler slurry was obtained in the same manner as in Synthesis Example 2 except that 100 g (10 parts relative to 100 parts of the silicon oxide compound) was added at a temperature of 50 ° C. while stirring with a three-one motor. .
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 2.
合成例１８
水道水３６６ｇに５％硫酸ナトリウム水溶液７４３ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの１０ｇ（酸化ケイ素化合物１００部に対し１部）をスリーワンモータで攪拌しながら温度４０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）６２ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸１８８ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表２に示す。
Synthesis Example 18
After adding 743 g of 5% aqueous sodium sulfate solution to 366 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, 10 g of calcium carbonate dispersion A (1 part with respect to 100 parts of silicon oxide compound) prepared as a core particle with a sand grinder so as to have an average particle diameter of 0.6 μm was stirred with a three-one motor. Added at 40 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / sec, 62 g of sulfuric acid (concentration 20%) was added for 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the above peripheral speed. Warm up. Next, 188 g of sulfuric acid was added over 40 minutes at the same temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 2.
合成例１９
水道水６０ｇに５％硫酸ナトリウム水溶液４３４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの３００ｇ（酸化ケイ素化合物１００部に対し３０部）をスリーワンモータで攪拌しながら温度６５℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）８２ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸２４７ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表２に示す。
Synthesis Example 19
After adding 434 g of 5% sodium sulfate aqueous solution to 60 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, as core particles, 300 g of calcium carbonate dispersion A adjusted to have an average particle size of 0.6 μm with a sand grinder (30 parts with respect to 100 parts of silicon oxide compound) was stirred with a three-one motor. Added at 65 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / sec, 82 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the above peripheral speed. Warm up. Next, 247 g of sulfuric acid was added over 40 minutes at the same temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 2.
合成例２０
水道水３５３ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの０．８ｇ（酸化ケイ素化合物１００部に対し０．０８部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）７４ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸１７４ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表３に示す。
Synthesis Example 20
After adding 754 g of 5% sodium sulfate aqueous solution to 353 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, 0.8 g (0.08 part relative to 100 parts of the silicon oxide compound) of calcium carbonate dispersion A adjusted to have an average particle diameter of 0.6 μm by a sand grinder was used as a core particle with a three-one motor. It was added at a temperature of 50 ° C. with stirring. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 74 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 174 g of sulfuric acid was added over 40 minutes at this temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 3.
合成例２１
水道水６６ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの３１７ｇ（酸化ケイ素化合物１００部に対し５０部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）７４ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸３０８ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表３に示す。
Synthesis Example 21
After adding 754 g of 5% sodium sulfate aqueous solution to 66 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, as core particles, 317 g of calcium carbonate dispersion A (50 parts with respect to 100 parts of silicon oxide compound) adjusted to have an average particle diameter of 0.6 μm with a sand grinder was stirred with a three-one motor. Added at 50 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 74 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Next, 308 g of sulfuric acid was added over 40 minutes at the same temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 3.
合成例２２
水道水１７６ｇに５％硫酸ナトリウム水溶液７５４ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液５０６ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの５ｇ（酸化ケイ素化合物１００部に対し０．５部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）５７ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸１９２ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表３に示す。
Synthesis Example 22
After adding 754 g of 5% sodium sulfate aqueous solution to 176 g of tap water, 506 g of commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, 5 g of calcium carbonate dispersion A (0.5 part with respect to 100 parts of silicon oxide compound) prepared as a core particle with a sand grinder so that the average particle diameter is 0.6 μm was stirred with a three-one motor. While at a temperature of 50 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 57 g of sulfuric acid (concentration 20%) was added in 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the above peripheral speed. Warm up. Next, 192 g of sulfuric acid was added over 40 minutes at the same temperature, and neutralization in the second stage was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 3.
