JP4743105B2 - Newspaper for cold offset printing - Google Patents
Newspaper for cold offset printing Download PDFInfo
- Publication number
- JP4743105B2 JP4743105B2 JP2006336482A JP2006336482A JP4743105B2 JP 4743105 B2 JP4743105 B2 JP 4743105B2 JP 2006336482 A JP2006336482 A JP 2006336482A JP 2006336482 A JP2006336482 A JP 2006336482A JP 4743105 B2 JP4743105 B2 JP 4743105B2
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- Prior art keywords
- calcium carbonate
- paper
- light calcium
- printing
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000007645 offset printing Methods 0.000 title claims description 51
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 200
- 239000000123 paper Substances 0.000 claims description 107
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 99
- 239000000049 pigment Substances 0.000 claims description 47
- 239000011248 coating agent Substances 0.000 claims description 34
- 238000000576 coating method Methods 0.000 claims description 34
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 22
- 229920002472 Starch Polymers 0.000 claims description 21
- 235000012211 aluminium silicate Nutrition 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 21
- 239000005995 Aluminium silicate Substances 0.000 claims description 20
- 239000011230 binding agent Substances 0.000 claims description 20
- 239000011164 primary particle Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 235000019698 starch Nutrition 0.000 claims description 17
- 239000008107 starch Substances 0.000 claims description 15
- 239000012756 surface treatment agent Substances 0.000 claims description 15
- 239000004816 latex Substances 0.000 claims description 12
- 229920000126 latex Polymers 0.000 claims description 12
- 239000011163 secondary particle Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 2
- 238000007639 printing Methods 0.000 description 80
- 239000012615 aggregate Substances 0.000 description 48
- 239000002245 particle Substances 0.000 description 33
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 229920001131 Pulp (paper) Polymers 0.000 description 28
- 239000002002 slurry Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 12
- 239000000920 calcium hydroxide Substances 0.000 description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 12
- 239000002270 dispersing agent Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000004513 sizing Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000000945 filler Substances 0.000 description 9
- 229910021532 Calcite Inorganic materials 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000000454 talc Substances 0.000 description 7
- 229910052623 talc Inorganic materials 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 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 5
- 229920002261 Corn starch Polymers 0.000 description 5
- 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 5
- 238000009825 accumulation Methods 0.000 description 5
- 229920006319 cationized starch Polymers 0.000 description 5
- 229940099112 cornstarch Drugs 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000149 penetrating effect Effects 0.000 description 5
- 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 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000002655 kraft paper Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000010893 paper waste Substances 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011122 softwood Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 239000008120 corn starch Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000013055 pulp slurry Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 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
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 102000011632 Caseins Human genes 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は、コールドオフセット型印刷輪転機を用いた多色カラー印刷において、インキ着肉性、印刷後不透明度を顕著に向上することができ、しかもネッパリ現象、ブランケットパイリングやセットオフ不良等のトラブルを発生することなく、良好な印刷作業性およびカラー印刷品質を有するコールドオフセット印刷用新聞用紙に関する。 The present invention can remarkably improve ink fillability and post-print opacity in multi-color printing using a cold offset printing press, and troubles such as Nepari phenomenon, blanket piling, and set-off defects. The present invention relates to a newsprint for cold offset printing having good printing workability and color printing quality without causing occurrences of the problem.
近年、コールドセットオフセット型輪転機が使用される新聞印刷においてはオフセット化、カラー化、高速化が急速に進んでおり、印刷媒体となる新聞用紙に関して、より優れたカラー印刷適性や印刷作業性を有する新聞用紙が求められている。加えて新聞広告をはじめとしたカラー画像には、より高い再現性を要求されるようになっている。刷版の製造工程や原画の鮮明さの進歩も顕著であるものの、通常の新聞用紙の条件でカラー印刷したものの色や鮮明さ等が通常の印刷用塗工紙などに比べ著しく劣るものであり、見た目に訴える力に欠けるものであった。 In recent years, newspaper printing using cold-set offset rotary presses has been rapidly offset, colorized, and speeded up, and has better color printing suitability and printing workability for newspapers that serve as printing media. There is a need for newsprint. In addition, color images such as newspaper advertisements are required to have higher reproducibility. Although the progress of the printing plate manufacturing process and the sharpness of the original image are remarkable, the color and sharpness of the color printed under normal newsprint conditions are significantly inferior to those of ordinary coated paper for printing. , Lacking in appealing power.
さらに、最近の新聞用紙には軽量化が求められており、これに伴い、印刷後も高い不透明度を維持しうる用紙の要求が強まっている。この要求に応えるため、紙の不透明度向上を目的としてホワイトカーボン、炭酸カルシウム、酸化チタンあるいはタルク等の無機顔料が抄紙時の填料として多く使われるようになった。また、環境面で重要視されているＤＩＰ（脱墨古紙パルプ）の高率配合化が進んできているが、ＤＩＰがＧＰやＲＧＰ、ＴＭＰ等のメカニカルパルプに比較し不透明度が出難いため、不透明度の改良とＤＩＰの高率配合化を両立させるのが極めて困難な状況となっている。 Furthermore, recent newspaper papers are required to be lighter, and accordingly, there is an increasing demand for papers that can maintain high opacity after printing. In order to meet this demand, inorganic pigments such as white carbon, calcium carbonate, titanium oxide, and talc have been used as fillers during papermaking in order to improve the opacity of paper. Moreover, although high-rate blending of DIP (deinked waste paper pulp), which is regarded as important in terms of the environment, has progressed, opacity is less likely to occur compared to mechanical pulps such as GP, RGP, and TMP. It is extremely difficult to achieve both improvement in opacity and high rate blending of DIP.
一方、原紙に顔料とバインダーからなる塗料を乾燥質量として、およそ８ｇ／ｍ２以上を塗工、乾燥せしめてなる塗工紙は、表面性が良く多色カラー印刷に適しているが、塗工紙印刷ではヒートセット装置を有した印刷輪転機と過熱蒸発乾燥性のインキを用いており、コールドオフセット型印刷輪転機と浸透乾燥性のインキを用いる新聞印刷とはインキ乾燥システムが異なるため、これらの塗工紙をコールドオフセット新聞輪転機で印刷するとインキ乾燥が十分でない場合に発生するセットオフ不良やコスレ汚れといった印面品質や印刷作業性に関わるトラブルを引き起こす可能性があり、事実上使用できない。 On the other hand, coated paper made by coating a base paper with a pigment and a binder having a dry weight of about 8 g / m 2 or more and having a dry surface has good surface properties and is suitable for multicolor printing. Paper printing uses a printing press with a heat-setting device and superheated evaporative drying ink, and the ink drying system differs between cold offset printing press and newspaper printing using penetrating drying ink. If the coated paper is printed on a cold offset newspaper rotary press, it may cause troubles related to printing surface quality and printing workability such as set-off failure and smearing that occur when the ink is not sufficiently dried.
コールドオフセット印刷用新聞用紙としては、針状顔料と吸油量が６５ｃｃ／以上の顔料を含有する塗工層を設ける技術が開示されている（特許文献１参照）。針状顔料を含有させることで塗工適性向上を狙っているが、針状顔料は裏抜け防止効果が低く、添加すればするほど印刷後不透明度には不利となってしまう。また、吸油量が極端に高い顔料を多量に含む塗工層は、湿潤状態での表面強度が弱くなる傾向があり、印刷機のブランケットへの顔料パイリングを起こしやすい。さらに、吸油量が高い顔料を多量に含む塗工層は、インキ中のビヒクル成分を急速に吸収するため紙面上のインキタックの急激な上昇を招き、印刷機ロールに高タックインキが付着して紙面を汚すことがあった。原紙の動的濡れ値を規定し、カオリンと平均粒径を規定した不定形顔料を併用することにより、インキセット適性やインキ濃度を向上させる技術が開示されているが、この方法では不透明度向上効果が小さく、また、インキセットが遅くなり、ベタツキの問題が発生することがあった（特許文献２参照）。また、凝集軽炭を塗工した印刷用紙に関する技術が開示されていが、いずれも熱転写受像用記録紙やマットグラビア用紙などの高塗工量が必須の製品が目的であり、用紙に高度なインキ吸収能力を必要とするコールドオフセット印刷には適用できない（特許文献３、４、５）。特許文献３の技術では、塗工量が少ない場合にはバインダーが不足しブランケットパイリングを引き起こしてしまう。また、インクジェット用紙を目的としたものであり、表面処理剤にカチオン高分子を配合するが、カチオン高分子は軽炭に対して強い凝集作用があるため粘度安定性が低く、塗工した場合に顔料の局在化が起こりやすいため、コールドオフセット印刷には不向きであった。特許文献４の技術では表面処理剤に重質炭酸カルシウムを配合するが、重質炭酸カルシウムは不定形なため軽質炭酸カルシウムに比べてインキ吸収能力が出にくく、これもやはりコールドオフセット印刷には不利となる。特許文献５の技術では、表面処理剤に粒子径３〜５μｍの凝集軽炭を配合するが、粒子径が大きいものはオフセット印刷時にはブランケットにとられやすいためバインダーを極端に増やす必要があるが、バインダーを多くしすぎると印刷後不透明度に対して悪影響が出てしまうため、コールドオフセット印刷用としては不十分であった。 A technology for providing a coating layer containing a needle pigment and a pigment having an oil absorption of 65 cc / or more is disclosed as a news paper for cold offset printing (see Patent Document 1). Although the improvement of the coating suitability is aimed at by containing the acicular pigment, the acicular pigment has a low effect of preventing the see-through, and the more it is added, the more disadvantageous it becomes for the opacity after printing. In addition, a coating layer containing a large amount of pigment having an extremely high oil absorption tends to have a weak surface strength in a wet state, and is likely to cause pigment piling on a blanket of a printing press. Furthermore, the coating layer containing a large amount of pigment with high oil absorption absorbs the vehicle components in the ink rapidly, causing a rapid rise in ink tack on the paper surface, and high tack ink adheres to the printing press roll. The paper surface was sometimes stained. The technology for improving the ink set suitability and the ink density by using dynamic pigment of the base paper and the use of kaolin and an irregular pigment with an average particle size is disclosed, but this method improves opacity. The effect is small, the ink setting becomes slow, and stickiness may occur (see Patent Document 2). In addition, technologies related to printing paper coated with agglomerated light coal have been disclosed, but all are intended for products that require a high coating amount, such as thermal transfer image-receiving recording paper and mat gravure paper. It cannot be applied to cold offset printing that requires absorption capacity (Patent Documents 3, 4, and 5). In the technique of Patent Document 3, when the coating amount is small, the binder is insufficient and blanket piling is caused. Also intended for inkjet paper, a cationic polymer is added to the surface treatment agent, but since the cationic polymer has a strong cohesive action on light coal, viscosity stability is low, Since the pigment is easily localized, it is not suitable for cold offset printing. In the technique of Patent Document 4, heavy calcium carbonate is blended in the surface treatment agent. However, heavy calcium carbonate is indefinite and less ink absorbing ability than light calcium carbonate, which is also disadvantageous for cold offset printing. It becomes. In the technique of Patent Document 5, a coagulated light coal having a particle size of 3 to 5 μm is blended with the surface treatment agent, but those having a large particle size need to increase the binder extremely because they are easily taken by a blanket during offset printing. If too much binder is used, it will have an adverse effect on the opacity after printing, which is insufficient for cold offset printing.