合成例２３
水道水１３７５ｇに５％硫酸ナトリウム水溶液４７ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）９２ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸１８３ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表３に示す。
Synthesis Example 23
After adding 47 g of 5% sodium sulfate aqueous solution to 1375 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, as core particles, 100 g of calcium carbonate dispersion A adjusted to have an average particle size of 0.6 μm with a sand grinder (10 parts with respect to 100 parts of the silicon oxide compound) was stirred with a three-one motor. Added at 50 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 92 g of sulfuric acid (concentration 20%) was added for 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 183 g of sulfuric acid was added over 40 minutes at the same temperature, and neutralization in the second stage was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 3.
合成例２４
水道水１３８３ｇに５％硫酸ナトリウム水溶液３２ｇを加えた後、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度５０℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）９９ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸１７６ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表３に示す。
合成例２５
５％硫酸ナトリウム水溶液６８６ｇに、市販の３号ケイ酸ナトリウム水溶液３３０ｇ（固形分濃度３８％）をスリーワンモータで撹拌しながら添加した。さらに、コア粒子として、サンドグラインダにて平均粒子径が０．６μｍになるように調整した炭酸カルシウムの分散液Ａの１００ｇ（酸化ケイ素化合物１００部に対し１０部）をスリーワンモータで攪拌しながら温度６５℃において添加した。その後、攪拌翼の周速を１０ｍ／秒に調整し、硫酸（濃度２０％）５９ｇを１５分間で添加して１段目の中和を行った後、上記周速の状態で９０℃まで昇温した。次いで、このままの温度で硫酸２１５ｇを４０分かけて添加し、２段目の中和を行って多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表３に示す。
Synthesis Example 24
After adding 32 g of 5% sodium sulfate aqueous solution to 1383 g of tap water, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, as core particles, 100 g of calcium carbonate dispersion A adjusted to have an average particle size of 0.6 μm with a sand grinder (10 parts with respect to 100 parts of the silicon oxide compound) was stirred with a three-one motor. Added at 50 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 99 g of sulfuric acid (concentration 20%) was added for 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 176 g of sulfuric acid was added over 40 minutes at this temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 3.
Synthesis Example 25
To 686 g of 5% aqueous sodium sulfate solution, 330 g of a commercially available No. 3 sodium silicate aqueous solution (solid content concentration 38%) was added while stirring with a three-one motor. Further, as core particles, 100 g of calcium carbonate dispersion A adjusted to have an average particle size of 0.6 μm with a sand grinder (10 parts with respect to 100 parts of the silicon oxide compound) was stirred with a three-one motor. Added at 65 ° C. Thereafter, the peripheral speed of the stirring blade was adjusted to 10 m / second, 59 g of sulfuric acid (concentration 20%) was added for 15 minutes to neutralize the first stage, and then the temperature was increased to 90 ° C. at the peripheral speed. Warm up. Subsequently, 215 g of sulfuric acid was added over 40 minutes at the same temperature, and the second stage neutralization was performed to obtain a porous filler slurry.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 3.
合成例２６
１段目の中和の後に９０℃まで昇温してから、このままの温度で硫酸１９１ｇを４０分かけて添加して、２段目の中和を行った以外は合成例１と同様にして、多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表４に示す。
Synthesis Example 26
After the first stage of neutralization, the temperature was raised to 90 ° C., and 191 g of sulfuric acid was added over 40 minutes at the same temperature, and the second stage of neutralization was performed. A porous filler slurry was obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 4.
合成例２７
１段目の中和の後に９０℃まで昇温してから、このままの温度で硫酸１８６ｇを４０分かけて添加して、２段目の中和を行った以外は合成例１と同様にして、多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表４に示す。
Synthesis Example 27
After the first stage neutralization, the temperature was raised to 90 ° C., and then 186 g of sulfuric acid was added over 40 minutes at the same temperature to carry out the second stage neutralization, and the same as in Synthesis Example 1 A porous filler slurry was obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 4.
合成例２８
１段目の中和の後に９０℃まで昇温してから、このままの温度で硫酸１７９ｇを４０分かけて添加して、２段目の中和を行った以外は合成例１と同様にして、多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表４に示す。
Synthesis Example 28
After the first stage neutralization, the temperature was raised to 90 ° C., and at this temperature, 179 g of sulfuric acid was added over 40 minutes, and the second stage neutralization was performed. A porous filler slurry was obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 4.