以上のような状況から、浸透乾燥性インキを使用するコールドセット型高速輪転機印刷において、インキセット性が良好で、かつ、印刷作業性に優れ、印刷後不透明度が高く、カラー多色印刷での色再現性や鮮明性の良好な印刷適性を有する新聞印刷用紙が強く要望されてきた。
本発明は、多色カラー印刷方式において、浸透乾燥性インキを用いたコールドオフセット印刷時のインキ着肉性および印刷後不透明度を顕著に向上することができ、しかもセットオフ不良などの印刷トラブルを発生することなく良好な印刷作業性及びカラー印刷品質を有するコールドオフセット用新聞印刷用紙を提供するものである。 The present invention can remarkably improve ink fillability and opacity after printing in cold offset printing using penetrable drying ink in a multicolor printing system, and can also prevent printing troubles such as defective set-off. It is an object of the present invention to provide a cold offset newsprint paper having good printing workability and color printing quality without occurrence.
本願は以下の発明を包含する。
（１）原紙上に、軽質炭酸カルシウムを含む顔料と澱粉を含むバインダーを含有する表面処理剤を塗布、乾燥し、製造されるオフセット印刷用紙において、前記軽質炭酸カルシウムが、平均一次粒子径が０．１〜２．０μｍである軽質炭酸カルシウム凝集体であり、軽質炭酸カルシウム凝集体の体積平均二次粒子径が１．０〜３．０μｍであり、軽質炭酸カルシウムが顔料１００質量部中５０〜１００質量部の割合で配合され、バインダーの顔料１００質量部に対する比率が３０質量部以上７０質量部未満であり、前記表面処理剤の固形分塗布量が片面当たり２．４ｇ／ｍ２以下であり、王研式平滑度が１０秒以上、１００秒未満であるコールドオフセット印刷用新聞用紙。
（２）前記軽質炭酸カルシウムが、平均一次粒子径０．１〜０．６μｍである立方体状軽質炭酸カルシウム凝集体、および／または一次粒子径の平均長さが０．７〜２．０μｍである紡錘状軽質炭酸カルシウム凝集体である（１）に記載のコールドオフセット印刷用新聞用紙。
（３）前記バインダーがガラス移転点温度が０℃以下であるスチレン−ブタジエン共重合体ラテックスを含有する（１）又は（２）に記載のコールドオフセット印刷用新聞用紙。
（４）前記顔料がカオリンを含有する（１）〜（３）のいずれか１項に記載のコールドオフセット印刷用新聞用紙。
（５）前記表面処理剤がフィルム転写型塗工装置で塗工される（１）〜（４）のいずれか１項に記載のコールドオフセット印刷用新聞用紙。
This application includes the following inventions.
(1) On an offset printing paper produced by applying a surface treatment agent containing a pigment containing light calcium carbonate and a binder containing starch on a base paper, the light calcium carbonate has an average primary particle size of 0. A light calcium carbonate aggregate having a diameter of 1 to 2.0 μm, a volume average secondary particle diameter of the light calcium carbonate aggregate being 1.0 to 3.0 μm, and light calcium carbonate being 50 to It is blended at a rate of 100 parts by mass, the ratio of the binder to 100 parts by mass of the pigment is 30 parts by mass or more and less than 70 parts by mass, and the solid content of the surface treatment agent is 2.4 g / m 2 or less per side. Newspaper for cold offset printing with Oken type smoothness of 10 seconds or more and less than 100 seconds.
(2) The light calcium carbonate is a cubic light calcium carbonate aggregate having an average primary particle diameter of 0.1 to 0.6 μm, and / or an average primary particle diameter of 0.7 to 2.0 μm. The newsprint for cold offset printing according to (1), which is a spindle-shaped light calcium carbonate aggregate.
(3) The newsprint for cold offset printing according to (1) or (2), wherein the binder contains a styrene-butadiene copolymer latex having a glass transition temperature of 0 ° C. or less.
(4) The newsprint for cold offset printing according to any one of (1) to (3), wherein the pigment contains kaolin.
(5) The newsprint for cold offset printing according to any one of (1) to (4), wherein the surface treatment agent is applied by a film transfer type coating apparatus.
本発明にかかるコールドオフセット印刷用新聞用紙は、コールドオフセット型輪転印刷機を用いた多色カラー印刷において、インキ着肉性、印刷後不透明度を顕著に向上することができ、しかもネッパリ現象、ブランケットパイリングやセットオフ不良等のトラブルを発生することなく、良好な印刷作業性およびカラー印刷品質を有するという利点がある。 The newsprint for cold offset printing according to the present invention can remarkably improve ink fillability and post-print opacity in multicolor printing using a cold offset type rotary printing press. There is an advantage of having good printing workability and color printing quality without causing problems such as piling and set-off defects.
本発明者等は浸透吸収タイプのインキを使用するコールドオフセット型新聞印刷において、新聞用紙表面に塗工される表面処理剤が印刷後不透明度、インキ着肉性などの印刷適性、およびインキセットなどの印刷作業性に与える影響について鋭意検討した。その結果、多色カラー印刷において、顔料塗工の性能が十分に発揮されるためには、ある一定範囲の大きさの軽質炭酸カルシウム凝集体を含む表面処理剤を少量塗布することが重要であることを見出した。また、特定のバインダーの配合量とすることで印刷後不透明度が向上し、同時にブランケットパイリングが抑制できること見出した。さらに平滑度を制御することで印面適性と印刷作業性を両立させうることを見出し、本発明を完成させるに至った。 In the cold offset type newspaper printing using the penetrating absorption type ink, the present inventors have applied the surface treatment agent applied to the newspaper paper surface, such as opacity after printing, printability such as ink fillability, ink set, etc. The effect on the printing workability was investigated. As a result, it is important to apply a small amount of a surface treatment agent containing light calcium carbonate aggregates in a certain range of size in order for pigment coating performance to be fully exerted in multicolor printing. I found out. Moreover, it discovered that the opacity after printing improved by making it the compounding quantity of a specific binder, and blanket piling can be suppressed simultaneously. Furthermore, it has been found that the printing surface suitability and the printing workability can be compatible by controlling the smoothness, and the present invention has been completed.
軽質炭酸カルシウムとしては針状、柱状、球状、紡錘状、立方体状等があり、本発明においてはいずれも使用可能であるが、カルサイト系軽質炭酸カルシウム、すなわち立方体状および紡錘状のものがより好ましい。カルサイト系軽質炭酸カルシウムが好適となる理由は定かではないが、カルサイト系軽質炭酸カルシウムはアラゴナイト系炭酸カルシウムやバテライト系炭酸カルシウムに比べて塗工層中で粗な構造をとりやすいためと考えられる。 Light calcium carbonate includes acicular, columnar, spherical, spindle, and cubic shapes, and any of them can be used in the present invention, but calcite light calcium carbonate, that is, cubic and spindle-shaped preferable. The reason why calcite light calcium carbonate is suitable is not clear, but it is thought that calcite light calcium carbonate tends to have a rough structure in the coating layer compared to aragonite calcium carbonate or vaterite calcium carbonate. It is done.
また、本発明における軽質炭酸カルシウム二次凝集体は、湿式消化した水酸化カルシウムと二酸化炭素含有ガスとの炭酸化反応工程において、一部炭酸化された、好ましくは炭酸化率１０〜５０％の膠質粒子状水酸化カルシウム懸濁液５〜３０質量％（水酸化カルシウム換算で）を反応初期に添加し、炭酸化率１００％になるまで反応させることにより作製した。 Moreover, the light calcium carbonate secondary aggregate in the present invention is partially carbonated in the carbonation reaction step of wet-digested calcium hydroxide and a carbon dioxide-containing gas, and preferably has a carbonation rate of 10 to 50%. It was prepared by adding 5-30% by mass (in terms of calcium hydroxide) of a colloidal calcium hydroxide suspension at the initial stage of the reaction and allowing the carbonation rate to reach 100%.
軽質炭酸カルシウム二次凝集体としては、平均一次粒子径が０．１〜２．０μｍである軽質炭酸カルシウムの二次凝集体が好適である。平均一次粒子径は、スラリーの場合にはレーザー回折式粒度分布測定装置で測定し、顔料の粉体または塗工紙の場合には表面を粒度分布の体積基準５０％粒子径であり、走査型電子顕微鏡を用いて凝集体を写真撮影し、画像解析装置（ＤＡ−６０００、王子計測機器製）を用いて電子顕微鏡写真を画像解析処理することで求めることが出来る。平均一次粒径が０．１μｍ未満では顔料の不透明性が出にくく、所望の印刷後不透明度が得られない。２．０μｍ以上では二次粒子内の空隙が小さくなりすぎ、インキのビヒクル吸収性がほとんどなくなってしまうため印刷後不透明度が向上しなくなってしまう。一次粒子が立方体状形質炭酸カルシウムである場合、その平均一次粒子径は０．１〜０．６μｍであることが望ましい。平均一次粒子径が０．１μｍ未満では、顔料の不透明性が得られにくく、０．６μｍを超えると安定な二次粒子を得るのが困難になる。一次粒子が紡錘状軽質炭酸カルシウムの場合は、平均長径が０．７〜２．０μｍであるものが好ましい。平均長径は走査型電子顕微鏡写真を画像解析することで求めることが出来る。平均長径が０．７μｍ未満では粒子間隙が非常に少なくなり、インキのビヒクル吸収性が低下してしまう。２．０μｍを超えると安定な二次粒子を得るのが困難になる。なお、本発明においては、顔料１００質量部当たりの分散剤量は０．１〜２．０質量部とする。分散剤量が２．０質量部を超えると分散性能が良くなりすぎ、シェアに対して安定な凝集体が得られなくなる。分散剤量が０．２質量部未満では、スラリー粘度が極端に高くなってしまいハンドリングに問題が発生する場合があるため、好ましくは分散剤を０．５〜１．５質量部、さらに好ましくは０．８〜１．２質量部添加する。分散剤については特に限定されるものではないが、ポリアクリル酸塩、ポリカルボン酸塩、ポリリン酸塩などの一般的な無機顔料用分散剤が使用できる。 As the light calcium carbonate secondary aggregate, a secondary aggregate of light calcium carbonate having an average primary particle diameter of 0.1 to 2.0 μm is preferable. The average primary particle size is measured with a laser diffraction particle size distribution measuring device in the case of slurry, and in the case of pigment powder or coated paper, the surface is the volume-based 50% particle size of the particle size distribution. The aggregate can be obtained by taking a photograph of the aggregate using an electron microscope and subjecting the electron micrograph to image analysis processing using an image analyzer (DA-6000, manufactured by Oji Scientific Instruments). If the average primary particle size is less than 0.1 μm, the opacity of the pigment is difficult to be obtained, and the desired opacity after printing cannot be obtained. If it is 2.0 μm or more, the voids in the secondary particles become too small, and the ink absorbability of the ink is almost lost, so that the opacity after printing is not improved. When the primary particles are cubic plasma calcium carbonate, the average primary particle size is preferably 0.1 to 0.6 μm. When the average primary particle diameter is less than 0.1 μm, it is difficult to obtain the opacity of the pigment, and when it exceeds 0.6 μm, it is difficult to obtain stable secondary particles. When the primary particles are spindle-shaped light calcium carbonate, those having an average major axis of 0.7 to 2.0 μm are preferable. The average major axis can be obtained by image analysis of a scanning electron micrograph. When the average major axis is less than 0.7 μm, the particle gap is very small, and the ink absorbability of the ink is lowered. If it exceeds 2.0 μm, it will be difficult to obtain stable secondary particles. In the present invention, the amount of the dispersant per 100 parts by mass of the pigment is 0.1 to 2.0 parts by mass. When the amount of the dispersant exceeds 2.0 parts by mass, the dispersion performance becomes too good, and aggregates stable against the shear cannot be obtained. If the amount of the dispersant is less than 0.2 parts by mass, the slurry viscosity becomes extremely high, which may cause a problem in handling. Therefore, the dispersant is preferably 0.5 to 1.5 parts by mass, more preferably 0.8 to 1.2 parts by mass are added. Although it does not specifically limit about a dispersing agent, Common dispersing agents for inorganic pigments, such as a polyacrylate, polycarboxylate, polyphosphate, can be used.
本発明において、軽質炭酸カルシウム二次凝集体の体積基準平均粒子径は１．０〜３．０μｍである。なお、平均二次粒子径が１．０μｍ未満の場合、二次凝集体に由来するインキのビヒクル吸収性が劣るため高い印刷後不透明度が得られにくくなる。一方、３．０μｍを超えると、バインダーによる顔料接着効果が極端に低下し、印刷工程においてブランケットパイリングなどのトラブルが発生しやすくなる。さらに、低塗工量の場合には紙面被覆率が低下し不透明性が得られにくくなる。なお、平均二次粒子径も平均一次粒子径と同様な手段で求めることが可能である。 In the present invention, the volume-based average particle size of the light calcium carbonate secondary aggregate is 1.0 to 3.0 μm. In addition, when the average secondary particle diameter is less than 1.0 μm, it is difficult to obtain high post-printing opacity because the vehicle absorbability of the ink derived from the secondary aggregate is poor. On the other hand, if it exceeds 3.0 μm, the pigment adhesion effect by the binder is extremely lowered, and troubles such as blanket piling are likely to occur in the printing process. Furthermore, in the case of a low coating amount, the paper coverage decreases and it becomes difficult to obtain opacity. The average secondary particle size can also be determined by the same means as the average primary particle size.
本発明において、軽質炭酸カルシウム二次凝集体配合量は顔料１００質量部中５０〜１００質量部の割合が好ましく、７０〜９０質量部とすることがさらに好ましい。５０質量部未満では印刷後不透明度に対する十分な効果が得られない。軽質炭酸カルシウム二次凝集体と併用される顔料は特に限定されないが、例えば、二次凝集体を形成していない軽質炭酸カルシウム、重質炭酸カルシウム、カオリン類、タルク類、硫酸カルシウム、硫酸バリウム、二酸化チタン、酸化亜鉛、硫化亜鉛、炭酸亜鉛、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、珪酸マグネシウム、水和珪酸、コロイダルシリカ、コロイダルアルミナ、擬ベーマイト、水酸化アルミニウム、アルミナリトポン、ゼオライト、加水ハロイサイト、炭酸マグネシウム、水酸化マグネシウム、多孔性炭酸マグネシウム、多孔性アルミナ等の白色無機顔料、スチレン系やアクリル系の中空、蜜実型のプラスチックピグメント、ポリエチレンビーズや尿素樹脂、メラミン樹脂等の有機顔料が挙げられる。なお、高速で運転される新聞輪転の場合には動摩擦係数が低いとウェブテンションが かかりにくくなりしわや紙流れ等を起こす恐れがあるが、高すぎてもしわになることがある上に版摩耗を起こす恐れがあるため、動摩擦係数を０．４５〜０．６５の範囲とすることが好ましい。動摩擦係数調整方法としては、顔料塗工量の調整だけでなく、ステアリン酸亜鉛やステアリン酸カルシウムなどの脂肪酸金属石鹸やアルキルケテンダイマー、エチレン系化合物などの一般に用いられている滑剤でも調整可能であるが、地汚れなどの印刷作業性の低下が発生しやすく、また、印刷後不透明度に影響を与える場合がある。印刷作業性や印刷後不透明度を低下させること無く動摩擦係数を調整する方法としては、板状顔料であるカオリンを塗料に配合することが好ましい。カオリンとしては一級カオリン、二級カオリン、微粒カオリン、エンジニアードカオリンなどのカオリンは動摩擦係数を低下させる場合に好適である。焼成カオリンや化学的構造化カオリンなどは動摩擦係数を上昇させる場合に用いることが出来る。カオリンの印刷後不透明度向上効果は炭酸カルシウムに比べると劣るが、サチンや水和珪酸、有機顔料等にくらべて接着剤の吸収が少ない上、表面平滑性への効果が大きいことから両者を併用することにより、少ない塗工量で表面性と印刷後不透明度のバランスをとることが可能となる。軽質炭酸カルシウム二次凝集体とカオリンは好ましくは５０：５０〜９５：５、さらに好ましくは７０：３０〜９０：１０の割合で配合する。カオリンとしてはレーザー法による平均粒子径が２〜８μｍであるエンジニアードカオリンが、不透明度向上効果が高いためより好ましい。なお、この平均粒子径は、分散剤（商品名；アロンＴ５０、東亞合成株式会社製）を０．２質量％添加混合したカオリンスラリーをレーザー回折式粒度分布測定装置 （形式：ＳＡＬＤ−２０００、島津製作所製）にて粒度分布を測定し得られたメディアン径のことをいう。 In the present invention, the light calcium carbonate secondary aggregate content is preferably 50 to 100 parts by mass, more preferably 70 to 90 parts by mass in 100 parts by mass of the pigment. If it is less than 50 parts by mass, a sufficient effect on the opacity after printing cannot be obtained. The pigment used in combination with the light calcium carbonate secondary aggregate is not particularly limited. For example, light calcium carbonate, heavy calcium carbonate, kaolins, talc, calcium sulfate, barium sulfate, which do not form a secondary aggregate, Titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, hydrated silicic acid, colloidal alumina, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina lithopon, zeolite, White inorganic pigments such as hydrous halloysite, magnesium carbonate, magnesium hydroxide, porous magnesium carbonate, porous alumina, styrene or acrylic hollow, honey-type plastic pigments, organics such as polyethylene beads, urea resins, melamine resins Pigments . In the case of newspaper rotation that is operated at high speed, if the dynamic friction coefficient is low, the web tension is less likely to be applied and wrinkles and paper flow may occur. Therefore, the dynamic friction coefficient is preferably in the range of 0.45 to 0.65. The dynamic friction coefficient adjustment method can be adjusted not only by adjusting the pigment coating amount, but also by commonly used lubricants such as fatty acid metal soaps such as zinc stearate and calcium stearate, alkyl ketene dimers, and ethylene compounds. Deterioration of printing workability such as background stains is likely to occur, and opacity after printing may be affected. As a method of adjusting the dynamic friction coefficient without reducing the printing workability and the opacity after printing, it is preferable to blend kaolin, which is a plate-like pigment, into the paint. As kaolin, kaolin such as primary kaolin, secondary kaolin, fine-grain kaolin, engineered kaolin and the like is suitable for reducing the dynamic friction coefficient. Firing kaolin and chemically structured kaolin can be used to increase the dynamic friction coefficient. Kaolin is less effective in improving opacity after printing than calcium carbonate, but both absorb less adhesive compared to satin, hydrated silicic acid, organic pigments, etc. By doing so, it becomes possible to balance the surface property and the opacity after printing with a small coating amount. The light calcium carbonate secondary aggregate and kaolin are preferably blended at a ratio of 50:50 to 95: 5, more preferably 70:30 to 90:10. As kaolin, engineered kaolin having an average particle diameter of 2 to 8 μm by a laser method is more preferable because of its high opacity improvement effect. The average particle size is determined by measuring a kaolin slurry in which 0.2% by mass of a dispersant (trade name; Aron T50, manufactured by Toagosei Co., Ltd.) is added and mixed with a laser diffraction particle size distribution analyzer (type: SALD-2000, Shimadzu). It means the median diameter obtained by measuring the particle size distribution at a manufacturer.
本発明では表面処理剤に前記顔料とともに、パイリングなどに代表される表面強度に纏わるトラブルを回避するために澱粉を含むバインダーを配合する。表面強度と不透明度の両者を高めるための接着剤としては、澱粉類が最も好ましい。また、顔料間の接着を向上させるために合成ラテックス類が好ましく配合される。これらの接着剤は顔料との相溶性が良好で、塗布時に粗大凝集などを起し難いため、特に好ましく用いられる。澱粉類は、親水性成分である繊維との接着能力が高く、固形分塗工量が片面あたり２．４ｇ／ｍ２以下となるような少ない塗工量の場合において紙表面から脱落し易い微細繊維なども強力に接着するため好ましい。前記澱粉類としては、酵素変性澱粉、酸化澱粉、エーテル化澱粉、エステル化澱粉、カチオン化澱粉、疎水化澱粉などが例示される。なお、カルボキシメチルセルロース、メチルセルロース、ヒドロキシアルキルセルロースなどの水溶性セルロース化合物、ポリビニルアルコール化合物やポリアクリルアミド類、カゼイン、大豆蛋白、合成蛋白などの蛋白質類などの通常の塗工紙用バインダーを一種類以上併用しても良い。なお、これらバインダーや添加剤としてはアニオン系の溶液または分散液であることが重要である。カチオン系のバインダーや添加剤を使用した場合、軽質炭酸カルシウム二次凝集体がさらに凝集を起こし、粗大凝集体が生成する場合があり、また、表面処理剤粘度が不安定になる傾向が見られるため好ましくない。 In the present invention, a binder containing starch is added to the surface treating agent together with the pigment in order to avoid troubles related to surface strength typified by piling and the like. As an adhesive for increasing both surface strength and opacity, starches are most preferable. In addition, synthetic latexes are preferably blended in order to improve adhesion between pigments. These adhesives are particularly preferably used because they have good compatibility with pigments and hardly cause coarse aggregation during coating. Starch has a high adhesive ability to fibers, which are hydrophilic components, and it is easy to drop off from the paper surface when the coating amount is so small that the solid coating amount is 2.4 g / m 2 or less per side. Fiber and the like are also preferable because they are strongly bonded. Examples of the starches include enzyme-modified starch, oxidized starch, etherified starch, esterified starch, cationized starch, and hydrophobic starch. In addition, one or more common binders for coated paper such as water-soluble cellulose compounds such as carboxymethylcellulose, methylcellulose, and hydroxyalkylcellulose, polyvinyl alcohol compounds, polyacrylamides, proteins such as casein, soybean protein, and synthetic proteins are used in combination. You may do it. It is important that these binders and additives are anionic solutions or dispersions. When a cationic binder or additive is used, the light calcium carbonate secondary agglomerates may further agglomerate to form coarse agglomerates, and the viscosity of the surface treatment agent tends to become unstable. Therefore, it is not preferable.
バインダーの顔料１００質量部に対する比率は３０質量部以上、７０質量部未満であることが望ましい。塗工量が片面当たり２．４ｇ／ｍ２以下の少量塗工の場合には原紙へ浸透するバインダーの比率が高くなり、３０質量部未満では塗工顔料および紙表面繊維に対する充分な接着力が得られない。一方、７０質量部以上では、塗工顔料および紙表面繊維の接着力は充分であるものの塗工顔料間の空隙がバインダーで埋められてしまい、インキ吸収性が阻害されてしまう。さらに、原紙中に浸透するバインダーが多くなり、不透明度が低下する虞がある。 The ratio of the binder to 100 parts by mass of the pigment is desirably 30 parts by mass or more and less than 70 parts by mass. When the coating amount is a small amount of coating of 2.4 g / m 2 or less per side, the ratio of the binder penetrating to the base paper becomes high. When the coating amount is less than 30 parts by mass, sufficient adhesion to the coating pigment and the paper surface fiber is obtained. I can't get it. On the other hand, at 70 parts by mass or more, although the adhesion between the coating pigment and the paper surface fiber is sufficient, the gap between the coating pigments is filled with the binder, and the ink absorbability is hindered. Furthermore, there is a possibility that the amount of binder penetrating into the base paper increases and the opacity decreases.