合成例２９
１段目の中和の後に９０℃まで昇温してから、このままの温度で硫酸１７４ｇを４０分かけて添加して、２段目の中和を行った以外は合成例１と同様にして、多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表４に示す。
Synthesis Example 29
The temperature was raised to 90 ° C. after neutralization at the first stage, and then 174 g of sulfuric acid was added over 40 minutes at the same temperature, and the neutralization at the second stage was carried out to carry out in the same manner as in Synthesis Example 1. A porous filler slurry was obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 4.
合成例３０
１段目の中和の後に９０℃まで昇温してから、このままの温度で硫酸１７１ｇを４０分かけて添加して、２段目の中和を行った以外は合成例１と同様にして、多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表４に示す。
Synthesis Example 30
After the first stage neutralization, the temperature was raised to 90 ° C., and then 171 g of sulfuric acid was added over 40 minutes at the same temperature, and the second stage neutralization was carried out in the same manner as in Synthesis Example 1. A porous filler slurry was obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 4.
合成例３１
１段目の中和の後に９０℃まで昇温してから、このままの温度で硫酸１２４ｇ、硫酸アルミニウム溶液（２０％）５８ｇを４０分かけて順次添加した以外は合成例１と同様にして、多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表４に示す。
Synthesis Example 31
After heating up to 90 ° C. after neutralization in the first stage, the same procedure as in Synthesis Example 1 was conducted except that 124 g of sulfuric acid and 58 g of aluminum sulfate solution (20%) were sequentially added over 40 minutes at this temperature. A porous filler slurry was obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 4.
合成例３２
１段目の中和の後に９０℃まで昇温してから、このままの温度で硫酸１７６ｇを４０分かけて添加して、２段目の中和を行った以外は合成例１と同様にして、多孔性填料スラリーを得た。
その際の全鉱酸および鉱酸の金属塩添加量、多孔性填料スラリーのｐＨ、電解質濃度、多孔性填料の平均粒子径および標準偏差、多孔性填料の比表面積、細孔径、コア粒子の質量割合を表４に示す。
多孔性填料スラリーはろ過・洗浄した後、水に再分散させた後、硫酸アルミニウム水溶液９．５ｇ（濃度２０％）を添加、攪拌し、手抄き評価に用いた。また、硫酸アルミニウム水溶液添加後スラリーのろ過・洗浄後のケーキの一部を１０５℃にて乾燥し、比表面積および細孔径を測定し、また、蛍光Ｘ線分析装置によるコア粒子質量割合の測定に供した。多孔性填料の比表面積、細孔径、コア粒子の質量割合を表４に示す。
Synthesis Example 32
After the first stage neutralization, the temperature was raised to 90 ° C., and then 176 g of sulfuric acid was added over 40 minutes at the same temperature to carry out the second stage neutralization, and the same as in Synthesis Example 1 A porous filler slurry was obtained.
Total mineral acid and metal salt addition amount of mineral acid, pH of porous filler slurry, electrolyte concentration, average particle diameter and standard deviation of porous filler, specific surface area of porous filler, pore diameter, mass of core particles The ratio is shown in Table 4.
The porous filler slurry was filtered and washed, and then redispersed in water. Then, 9.5 g (concentration 20%) of an aqueous aluminum sulfate solution was added and stirred, and used for handsheet evaluation. In addition, a portion of the cake after filtration and washing of the slurry after addition of the aqueous aluminum sulfate solution is dried at 105 ° C., the specific surface area and the pore diameter are measured, and the measurement of the core particle mass ratio using a fluorescent X-ray analyzer Provided. Table 4 shows the specific surface area, pore diameter, and core particle mass ratio of the porous filler.
上記合成例１〜３２の条件を表１〜４にまとめた。
ｐＨが６．６〜７．８の合成例５，１３，２７〜３２の多孔性填料スラリーは、配管腐食性が低く、また、粘度が低く、取り扱い性に優れていた。
The conditions of the synthesis examples 1 to 32 are summarized in Tables 1 to 4.