本発明においては、接着剤として澱粉とともに好ましくは合成ラテックスが併用される。ラテックスのＴｇとしては特に制限は無いが、表面強度とネッパリのバランスを考慮して２０℃以下のものが好ましく、０℃以下のものがさらに好ましい。このＴｇ範囲にあるものは常温では粘着性を発現し顔料／填料への接着性が良好となるが、分子の極性が非常に低く、強親水性のセルロース繊維に接着性が出にくいため、セルロース繊維との接着力が高い澱粉と併用し、澱粉のみでは弱い顔料／填料への接着性をカバーする働きを持つ。本発明のような低塗工量の場合にはこのラテックスと澱粉の相互の働きの効果が大きく影響することがある。ラテックスとしてはコアシェル型も用いることが出来るが、この場合にはコアのＴｇが０℃以下のものが好ましく用いられる。なお、濃度勾配型と呼ばれる、粒子の内部から外部への組成が連続的に変化しているラテックスについても同様の効果があるが、この場合は平均Ｔｇが０℃以下のものが好適である。澱粉１００質量部に対するラテックスの比率は特に限定されないが、１０〜１００質量部が好ましく、１０〜７０質量部がさらに好ましい。ラテックス比率が１０質量部未満では顔料や填料に対する接着性が不足し、印刷機上でパイリングなどのトラブルが起こりやすくなる。１００質量部を超えると、インキ中のビヒクル分が急速に吸収されてインキタックが上昇して印刷機のロールに付着・堆積し、これに起因するコスレ汚れトラブルが起こる可能性がある。また、ドライピックが悪化することによる印面カスレの懸念がある。なお、ラテックスの配合により紙表面の水に対する接触角を向上できるが、水滴下後０．１秒後の接触角が８０°以上であることが望ましい。水滴下後０．１秒後の接触角が８０°以上では、インキに対しての充分な親和性が確保され、インキ着肉性が良好となる。また、コールドオフセット新聞印刷において必要とされるウェット表面強度が得やすくなる。なお、表面接触角は、例えば動的表面接触角測定装置（Ｆｉｂｒｏ社製、ダイナミックアブソープションテスタＤＡＴ１１００）を用いれば、水滴を滴下後０．１〜５．０秒程度の間の任意の経過時間における表面接触角を測定することが出来る。 In the present invention, a synthetic latex is preferably used in combination with starch as an adhesive. Although there is no restriction | limiting in particular as Tg of latex, The thing of 20 degrees C or less is preferable in consideration of the balance of surface strength and Nepari, and the thing of 0 degrees C or less is further more preferable. Those in this Tg range exhibit tackiness at room temperature and have good adhesion to the pigment / filler, but the polarities of the molecules are very low and adhesion to strong hydrophilic cellulose fibers is difficult. It is used in combination with starch that has high adhesive strength to the fiber, and starch alone has the function of covering adhesion to weak pigments / fillers. In the case of a low coating amount as in the present invention, the effect of the interaction between the latex and starch may be greatly affected. As the latex, a core-shell type can also be used. In this case, a core having a Tg of 0 ° C. or less is preferably used. A latex called a concentration gradient type, in which the composition from the inside of the particle to the outside continuously changes, has the same effect, but in this case, an average Tg of 0 ° C. or less is suitable. Although the ratio of the latex with respect to 100 mass parts of starch is not specifically limited, 10-100 mass parts is preferable and 10-70 mass parts is more preferable. If the latex ratio is less than 10 parts by mass, the adhesion to pigments and fillers is insufficient, and troubles such as piling are likely to occur on the printing press. When the amount exceeds 100 parts by mass, the vehicle component in the ink is rapidly absorbed, the ink tack rises, adheres to and accumulates on the roll of the printing press, and there is a possibility of causing a smearing trouble due to this. In addition, there is a concern that the printing surface may be blurred due to deterioration of dry pick. Although the contact angle of water on the paper surface can be improved by blending the latex, the contact angle 0.1 seconds after the dropwise addition of water is desirably 80 ° or more. When the contact angle 0.1 seconds after water dripping is 80 ° or more, sufficient affinity for the ink is ensured and the ink deposition property is good. In addition, the wet surface strength required in cold offset newspaper printing can be easily obtained. The surface contact angle is, for example, an arbitrary progress between about 0.1 to 5.0 seconds after the water droplet is dropped by using a dynamic surface contact angle measuring device (Fibro, dynamic absorption tester DAT1100). The surface contact angle in time can be measured.
顔料と接着剤を主成分とする表面処理剤は、片面あたり塗工量が２．４ｇ／ｍ２以下であることが好ましく、０．５〜１．４ｇ／ｍ２であることがさらに好ましく、０．７〜１．１ｇ／ｍ２であることがより好ましい。２．４ｇ／ｍ２を超えるとインキセットが遅くなるため、セットオフや文字ダブリなどの印刷品質に問題が発生することがある。 Surface treatment agent composed mainly of a pigment and an adhesive is preferably the amount coated per surface engineering is 2.4 g / m 2 or less, further preferably 0.5~1.4g / m 2, More preferably, it is 0.7-1.1 g / m < 2 >. If it exceeds 2.4 g / m 2 , the ink setting becomes slow, which may cause problems in print quality such as set-off and character double .
本発明においては、王研式平滑度が１０秒以上、１００秒未満であることが必要である。表面平滑性が高いほうがインキ着肉が良好であるため好ましいが、１００秒以上ではインキ吸収性が極端に低下するためセットオフなどのトラブルが発生しやすくなる。一方、１０秒未満では表面が粗すぎて、インキ着肉が悪化し、印面もガサツキ傾向となるため好ましくない。王研式平滑度を１０秒以上、１００秒未満とすることで、表面処理剤の効果を充分に出すことが可能となる。 In the present invention, the Oken smoothness is required to be 10 seconds or more and less than 100 seconds. Higher surface smoothness is preferable because ink deposition is better, but if it is 100 seconds or longer, ink absorbability is extremely lowered, and troubles such as set-off are likely to occur. On the other hand, when the time is less than 10 seconds, the surface is too rough, ink deposition is deteriorated, and the printed surface also tends to be rough. By setting the Oken type smoothness to 10 seconds or more and less than 100 seconds, the effect of the surface treatment agent can be sufficiently exerted.
塗料組成物をオフセット印刷用紙原紙へ塗布するための装置としては、例えばインクラインまたはバーティカルツーロールサイズプレス、ブレードメタリングサイズプレス、ロッドメタリングサイズプレス、ゲートロールコータなどのロールコーター、トレーリング、フレキシブル、ロールアプリケーション、ファウンテンアプリケーション、ショートドゥエルなどのベベルタイプやベントタイプのブレードコーター、ロッドブレードコーター、バーコーター、エアーナイフコーター、カーテンコーター、スプレーコーター、グラビアコーターなどの公知公用の装置が適宜使用されるが、ブレードメタリングサイズプレス、ロッドメタリングサイズプレス、ゲートロールコータなどのフィルム転写型塗工装置が好ましく用いられる。フィルム転写型塗工装置は低濃度でも塗工液が浸透しにくく、表面処理剤を効果的に紙表面にとどめることが可能である。これらの塗工機はオンマシンでもオフマシンでも良いが、生産性などを考慮するとオンマシンでの塗工が好ましい。なお、表面処理剤組成物を塗布後の湿潤塗工層を乾燥する方法としては、例えば、蒸気乾燥、ガスヒーター乾燥、電機ヒーター乾燥、赤外線ヒーター乾燥などの各種方式が採用できる。 As an apparatus for applying the coating composition to the base paper of offset printing paper, for example, an ink line or vertical to roll size press, a blade metalling size press, a rod metalling size press, a roll coater such as a gate roll coater, trailing, Known and publicly used equipment such as bevel type, bent type blade coater, rod blade coater, bar coater, air knife coater, curtain coater, spray coater, gravure coater such as flexible, roll application, fountain application, short dwell etc. are used as appropriate However, a film transfer type coating apparatus such as a blade metering size press, a rod metering size press, or a gate roll coater is preferably used. The film transfer type coating apparatus is difficult to penetrate the coating liquid even at a low concentration, and can effectively keep the surface treatment agent on the paper surface. These coating machines may be on-machine or off-machine, but on-machine coating is preferred in consideration of productivity. In addition, as a method of drying the wet coating layer after apply | coating a surface treating agent composition, various systems, such as vapor | steam drying, gas heater drying, electric heater drying, and infrared heater drying, are employable, for example.
本発明のコールドオフセット用新聞印刷用紙の製造に関しては、塗料組成物の塗工層を形成後に、各種キャレンダー装置にて平滑化処理が施されるが、かかるキャレンダー装置としては、スーパーキャレンダー、ソフトキャレンダー、グロスキャレンダー、コンパクトキャレンダー、マットスーパーキャレンダー、マットキャレンダーなどの一般に使用されているキャレンダー装置が適宜使用される。キャレンダー仕上げ条件としては、剛性ロールの温度、キャレンダー圧力、ニップ数、ロール速度、キャレンダー前水分などが要求される品質に応じて適宜選択される。さらに、キャレンダー装置は、コーターと別であるオフタイプとコーターと一体になっているオンタイプがあるが、どちらにおいても使用できる。使用するキャレンダー装置の材質は、剛性ロールでは、金属もしくは、その表面に硬質クロムメッキなどで鏡面処理したロールである。また弾性ロールはウレタン樹脂、エポキシ樹脂、ポリアミド樹脂、フェノール樹脂、ポリアクリレート樹脂などの樹脂ロール、コットン、ナイロン、アラミド樹脂などを成形したロールが適宜使用される。なお、キャレンダーによる仕上げ後の塗工紙の調湿、加湿のための水塗り装置、静電加湿装置、蒸気加湿装置などを適宜組み合わせて使用することも可能である。 Regarding the production of the cold offset newspaper printing paper of the present invention, after forming the coating layer of the coating composition, smoothing treatment is performed in various calendar devices. As such a calendar device, a super calender is used. Commonly used calendar devices such as a soft calendar, a gloss calendar, a compact calendar, a mat super calendar, and a mat calendar are appropriately used. As the calender finishing conditions, the temperature of the rigid roll, the calender pressure, the number of nips, the roll speed, the moisture before the calender, etc. are appropriately selected according to the required quality. Furthermore, the calendar device has an off type that is different from the coater and an on type that is integrated with the coater, but can be used in either case. The material of the calendar apparatus to be used is a roll that is mirror-finished with a metal or hard chrome plating on the surface of the rigid roll. As the elastic roll, a roll formed by molding a resin roll such as urethane resin, epoxy resin, polyamide resin, phenol resin, polyacrylate resin, cotton, nylon, aramid resin or the like is used as appropriate. In addition, it is also possible to use a suitable combination of a water coating device, an electrostatic humidifier, a steam humidifier, and the like for humidity control and humidification of the coated paper after finishing with a calendar.
本発明にかかるコールドオフセット用新聞印刷用紙の原紙は、以下の如くして得られる。まず、原料パルプとして化学パルプ（ＮＢＫＰ、ＬＢＫＰなど）、機械パルプ（ＧＰ、ＣＧＰ、ＲＧＰ、ＰＧＷ、ＴＭＰなど）、古紙パルプ（ＤＩＰなど）の１種以上が適宜混合されて、紙料の調成が行なわれる。古紙パルプを多く配合すると原紙のインキ吸収性が低下しやすいが、本発明においてはインキ吸収性が高い表面処理をするため、古紙パルプを５０％以上配合することが好ましく、６０％以上配合することがさらに好ましい。次いで、紙料中に必要に応じてホワイトカーボン、クレー、無定形シリカ、タルク、酸化チタン、あるいは炭酸カルシウム等の填料を添加するが、紙中灰分としては５〜１５％となるように添加するのが好ましく、７〜１１％となるように添加するのがさらに好ましい。紙中灰分は高いほうが不透明度が高くなるため好ましいが、高すぎると剛度低下を引き起こし、印刷機上でシワやスタッカージャミングなどのトラブル原因となる虞がある。さらに必要に応じて、紙力増強剤、歩留り向上剤、強化ロジンサイズ剤、エマルジョンサイズ剤などの内添サイズ剤、耐水化剤、紫外線防止剤などの一般に公知公用の抄紙用薬品が添加されて、従来から慣用されている抄紙機により抄紙して原紙が製造される。抄紙ｐＨは特に限定されないが、ｐＨ＝４〜７の酸性〜中性が経済的に好ましい。製品坪量としては５２ｇ／ｍ２以下、より好ましくは３５〜４５ｇ／ｍ２としたときに、本発明が所望とする効果が極めて顕著に発揮されるので、特に望ましい。かくして得られるコールドオフセット印刷用新聞用紙は、キャレンダー通紙により、表面平滑化処理が施される。その場合、両面金属ロールによるマシンキャレンダー仕上げや、金属ロールと弾性ロールからなる加圧ニップ部に通紙するソフトキャレンダー仕上げが適宜施される。 The base paper of the cold offset newspaper printing paper according to the present invention is obtained as follows. First, as a raw material pulp, one or more kinds of chemical pulp (NBKP, LBKP, etc.), mechanical pulp (GP, CGP, RGP, PGW, TMP, etc.), waste paper pulp (DIP, etc.) are appropriately mixed to prepare a stock. Is done. If a large amount of waste paper pulp is blended, the ink absorbability of the base paper tends to be reduced, but in the present invention, it is preferable to blend 50% or more of waste paper pulp, and to blend 60% or more in order to perform surface treatment with high ink absorbability. Is more preferable. Next, a filler such as white carbon, clay, amorphous silica, talc, titanium oxide, or calcium carbonate is added to the paper as necessary, but is added so that the ash content in the paper is 5 to 15%. Is preferable, and it is more preferable to add so that it may become 7 to 11%. A higher ash content in the paper is preferable because the opacity is higher, but an excessively high ash content causes a decrease in stiffness and may cause problems such as wrinkles and stacker jamming on the printing press. In addition, generally known and commonly used papermaking chemicals such as paper strength enhancers, yield improvers, reinforced rosin sizing agents, internal sizing agents such as emulsion sizing agents, water resistance agents, and UV protection agents are added as necessary. A base paper is produced by making paper with a conventionally used paper machine. The papermaking pH is not particularly limited, but acidic to neutral pH = 4-7 is economically preferable. 52 g / m 2 or less as a product basis weight, and more preferably when the 35~45g / m 2, the effect of the present invention as desired is very remarkably exhibited particularly desirable. The newspaper for cold offset printing thus obtained is subjected to a surface smoothing process by calendar feeding. In that case, machine calender finishing by a double-sided metal roll and soft calender finishing by passing paper through a pressure nip composed of a metal roll and an elastic roll are appropriately performed.
また、サイズプレス、ビルブレード、ゲートロールコータ、プレメタリングサイズプレスを使用して、澱粉、ポリビニルアルコールなどを予備塗工した原紙や、ピグメントと接着剤を含む塗工液を１層以上予備塗工した塗工原紙も使用可能である。この原紙の物性は浸透乾燥性インキをコールドセット型高速輪転機で印刷できるに足るものである必要があり、一般の新聞用紙並みの引張強度、引裂強度、伸び等の物理的強度を有するものであればよい。 Also, use a size press, bill blade, gate roll coater, or pre-metering size press to pre-coat one or more layers of base paper pre-coated with starch, polyvinyl alcohol, etc., or a coating solution containing pigment and adhesive. The coated coated paper can also be used. The physical properties of this base paper need to be sufficient to allow penetrating and drying ink to be printed on a cold set type high-speed rotary press, and have physical strength such as tensile strength, tear strength, and elongation equivalent to that of general newsprint. I just need it.
本発明のコールドオフセット用新聞印刷用紙の白色度は高いほうが印刷発色コントラストを得られるためカラー印刷では特に高いほうがよく、具体的には白色度５３％以上が好ましく、５５％以上がより好ましい。また印刷後不透明度も高ければ高いほうが良く、９０％以上が好ましい。印刷後不透明度が低いと両面に印刷を行う新聞用紙の場合には裏面の印刷品質を低下させるため好ましくない。本発明のコールドセットオフセット印刷用新聞用紙は印刷適性すぐれ、特にカラー多色印刷時に網点の太りがなく、裏抜けも少ないため高品質な画像を得ることが可能となる。 The higher the whiteness of the cold offset newsprint paper of the present invention, the higher the whiteness of the color printing, and therefore the higher the whiteness, the more preferred is the whiteness of 53% or more, and the more preferred is 55% or more. Moreover, the higher the opacity after printing, the better, and 90% or more is preferable. A low opacity after printing is not preferable in the case of newsprint that prints on both sides because the printing quality on the back side is lowered. The newsprint paper for cold set offset printing according to the present invention has excellent printability, and in particular, when printing in multi-color, there is no thickening of halftone dots and little back-through, so that a high-quality image can be obtained.
以下に実施例を挙げて、本発明を具体的に説明する。勿論、本発明はそれらの例に限定されるものではない。また、例中の部および％は特に断らない限り、それぞれ質量部および質量％を示す。
後述のようにして得た実施例及び比較例となるコールドオフセット用新聞印刷用紙について、下記の物性を測定し、その結果を表１に示した。
The present invention will be specifically described below with reference to examples. Of course, the present invention is not limited to these examples. Moreover, unless otherwise indicated, the part and% in an example show a mass part and mass%, respectively.
The following physical properties were measured for the cold offset newsprint papers as Examples and Comparative Examples obtained as described below, and the results are shown in Table 1.
（平均粒子径）
顔料スラリーについて、レーザー回折式粒度分布測定装置 （形式：ＳＡＬＤ−２０００、島津製作所製）で測定し、メディアン径を平均粒子径とした。
(Average particle size)
The pigment slurry was measured with a laser diffraction particle size distribution analyzer (type: SALD-2000, manufactured by Shimadzu Corporation), and the median diameter was defined as the average particle diameter.
（白色度）
本発明におけるコールドオフセット印刷新聞用紙の白色度は、分光白色度測色計（スガ試験機社製）を使用してＩＳＯ ３６８８に記載の方法で測定した。
（動摩擦係数）
ＪＩＳ Ｐ ８１４７に準拠した。
表裏−縦縦での測定で、引張速度は２００ｍｍ／ｍｉｎで測定。
（平滑度）
ＪＡＰＡＮ ＴＡＰＰＩＮｏ．５の王研式平滑度試験器により測定。
（コールドオフセット印刷用新聞用紙の水滴下０．１秒後の表面接触角）
２３℃、５０％ＲＨ雰囲気下で、動的表面接触角測定装置（ダイナミックアブソープションテスタ ＤＡＴ１１００、Ｆｉｂｒｏ社製）を用い、水滴を滴下後０．１秒後の表面接触角を測定した。
(Whiteness)
The whiteness of the cold offset newsprint in the present invention was measured by the method described in ISO 3688 using a spectral whiteness colorimeter (manufactured by Suga Test Instruments Co., Ltd.).
(Dynamic friction coefficient)
Conforms to JIS P 8147.
Measurement at front and back-vertical and vertical, with a tensile speed of 200 mm / min.
(Smoothness)
JAPAN TAPPI No. Measured with 5 Kenken type smoothness tester.
(Surface contact angle 0.1 seconds after dripping water on newsprint for cold offset printing)
Using a dynamic surface contact angle measuring device (Dynamic Absorption Tester DAT1100, manufactured by Fibro) under a 23 ° C., 50% RH atmosphere, the surface contact angle 0.1 seconds after dropping a water droplet was measured.
（印刷後不透明度）
ＪＡＰＡＮ ＴＡＰＰＩ Ｎｏ．４５に準拠した。
（接触角）
各実施例及び比較例で得たオフセット印刷用新聞用紙について２３℃５０ＲＨ雰囲気下で動的表面接触各測定装置（ダイナミックアブソープションテスタＤＡＴ１１００、Ｆｉｂｒｏ社製）を用い、水滴を滴下後１秒後の表面接触各を測定した。
(Opacity after printing)
JAPAN TAPPI No. 45.
(Contact angle)
1 second after dropping water droplets on the newspaper for offset printing obtained in each of Examples and Comparative Examples using a dynamic surface contact measuring device (Dynamic Absorption Tester DAT1100, manufactured by Fibro) at 23 ° C. and 50 RH. Each surface contact was measured.
（ブランケットパイリング）
各実施例および比較例で得たオフセット印刷用新聞用紙について、オフセット印刷機（三菱リソピアＬ−ＢＴ３−１１００）を使用して用紙ワイヤー側のカラー４色刷り片面印刷を行い、５０００部印刷を行った後、１胴目のブランケット非画線部の堆積物をＰＥＴ透明テープで採取し、画像解析装置（ＤＡ−６０００、王子計測機器製）にて堆積物面積率を測定した。評価は次の５段階評価で行った。
〈評価基準〉
５：面積率が０．５％以下であり、紙粉の堆積度合いが明確に低い
４：面積率が０．５〜１．０％であり、紙粉の堆積度合いがやや低い
３：面積率が１．０〜３．０％であり、紙粉の堆積度合いは実用上問題ないレベル
２：面積率が３．０〜５．０％であり、紙粉の堆積度合いがやや高い
１：面積率が５．０％以上であり、紙粉の堆積度合いが明確に高い
なお、評価が３未満のものは、実用上問題がある。
(Blanket Piling)
The newsprint paper for offset printing obtained in each of the examples and comparative examples was printed on a paper wire side by color four-color single-sided printing using an offset printer (Mitsubishi Lithopia L-BT3-1100), and 5000 copies were printed. After that, the deposit on the first blanket non-image area was collected with a PET transparent tape, and the deposit area ratio was measured with an image analyzer (DA-6000, manufactured by Oji Scientific Instruments). Evaluation was performed by the following five-step evaluation.
<Evaluation criteria>
5: Area ratio is 0.5% or less, and the degree of paper powder accumulation is clearly low 4: Area ratio is 0.5 to 1.0%, and the degree of paper powder accumulation is slightly low 3: Area ratio Is 1.0 to 3.0%, and the degree of paper dust accumulation is practically acceptable. Level 2: The area ratio is 3.0 to 5.0%, and the degree of paper dust accumulation is slightly high. The rate is 5.0% or more, and the degree of paper dust accumulation is clearly high.