The porous filler slurries of Synthesis Examples 5, 13, and 27 to 32 having a pH of 6.6 to 7.8 were low in pipe corrosivity, low in viscosity, and excellent in handleability.
製造例１
カナダ標準濾水度（ＣＳＦ）が４５０ｍＬある晒化学パルプ（ＢＫＰ）スラリーに、合成例１で得られた多孔性填料を紙質量当たり７部になるよう添加し、さらに絶乾パルプ量１００部当たり、澱粉１．０部、アルキルケテンダイマー０．０３部、及び硫酸バンドを０．５部、歩留向上剤０．０２部（ＤＲ−１５００、ハイモ社製）となるように添加して紙料を調製した。その紙料を、角型手抄き装置を用いて目標坪量が風乾で７０ｇ／ｍ２となるように抄造し、プレスにより脱水後、シリンダードライヤーを用いて乾燥しシートを作製した。その後、線圧２５ｋｇ／ｃｍでキャレンダー処理を施して成紙を得た。
Production Example 1
To the bleached chemical pulp (BKP) slurry with 450 mL Canadian Standard Freeness (CSF), the porous filler obtained in Synthesis Example 1 is added to 7 parts per mass of paper, and further per 100 parts of absolute dry pulp quantity. , 1.0 part of starch, 0.03 part of alkyl ketene dimer, 0.5 part of sulfuric acid band and 0.02 part of yield improver (DR-1500, manufactured by Hymo Co., Ltd.) Was prepared. The stock was made using a square handmaking device so that the target basis weight was 70 g / m 2 when air-dried, dehydrated by a press, and then dried using a cylinder dryer to produce a sheet. Thereafter, a calendering process was performed at a linear pressure of 25 kg / cm to obtain a synthetic paper.
製造例２〜３２
製造例１における合成例１で得られた多孔性填料を、表１〜４に示すような合成例２〜３２で得られたものに各々変更したこと以外は、製造例１と同一条件で成紙を得た。
Production Examples 2-32
The porous filler obtained in Synthesis Example 1 in Production Example 1 was changed under the same conditions as in Production Example 1 except that the porous fillers obtained in Synthesis Examples 2 to 32 as shown in Tables 1 to 4 were respectively changed. I got paper.
各製造例の紙について、以下のように評価した。評価結果を表５〜８に示す。
・米坪：ＪＩＳ Ｐ ８１２４に基づいて測定した。
・紙の緊度（密度）：ＪＩＳ Ｐ ８１１８により測定した。
・灰分：ＪＩＳ Ｐ ８２５１に基づき５２５℃で灰化して測定した。
・不透明度：ＪＩＳ Ｐ ８１４９に従って測定した。
・内部結合強度：Ｊ．ＴＡＰＰＩ Ｎｏ．１８−２に従い測定した。
・表面強度（印刷強度）：ＲＩ印刷機（明製作所製）にてオフセットインキＴ１３を用いて印刷し、その際の紙の表面強度を評価した。
◎：強度が高く、実用上問題なく、品質も優れている。
○：強度が高く、実用上問題ない。
△：強度がやや劣り、実用上問題ある。
×：強度が著しく劣り、実用上問題であり、品質も著しく劣っている。
The paper of each production example was evaluated as follows. The evaluation results are shown in Tables 5-8.
-Yonetsubo: Measured based on JIS P 8124.
Paper tightness (density): Measured according to JIS P 8118.
Ash content: Measured by ashing at 525 ° C. based on JIS P 8251.
Opacity: Measured according to JIS P 8149.
-Internal bond strength: TAPPI No. It measured according to 18-2.
-Surface strength (printing strength): Printing was performed using an offset ink T13 with an RI printer (manufactured by Meisei Seisakusho), and the surface strength of the paper at that time was evaluated.
A: High in strength, practically satisfactory, and excellent in quality.
○: Strength is high and there is no practical problem.