（インキセット）
各実施例及び比較例で得た、コールドオフセット用新聞印刷用紙を短冊状に切り、サンプル台紙（ＯＫ特アートポスト ２５６ｇ／ｍ２）に横並びに貼り付けたものを作成する。インキ練り用のゴムロールを４胴目にセットしたＲＩ印刷試験機（石川島産業機械製）にて該当する金属ロールとの間でオフセット輪転機用新聞印刷インキ（ＮＥＷＳ ＷＥＢＭＡＳＴＥＲ／プロセス墨Ｇ２：サカタインクス株式会社製）を０．５ｃｃ練った後、インキ練り用のゴムロールを２胴目に移動し、新たに４胴目に比較的平滑性の高いインキ転写用片面塗工紙を巻いたゴムロールを装着し、２胴目で印刷を行う。４胴目のロールにタッチした時点で一旦回転を止め、そこから一定時間毎に２ｃｍずつ４胴目のロールにインキを転写し、その転写濃度変化を目視評価した。評価は５段階で行った。なお、下記において基準品とは比較例１で得られたコールドオフセット用印刷用紙である。
(Ink set)
The cold offset newsprint paper obtained in each of the examples and comparative examples was cut into strips, and a sample paper (OK special art post 256 g / m 2 ) was attached side by side. Newspaper printing ink (NEWS WEBMASTER / process ink G2: Sakata Inx Co., Ltd) Manufactured) 0.5 cc kneaded, moved the ink kneading rubber roll to the second cylinder, and newly installed a rubber roll wrapped with relatively smooth one-side coated paper for ink transfer on the fourth cylinder, Printing is performed on the second cylinder. When the 4th roll was touched, the rotation was temporarily stopped, and from there, the ink was transferred to the 4th roll by 2 cm at regular intervals, and the transfer density change was visually evaluated. Evaluation was performed in five stages. In the following, the reference product is the cold offset printing paper obtained in Comparative Example 1.
〈評価基準〉
５：基準品と比較して、印刷終了後のコールドオフセット用新聞印刷用紙の表面を転写した片面塗工紙のインキ濃度が明確に低い
４：基準品と比較して、印刷終了後のコールドオフセット用新聞印刷用紙の表面を転写した片面塗工紙のインキ濃度がやや低い
３：基準品と同等のインキ濃度。
２：基準品と比較して、印刷終了後のコールドオフセット用新聞印刷用紙の表面を転写した片面塗工紙のインキ濃度がやや高い
１：基準品と比較して、印刷終了後のコールドオフセット用新聞印刷用紙の表面を転写した片面塗工紙のインキ濃度が明確に高い
なお、評価が３未満のものは、実用上問題がある。
<Evaluation criteria>
5: Compared with the standard product, the ink density of the single-sided coated paper that transferred the surface of the newspaper printing paper for cold offset after printing is clearly lower. 4: The cold offset after printing is finished compared with the standard product The ink density of single-sided coated paper with the surface of newspaper printing paper used for printing is slightly low 3: Ink density equivalent to the standard product.
2: Compared with the standard product, the ink density of the single-sided coated paper that transfers the surface of the newspaper printing paper for printing after printing is slightly higher. 1: For cold offset after printing compared with the standard product The ink density of single-side coated paper to which the surface of newspaper printing paper has been transferred is clearly high.
（ネッパリ）
各実施例および比較例で得たオフセット印刷用新聞用紙について、非画線部のみのアルミ版とブランケット（ＤＡＹインターナショナル製ＤＡＹブランケット８８９１）をセットしたオフセット印刷機（三菱リソピアＬ−ＢＴ３−１１００）を用いて、インキをのせずに１〜４胴すべてで水刷りを行い、２００部印刷を行った後、水供給を停止し、新聞用紙のブランケットへの貼りつき度合いを目視にて判定した。評価は次の５段階評価で行った。
(Neppali)
For the newsprint for offset printing obtained in each example and comparative example, an offset printing machine (Mitsubishi Lithopia L-BT3-1100) in which an aluminum plate having only a non-image area and a blanket (DAY blanket 8891 manufactured by DAY International) was set was used. Using this, water printing was performed on all the cylinders 1 to 4 without applying ink, and after 200 copies were printed, the water supply was stopped, and the degree of sticking of newsprint paper to the blanket was visually determined. Evaluation was performed by the following five-step evaluation.
〈評価基準〉
５：繊維の取られが全く発生しない。
４：ごくわずかに繊維の取られが発生。
３：繊維の取られは発生するが、実用上問題のないレベル。
２：一部で紙層破壊発生。
１：全面で紙層破壊発生。
なお、評価が３未満のものは、実用上問題がある。
<Evaluation criteria>
5: No fiber removal occurs.
4: A very small amount of fiber was removed.
3: A level where there is no problem in practical use although fibers are removed.
2: Paper layer breakage occurred in part.
1: Paper layer breakage occurred on the entire surface.
Those with an evaluation of less than 3 have practical problems.
コールドオフセット印刷用新聞用紙紙原紙（Ａ）の製造
針葉樹漂白クラフトパルプ（ＮＢＫＰ）１０部、サーモメカニカルパルプ（ＴＭＰ）２６部、チラシを４０％含む新聞脱墨パルプ（ＤＩＰ）６４部の割合で混合して離解し、レファイナーで叩解処理したパルプスラリーに、カチオン化澱粉（Ｐ３Ｙ、ＰＩＲＡＡＢ ＳＴＡＲＣＨ Ｃｏ．Ｌｔｄ製）を０．５％、ロジンサイズ剤（ＡＬ−１２０８、荒川化学株式会社製）を０．２％、填料としてタルクを２％、ホワイトカーボン（自製品）を２％、これら全てを対絶乾パルプ質量％の割合で添加し、硫酸バンドで抄紙ｐＨを４．５に調整後、得られた紙料をギャップフォーマー抄紙機で抄紙し、米坪４２．０ｇ／ｍ２のコールドオフセット用新聞印刷用紙原紙を得た。
Manufacture of newsprint base paper (A) for cold offset printing 10 parts of softwood bleached kraft pulp (NBKP), 26 parts of thermomechanical pulp (TMP), 64 parts of newspaper deinked pulp (DIP) containing 40% leaflet Then, 0.5% cationized starch (P3Y, manufactured by PIRAAB STARCH Co. Ltd) and rosin sizing agent (AL-1208, manufactured by Arakawa Chemical Co., Ltd.) were added to the pulp slurry that had been disaggregated and beaten with a refiner. 2%, 2% of talc as filler, 2% of white carbon (own product), all of which are added in the proportion of mass% of dry pulp and adjusted after adjusting the papermaking pH to 4.5 with sulfuric acid band. The paper stock was made with a gap former paper machine to obtain a cold offset newsprint base paper of 42.0 g / m 2 .
コールドオフセット印刷用新聞用紙紙原紙（Ｂ）の製造
針葉樹漂白クラフトパルプ（ＮＢＫＰ）１０部、サーモメカニカルパルプ（ＴＭＰ）２６部、チラシを４０％含む新聞脱墨パルプ（ＤＩＰ）６４部の割合で混合して離解し、レファイナーで叩解処理したパルプスラリーに、カチオン化澱粉（Ｐ３Ｙ、ＰＩＲＡＡＢ ＳＴＡＲＣＨ Ｃｏ．Ｌｔｄ製）を０．５％、ロジンサイズ剤（ＡＬ−１２０８、荒川化学株式会社製）を０．２％、填料としてタルクを２％、ホワイトカーボン（自製品）を２％、これら全てを対絶乾パルプ質量％の割合で添加し、硫酸バンドで抄紙ｐＨを４．５に調整後、得られた紙料をギャップフォーマー抄紙機で抄紙し、米坪４３．０ｇ／ｍ２のコールドオフセット用新聞印刷用紙原紙を得た。
Production of base paper for cold offset printing (B) 10 parts of softwood bleached kraft pulp (NBKP), 26 parts of thermomechanical pulp (TMP), 64 parts of newspaper deinked pulp (DIP) containing 40% leaflet Then, 0.5% cationized starch (P3Y, manufactured by PIRAAB STARCH Co. Ltd) and rosin sizing agent (AL-1208, manufactured by Arakawa Chemical Co., Ltd.) were added to the pulp slurry that had been disaggregated and beaten with a refiner. 2%, 2% of talc as filler, 2% of white carbon (own product), all of which are added in the proportion of mass% of dry pulp and adjusted after adjusting the papermaking pH to 4.5 with sulfuric acid band. The paper stock was made with a gap former paper machine to obtain a newsprint base paper for cold offset of 43.0 g / m 2 .
コールドオフセット印刷用新聞用紙紙原紙（Ｃ）の製造
針葉樹漂白クラフトパルプ（ＮＢＫＰ）１０部、サーモメカニカルパルプ（ＴＭＰ）２６部、チラシを４０％含む新聞脱墨パルプ（ＤＩＰ）６４部の割合で混合して離解し、レファイナーで叩解処理したパルプスラリーに、カチオン化澱粉（Ｐ３Ｙ、ＰＩＲＡＡＢ ＳＴＡＲＣＨ Ｃｏ．Ｌｔｄ製）を０．５％、ロジンサイズ剤（ＡＬ−１２０８、荒川化学株式会社製）を０．２％、填料としてタルクを２％、ホワイトカーボン（自製品）を２％、これら全てを対絶乾パルプ質量％の割合で添加し、硫酸バンドで抄紙ｐＨを４．５に調整後、得られた紙料をギャップフォーマー抄紙機で抄紙し、米坪３７．０ｇ／ｍ２のコールドオフセット用新聞印刷用紙原紙を得た。
Manufacture of newsprint base paper (C) for cold offset printing 10 parts of softwood bleached kraft pulp (NBKP), 26 parts of thermomechanical pulp (TMP), 64 parts of newspaper deinked pulp (DIP) containing 40% leaflet Then, 0.5% cationized starch (P3Y, manufactured by PIRAAB STARCH Co. Ltd) and rosin sizing agent (AL-1208, manufactured by Arakawa Chemical Co., Ltd.) were added to the pulp slurry that had been disaggregated and beaten with a refiner. 2%, 2% of talc as filler, 2% of white carbon (own product), all of which are added in the proportion of mass% of dry pulp and adjusted after adjusting the papermaking pH to 4.5 with sulfuric acid band. The paper stock was made with a gap former paper machine to obtain a cold offset newsprint base paper of 37.0 g / m 2 .
コールドオフセット印刷用新聞用紙紙原紙（Ｄ）の製造
針葉樹漂白クラフトパルプ（ＮＢＫＰ）１０部、サーモメカニカルパルプ（ＴＭＰ）２６部、脱墨パルプ（ＤＩＰ）６４部の割合で混合して離解し、レファイナーで叩解処理したパルプスラリーに、カチオン化澱粉（Ｐ３Ｙ、ＰＩＲＡＡＢ ＳＴＡＲＣＨ Ｃｏ．Ｌｔｄ製）を０．５％、中性ロジンサイズ剤（Ｎ８１５、荒川化学株式会社製）を０．８％、填料としてタルクを２％、ホワイトカーボン（自製品）を２％、これら全てを対絶乾パルプ質量％の割合で添加し、硫酸バンドで抄紙ｐＨを６．５に調整後、得られた紙料をギャップフォーマー抄紙機で抄紙し、米坪４２．０ｇ／ｍ２のコールドオフセット用新聞印刷用紙原紙を得た。
Manufacture of newsprint base paper (D) for cold offset printing 10 parts of softwood bleached kraft pulp (NBKP), 26 parts of thermomechanical pulp (TMP), 64 parts of deinked pulp (DIP) 0.5% of cationized starch (P3Y, manufactured by Piraab Starch Co. Ltd), 0.8% of neutral rosin sizing agent (N815, manufactured by Arakawa Chemical Co., Ltd.), talc as filler 2%, white carbon (own product) 2%, all of these in the proportion of dry pulp mass%, and after adjusting the papermaking pH to 6.5 with sulfuric acid band, Paper was made with a mer paper machine to obtain a newsprint base paper for cold offset of 42.0 g / m 2 .
実施例１
顔料として下記のようにして作製した軽質炭酸カルシウム二次凝集体Ａスラリーの固形分として１００部、接着剤として糊化溶解した酸化トウモロコシ澱粉（商品名：王子エースＡ、王子コーンスターチ株式会社製）の固形分として５０部、表面サイズ剤としてオレフィン系表面サイズ剤（商品名：ＯＴ２５、荒川化学工業株式会社製）を固形分として５部を加え、固形分濃度２０％の塗料を調製し、これを上記原紙（Ａ）の両面に、ゲートロールコータを使用して乾燥後の塗工量が片面あたり０．８３ｇ／ｍ２となるように塗布、乾燥して実量４３．７ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Example 1
100 parts as a solid content of the light calcium carbonate secondary aggregate A slurry prepared as described below as a pigment, and oxidized corn starch gelatinized and dissolved as an adhesive (trade name: Oji Ace A, manufactured by Oji Corn Starch Co., Ltd.) 50 parts as a solid content, 5 parts as an olefin surface sizing agent (trade name: OT25, manufactured by Arakawa Chemical Co., Ltd.) as a solid content, and a paint with a solid content concentration of 20% are prepared. on both surfaces of the base paper (a), applied as a coating amount after drying using a gate roll coater is per side 0.83 g / m 2, dried for actual amount 43.7 g / m 2 cold A newsprint for offset printing was obtained.
（軽質炭酸カルシウム二次凝集体Ａの作製）
軽質炭酸カルシウム二次凝集体Ａは、水酸化カルシウムと二酸化炭素含有ガスとの炭酸化反応工程において、原料石灰乳に炭酸化率２０％の膠質粒子状水酸化カルシウム懸濁液を水酸化カルシウム換算で２３質量部添加し、反応開始温度５０℃で炭酸ガス濃度３０％の炭酸ガス含有ガスを吹き込み、炭酸化率が１００％になるまで反応させ、ＢＥＴ比表面積２８．９ｍ２／ｇの軽質炭酸カルシウム凝集体を得た。得られた軽質炭酸カルシウム凝集体をフィルタープレスにより脱水し、炭酸カルシウムに対しポリアクリル酸系の分散剤（商品名；アロンＴ５０、東亞合成株式会社製）を１．２質量部加えてコーレスミキサーで分散処理を施し、固形分濃度４５％のスラリーを作製した。この軽質炭酸カルシウム一次粒子は、平均粒子径０．２５μｍのカルサイト系立方体状軽質炭酸カルシウムであり、二次凝集体を形成して平均粒子径が２．５μｍとなっていた。この軽質炭酸カルシウムを二次凝集体Ａとした。
(Preparation of light calcium carbonate secondary aggregate A)
Light calcium carbonate secondary agglomerate A is a calcium hydroxide equivalent of a 20% carbonization suspension of colloidal particles in raw lime milk in the carbonation reaction step of calcium hydroxide and carbon dioxide-containing gas. Is added at a reaction start temperature of 50 ° C., and a carbon dioxide-containing gas having a carbon dioxide concentration of 30% is blown into the reaction mixture until the carbonation rate reaches 100%. Light carbon dioxide having a BET specific surface area of 28.9 m 2 / g Calcium aggregates were obtained. The obtained light calcium carbonate aggregate was dehydrated with a filter press, and 1.2 parts by mass of a polyacrylic acid-based dispersant (trade name; Aron T50, manufactured by Toagosei Co., Ltd.) was added to the calcium carbonate. Dispersion treatment was performed to prepare a slurry having a solid content concentration of 45%. The light calcium carbonate primary particles are calcite cubic light calcium carbonate having an average particle diameter of 0.25 μm, forming secondary aggregates and having an average particle diameter of 2.5 μm. This light calcium carbonate was designated as secondary aggregate A.
実施例２
実施例１の接着剤として酸化トウモロコシ澱粉量を４０部、スチレンブタジエンラテックス（商品名：Ｔ２６３５Ｒ、ＪＳＲ株式会社製）を１０部とし、表面サイズ剤を使用せず、乾燥後の塗工量を片面当たり０．８ｇ／ｍ２とした以外は実施例１と同様にして、実量４３．６ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Example 2
As the adhesive of Example 1, the amount of oxidized corn starch was 40 parts, the styrene butadiene latex (trade name: T2635R, manufactured by JSR Corporation) was 10 parts, the surface sizing agent was not used, and the coating amount after drying was one side. Except for using 0.8 g / m 2 per unit, a cold offset printing newsprint with an actual amount of 43.6 g / m 2 was obtained in the same manner as in Example 1.
実施例３
実施例２の顔料として軽質炭酸カルシウム二次凝集体Ａを固形分として６０部、カオリン（商品名：ミラグロスＪ、シール株式会社製）を４０部とした以外は実施例２と同様にして、実量４３．６ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Example 3
The same procedure as in Example 2 was repeated except that 60 parts of light calcium carbonate secondary aggregate A as a solid content and 40 parts of kaolin (trade name: Milagros J, manufactured by Seal Co., Ltd.) were used as the pigment of Example 2. A newsprint paper for cold offset printing having an amount of 43.6 g / m 2 was obtained.
実施例４
実施例２の顔料として軽質炭酸カルシウム二次凝集体Ａを固形分として８０部、カオリンを２０部とした以外は実施例２と同様にして、実量４３．６ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Example 4
For cold offset printing with an actual amount of 43.6 g / m 2 in the same manner as in Example 2 except that the light calcium carbonate secondary aggregate A is 80 parts as solids and 20 parts of kaolin is used as the pigment of Example 2. I got a newspaper.
実施例５
実施例２の顔料として軽質炭酸カルシウム二次凝集体Ａを固形分として８０部、カオリンを２０部、接着剤として澱粉を２０部、スチレンブタジエンラテックスを２０部とした以外は実施例２と同様にして、実量４３．６ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Example 5
The same procedure as in Example 2 was repeated except that light calcium carbonate secondary aggregate A was used as the pigment of Example 2 and the solid content was 80 parts, kaolin was 20 parts, starch was 20 parts, and styrene butadiene latex was 20 parts. Thus, newsprint paper for cold offset printing having an actual amount of 43.6 g / m 2 was obtained.
実施例６
実施例４の軽質炭酸カルシウム二次凝集体Ａに替えて次のようにして作製した軽質炭酸カルシウム二次凝集体Ｂを用いた以外は実施例４と同様にして、実量４３．６ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Example 6
An actual amount of 43.6 g / m was obtained in the same manner as in Example 4 except that the light calcium carbonate secondary aggregate A produced as follows was used instead of the light calcium carbonate secondary aggregate A of Example 4. 2 news paper for cold offset printing was obtained.
（軽質炭酸カルシウム二次凝集体Ｂの作製）
水酸化カルシウムと炭酸ガスとの炭酸化反応を利用して軽質炭酸カルシウムを合成し、固形分濃度２５％、平均粒子径４．７μｍの軽質炭酸カルシウムスラリーを得た。この軽質炭酸カルシウム一次粒子は平均粒子径１．１μｍのカルサイト系紡錘状軽質炭酸カルシウムであり、二次凝集体を形成して平均粒子径が４．７μｍとなっていた。この炭酸カルシウムスラリーにポリアクリル酸系の分散剤（商品名；アロンＴ５０、東亞合成株式会社製）を０．５部添加後、横型サンドグラインダー（商品名；ＵＶＭ−６０、アイメックス株式会社製）を用いて、処理流量５Ｌ／ｍｉｎで粉砕処理し、スラリー粘度２２０ｍＰａ・ｓの粉砕軽質炭酸カルシウムスラリーを得た。この粉砕品スラリーを１０分間の超音波処理後に測定した平均粒子径は２．１μｍであり、軽質炭酸カルシウム二次凝集体Ｂとした。
(Preparation of light calcium carbonate secondary aggregate B)
Light calcium carbonate was synthesized using a carbonation reaction between calcium hydroxide and carbon dioxide gas to obtain a light calcium carbonate slurry having a solid concentration of 25% and an average particle size of 4.7 μm. The light calcium carbonate primary particles were calcite spindle light calcium carbonate having an average particle diameter of 1.1 μm, and formed secondary aggregates and had an average particle diameter of 4.7 μm. After adding 0.5 parts of a polyacrylic acid-based dispersant (trade name; Aron T50, manufactured by Toagosei Co., Ltd.) to this calcium carbonate slurry, a horizontal sand grinder (trade name; UVM-60, manufactured by Imex Corporation) was added. And pulverized at a processing flow rate of 5 L / min to obtain a pulverized light calcium carbonate slurry having a slurry viscosity of 220 mPa · s. The average particle diameter of this pulverized product slurry measured after ultrasonic treatment for 10 minutes was 2.1 μm, and a light calcium carbonate secondary aggregate B was obtained.
実施例７
実施例１の原紙Ａに替えて原紙Ｄを用いた以外は実施例１と同様にして、実量４３．７ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Example 7
Cold offset printing newsprint with an actual amount of 43.7 g / m 2 was obtained in the same manner as in Example 1 except that the base paper D was used in place of the base paper A of Example 1.
比較例１
糊化溶解した酸化トウモロコシ澱粉（商品名：王子エースＡ、王子コーンスターチ株式会社製）の固形分として１００部、表面サイズ剤としてオレフィン系表面サイズ剤（商品名：ＯＴ２５、荒川化学工業株式会社製）を固形分として５部を加え、固形分濃度１０％の塗料を調製し、これを上記原紙（Ｂ）の両面に、ゲートロールコータを使用して乾燥後の塗工量が片面あたり０．３ｇ／ｍ２となるように塗布、乾燥して実量４３．６ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Comparative Example 1
100 parts as the solid content of gelatinized and dissolved oxidized corn starch (trade name: Oji Ace A, manufactured by Oji Cornstarch Co., Ltd.), and olefin-based surface sizing agent as the surface sizing agent (trade name: OT25, manufactured by Arakawa Chemical Industries, Ltd.) As a solid content, 5 parts is added to prepare a coating material having a solid content concentration of 10%. The coating amount after drying using a gate roll coater on both sides of the base paper (B) is 0.3 g per side. / m 2 and so as applied to obtain a cold offset printing newsprint dried actual amount 43.6 g / m 2.
比較例２
実施例１の接着剤として澱粉１００部、塗料固形分濃度を１８％とし、乾燥後の塗工量が片面あたり１．０５ｇ／ｍ２となるように塗布、乾燥した以外は実施例１と同様にして、実量４４．１ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Comparative Example 2
As in Example 1, except that 100 parts of starch as the adhesive of Example 1, the solid content concentration of the paint was 18%, and the coating amount after drying was 1.05 g / m 2 per side. Thus, newsprint paper for cold offset printing having an actual amount of 44.1 g / m 2 was obtained.