Δ: The strength is slightly inferior, and there is a problem in practical use.
X: The strength is remarkably inferior, it is a problem in practical use, and the quality is remarkably inferior.
コア粒子とコア粒子の周囲に配置された酸化ケイ素化合物とを含有し、特定の製法で製造され、特定の比表面積および細孔径を有する製造例１〜１９および製造例２６〜３２の多孔性填料は、パルプスラリー調製時の剪断力およびプレス圧およびキャレンダー圧による潰れが防止されており、紙の嵩高化効果が高い上に、白紙での不透明度が高かった。また、適切な平均粒子径および狭い粒度分布を有するため、紙の表面強度および内部結合強度が高かった。
これに対し、コア粒子の質量割合が少ない製造例２０の多孔性填料は、内部結合強度、表面強度で満足する結果が得られなかった。
コア粒子が４０質量部を超える製造例２１の多孔性填料は、嵩高化効果、内部結合強度、表面強度が不足していた。
比表面積が２０ｍ２／ｇ未満の製造例２２の多孔性填料は、内部結合強度、表面強度が不足していた。
比表面積が２００ｍ２／ｇを超える製造例２３の多孔性填料は、嵩高化効果が不足していた。
細孔径が０．１０μｍ未満の製造例２４の多孔性填料は、嵩高化効果が不足していた。
細孔径が０．８０μｍを超える製造例２５の多孔性填料は、表面強度が不足していた。
Porous fillers of Production Examples 1 to 19 and Production Examples 26 to 32, each comprising a core particle and a silicon oxide compound disposed around the core particle, produced by a specific production method and having a specific specific surface area and pore diameter Was prevented from being crushed by shearing force, pressing pressure and calendar pressure during pulp slurry preparation, and had a high paper bulking effect and high opacity on white paper. Moreover, since it has a suitable average particle diameter and narrow particle size distribution, the paper surface strength and internal bond strength were high.
On the other hand, the porous filler of Production Example 20 having a small mass ratio of the core particles could not obtain satisfactory results in the internal bond strength and surface strength.
The porous filler of Production Example 21 in which the core particles exceeded 40 parts by mass had insufficient bulking effect, internal bond strength, and surface strength.
The porous filler of Production Example 22 having a specific surface area of less than 20 m 2 / g was insufficient in internal bond strength and surface strength.
The porous filler of Production Example 23 having a specific surface area exceeding 200 m 2 / g was insufficient in bulking effect.
The porous filler of Production Example 24 having a pore diameter of less than 0.10 μm was insufficient in bulking effect.
The porous filler of Production Example 25 having a pore diameter exceeding 0.80 μm had insufficient surface strength.
Claims (6)
前記酸化ケイ素化合物は、二酸化ケイ素および／またはケイ酸塩であり、前記ケイ酸塩が、一般式ｘＭ ２ Ｏ・ｙＳｉＯ ２ 、ｘＭＯ・ｙＳｉＯ ２ 、ｘＭ ２ Ｏ ３ ・ｙＳｉＯ ２ （ＭはＡｌ，Ｆｅ，Ｃａ，Ｍｇ，Ｎａ，Ｋ，Ｔｉ，Ｚｎのいずれかであり、ｘ，ｙは任意の正の数値である。）のいずれかで表され、
コア粒子の質量割合が酸化ケイ素化合物１００質量部に対して１〜２４質量部であり、
比表面積が２０〜２００ｍ２／ｇ、かつ、細孔径が０．１０〜０．８０μｍであることを特徴とする紙用多孔性填料。 A porous filler for paper having an average particle size of 10 to 40 μm having core particles and a silicon oxide compound attached around the core particles,
The silicon oxide compound is silicon dioxide and / or silicate, and the silicate has a general formula xM 2 O · ySiO 2 , xMO · ySiO 2 , xM 2 O 3 · ySiO 2 (M is Al, Fe , Ca, Mg, Na, K, Ti, Zn, and x and y are arbitrary positive numerical values).
The mass ratio of the core particles is 1 to 24 parts by mass with respect to 100 parts by mass of the silicon oxide compound,
A porous filler for paper , which has a specific surface area of 20 to 200 m 2 / g and a pore diameter of 0.10 to 0.80 μm.
前記酸化ケイ素化合物は、二酸化ケイ素および／またはケイ酸塩であり、前記ケイ酸塩が、一般式ｘＭ ２ Ｏ・ｙＳｉＯ ２ 、ｘＭＯ・ｙＳｉＯ ２ 、ｘＭ ２ Ｏ ３ ・ｙＳｉＯ ２ （ＭはＡｌ，Ｆｅ，Ｃａ，Ｍｇ，Ｎａ，Ｋ，Ｔｉ，Ｚｎのいずれかであり、ｘ，ｙは任意の正の数値である。）のいずれかで表されたものであり、
コア粒子の質量割合が酸化ケイ素化合物１００質量部に対して１〜２４質量部であり、
鉱酸、鉱酸の金属塩およびケイ酸アルカリに由来するイオンを含む電解質の濃度が３５〜８０ｇ／Ｌであることを特徴とする紙用多孔性填料スラリー。 A porous filler slurry for paper containing a core filler and a porous filler for paper having an average particle size of 10 to 40 μm having a core particle and a silicon oxide compound attached around the core particle,
The silicon oxide compound is silicon dioxide and / or silicate, and the silicate has a general formula xM 2 O · ySiO 2 , xMO · ySiO 2 , xM 2 O 3 · ySiO 2 (M is Al, Fe , Ca, Mg, Na, K, Ti, and Zn, and x and y are arbitrary positive numerical values).
The mass ratio of the core particles is 1 to 24 parts by mass with respect to 100 parts by mass of the silicon oxide compound,
A porous filler slurry for paper , wherein the concentration of the electrolyte containing mineral acid, metal salt of mineral acid and ions derived from alkali silicate is 35 to 80 g / L.
コア粒子の添加量が、生成する酸化ケイ素化合物１００質量部に対して１〜２４質量部になるように、紙用多孔性填料スラリー中の、鉱酸、鉱酸の金属塩およびケイ酸アルカリに由来するイオンを含む電解質の濃度を３５〜８０ｇ／Ｌにし、
前記酸化ケイ素化合物は、二酸化ケイ素および／またはケイ酸塩であり、前記ケイ酸塩が、一般式ｘＭ ２ Ｏ・ｙＳｉＯ ２ 、ｘＭＯ・ｙＳｉＯ ２ 、ｘＭ ２ Ｏ ３ ・ｙＳｉＯ ２ （ＭはＡｌ，Ｆｅ，Ｃａ，Ｍｇ，Ｎａ，Ｋ，Ｔｉ，Ｚｎのいずれかであり、ｘ，ｙは任意の正の数値である。）のいずれかで表されたものであることを特徴とする紙用多孔性填料の製造方法。 After the core particles are added to the alkali silicate aqueous solution, a mineral acid solution and / or a metal salt solution of a mineral acid is added and neutralized to precipitate a silicon oxide compound around the core particles, so that the average particle size is 10 preparing a porous filler slurries for paper, including paper for porous fillers ～40Myuemu, method for producing a porous filler for paper and a step of recovering a porous filler for paper from a porous filler slurry the paper Because
The mineral acid, the metal salt of the mineral acid, and the alkali silicate in the porous filler slurry for paper so that the amount of the core particles added is 1 to 24 parts by mass with respect to 100 parts by mass of the silicon oxide compound to be produced. The concentration of the electrolyte containing the ions derived from 35 to 80 g / L ,
The silicon oxide compound is silicon dioxide and / or silicate, and the silicate has a general formula xM 2 O · ySiO 2 , xMO · ySiO 2 , xM 2 O 3 · ySiO 2 (M is Al, Fe , Ca, Mg, Na, K , Ti, is any of Zn, x, y is any positive number.) for paper porosity, characterized in der Rukoto those represented by any one of A method for producing sex fillers.
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