比較例３
実施例１の軽質炭酸カルシウム二次凝集体Ａに替えて次のようにして作製した軽質炭酸カルシウム二次凝集体Ｃを用いた以外は実施例１と同様にして、実量４３．７ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Comparative Example 3
The actual amount was 43.7 g / m in the same manner as in Example 1 except that the light calcium carbonate secondary aggregate C produced as follows was used instead of the light calcium carbonate secondary aggregate A in Example 1. 2 news paper for cold offset printing was obtained.
（軽質炭酸カルシウム二次凝集体Ｃの作製）
軽質炭酸カルシウム二次凝集体Ｃの製造方法は、水酸化カルシウムと二酸化炭素含有ガスとの炭酸化反応工程において、原料石灰乳に炭酸化率２０％の膠質粒子状水酸化カルシウム懸濁液を水酸化カルシウム換算で２８質量部添加し、反応開始温度５０℃で炭酸ガス濃度３０％の炭酸ガス含有ガスを吹き込み、炭酸化率が１００％になるまで反応させ、ＢＥＴ比表面積３２．８ｍ２／ｇの軽質炭酸カルシウム凝集体を得た。得られた軽質炭酸カルシウム凝集体をフィルタープレスにより脱水し、炭酸カルシウムに対しポリアクリル酸系の分散剤（商品名；アロンＴ５０、東亞合成株式会社製）を１．５質量部加えてコーレスミキサーで分散処理を施し、固形分濃度３０％のスラリーを作製した。この軽質炭酸カルシウム一次粒子は平均粒子径０．２１μｍのカルサイト系立方体状軽質炭酸カルシウムであり、二次凝集体を形成して平均粒子径が３．２μｍとなっていた。このスラリーを軽質炭酸カルシウム二次凝集体Ｃとした。
(Preparation of light calcium carbonate secondary aggregate C)
The light calcium carbonate secondary agglomerate C is produced in the carbonation reaction step of calcium hydroxide and carbon dioxide-containing gas by using a raw material lime milk with a colloidal calcium hydroxide suspension having a carbonation rate of 20% as water. 28 parts by mass in terms of calcium oxide was added, a carbon dioxide containing gas having a carbon dioxide concentration of 30% was blown at a reaction start temperature of 50 ° C., and the reaction was carried out until the carbonation rate reached 100%, and a BET specific surface area of 32.8 m 2 / g. Of light calcium carbonate aggregate was obtained. The obtained light calcium carbonate aggregate was dehydrated with a filter press, and 1.5 parts by mass of a polyacrylic acid-based dispersant (trade name; Aron T50, manufactured by Toagosei Co., Ltd.) was added to the calcium carbonate with a Coreless mixer. Dispersion treatment was performed to prepare a slurry having a solid content concentration of 30%. The light calcium carbonate primary particles are calcite-based cubic light calcium carbonate having an average particle diameter of 0.21 μm, forming secondary aggregates and having an average particle diameter of 3.2 μm. This slurry was designated as light calcium carbonate secondary aggregate C.
比較例４
実施例１の軽質炭酸カルシウム二次凝集体Ａに替えて次のようにして作製した軽質炭酸カルシウム分散体Ｄを用いた以外は実施例１と同様にして、実量４３．７ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Comparative Example 4
An actual amount of 43.7 g / m 2 was obtained in the same manner as in Example 1 except that the light calcium carbonate dispersion D produced as follows was used in place of the light calcium carbonate secondary aggregate A of Example 1. A newsprint for cold offset printing was obtained.
（軽質炭酸カルシウム分散体Ｄの作製）
軽質炭酸カルシウム分散体Ｄの製造方法は、水酸化カルシウムと二酸化炭素含有ガスとの炭酸化反応工程において、多段炭酸化反応により得られた中間体水性懸濁液に、炭酸化率３０％の膠質粒子状水酸化カルシウムをＣａ化合物のモル比が１００：８になるように混合したのち、反応開始温度１５℃で炭酸ガス濃度３０％の炭酸ガス含有ガスを吹き込み、炭酸化率が１００％になるまで反応させ、ＢＥＴ比表面積１５ｍ２／ｇの立方体状の軽質炭酸カルシウム分散体を得た。得られた軽質炭酸カルシウム凝集体をフィルタープレスにより脱水し、炭酸カルシウムに対しポリアクリル酸系の分散剤（商品名；アロンＴ５０、東亞合成株式会社製）を１．５質量部加えてコーレスミキサーで分散処理を施し、固形分濃度６０％のスラリーを作製した。この軽質炭酸カルシウム一次粒子は平均粒子径０．６１μｍのカルサイト系立方体状軽質炭酸カルシウムであり、二次凝集体を形成していなかった。この分散体スラリーを軽質炭酸カルシウム分散体Ｄとした。
(Preparation of light calcium carbonate dispersion D)
A light calcium carbonate dispersion D is produced by a method of producing a colloid having a carbonation rate of 30% in an intermediate aqueous suspension obtained by a multistage carbonation reaction in a carbonation reaction step of calcium hydroxide and a carbon dioxide-containing gas. After mixing the particulate calcium hydroxide so that the molar ratio of the Ca compound is 100: 8, carbon dioxide containing gas having a carbon dioxide concentration of 30% is blown at a reaction start temperature of 15 ° C., and the carbonation rate becomes 100%. To obtain a cubic light calcium carbonate dispersion having a BET specific surface area of 15 m 2 / g. The obtained light calcium carbonate aggregate was dehydrated with a filter press, and 1.5 parts by mass of a polyacrylic acid-based dispersant (trade name; Aron T50, manufactured by Toagosei Co., Ltd.) was added to the calcium carbonate with a Coreless mixer. Dispersion treatment was performed to prepare a slurry having a solid concentration of 60%. The light calcium carbonate primary particles were calcite cubic light calcium carbonate having an average particle diameter of 0.61 μm, and no secondary aggregates were formed. This dispersion slurry was designated as light calcium carbonate dispersion D.
比較例５
実施例１の軽質炭酸カルシウム二次凝集体Ａに替えて、次のようにして作製した軽質炭酸カルシウムＥを用いた以外は実施例１と同様にして、実量４３．７ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Comparative Example 5
In place of the light calcium carbonate secondary aggregate A of Example 1, a cold calcium having an actual amount of 43.7 g / m 2 was obtained in the same manner as in Example 1 except that the light calcium carbonate E produced as follows was used. A newsprint for offset printing was obtained.
（軽質炭酸カルシウム分散体Ｅの作製）
水酸化カルシウムと炭酸ガスとの炭酸化反応を利用して軽質炭酸カルシウムを合成し、固形分濃度２５％、平均粒子径４．７μｍの軽質炭酸カルシウムスラリーを得た。この軽質炭酸カルシウム一次粒子は平均粒子径１．１μｍのカルサイト系紡錘状軽質炭酸カルシウムであり、二次粒子を形成して平均粒子径が４．７μｍとなっていた。この炭酸カルシウムスラリーに分散剤（商品名；アロンＴ５０、東亞合成株式会社製）を０．８部添加後、横型サンドグラインダー（商品名；ＵＶＭ−６０、アイメックス株式会社製）を用いて、処理流量９Ｌ／ｍｉｎで粉砕処理し、スラリー粘度２ｍＰａ・ｓの粉砕軽質炭酸カルシウムスラリーを得た。この粉砕品は二次凝集体を形成しておらず、平均粒子径は０．６９μｍであった。このスラリーを軽質炭酸カルシウム分散体Ｅとした。
(Preparation of light calcium carbonate dispersion E)
Light calcium carbonate was synthesized using a carbonation reaction between calcium hydroxide and carbon dioxide gas to obtain a light calcium carbonate slurry having a solid concentration of 25% and an average particle size of 4.7 μm. The light calcium carbonate primary particles were calcite-type spindle-shaped light calcium carbonate having an average particle diameter of 1.1 μm, and formed secondary particles with an average particle diameter of 4.7 μm. After adding 0.8 parts of a dispersant (trade name; Aron T50, manufactured by Toagosei Co., Ltd.) to this calcium carbonate slurry, a processing flow rate is obtained using a horizontal sand grinder (trade name; UVM-60, manufactured by Imex Corporation). The pulverization process was performed at 9 L / min to obtain a pulverized light calcium carbonate slurry having a slurry viscosity of 2 mPa · s. This pulverized product did not form secondary aggregates, and the average particle size was 0.69 μm. This slurry was designated as light calcium carbonate dispersion E.
比較例６
実施例１の軽質炭酸カルシウム二次凝集体Ａに替えて、次のようにして作製した軽質炭酸カルシウム二次凝集体Ｆを用いた以外は実施例１と同様にして、実量４３．７ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Comparative Example 6
In place of the light calcium carbonate secondary aggregate A of Example 1, the light calcium carbonate secondary aggregate F produced as follows was used in the same manner as in Example 1 except that the actual amount was 43.7 g / A newsprint for cold offset printing of m 2 was obtained.
（軽質炭酸カルシウム二次凝集体Ｆの作製）
水酸化カルシウムと二酸化炭素含有ガスとの炭酸化反応を利用して軽質炭酸カルシウムを合成し、固形分濃度２５％、平均粒子径４．７μｍの軽質炭酸カルシウムスラリーを得た。この軽質炭酸カルシウム一次粒子は平均粒子径１．１μｍのカルサイト系紡錘状軽質炭酸カルシウムであり、二次凝集体を形成して平均粒子径が４．７μｍとなっていた。この軽質炭酸カルシウムを二次凝集体Ｆとした。
(Preparation of light calcium carbonate secondary aggregate F)
Light calcium carbonate was synthesized using a carbonation reaction between calcium hydroxide and a carbon dioxide-containing gas to obtain a light calcium carbonate slurry having a solid concentration of 25% and an average particle size of 4.7 μm. The light calcium carbonate primary particles were calcite spindle light calcium carbonate having an average particle diameter of 1.1 μm, and formed secondary aggregates and had an average particle diameter of 4.7 μm. This light calcium carbonate was designated as secondary aggregate F.
比較例７
実施例１の原紙Ａに替えて原紙Ｃを用い、塗料固形分濃度を２６％とし、乾燥後の塗工量が片面あたり３．３ｇ／ｍ２となるように塗布、乾燥した以外は実施例１と同様にして、実量４３．６ｇ／ｍ２のコールドオフセット印刷用新聞用紙を得た。
Comparative Example 7
Example except that base paper C was used instead of base paper A of Example 1, the solid content concentration of the paint was 26%, and the coating amount after drying was 3.3 g / m 2 per side. In the same manner as in No. 1, news paper for cold offset printing having an actual amount of 43.6 g / m 2 was obtained.
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| JP2010013785A (en) * | 2008-07-07 | 2010-01-21 | Marusumi Paper Co Ltd | Coated newsprint for offset printing |
| JP5466912B2 (en) * | 2009-10-07 | 2014-04-09 | 大王製紙株式会社 | Newspaper roll |
| CN102877365B (en) * | 2012-10-22 | 2015-04-08 | 中冶纸业银河有限公司 | Manufacturing method of high-bulk coating printing paper |
| JP6520702B2 (en) * | 2015-12-25 | 2019-05-29 | 王子ホールディングス株式会社 | Offset printing newsprint and method of manufacturing offset printing newsprint |
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| WO2004108597A1 (en) * | 2003-06-05 | 2004-12-16 | Okutama Kogyo Co., Ltd. | Light calcium carbonate, method for production thereof and loading material for loading into paper |
| JP2006076828A (en) * | 2004-09-09 | 2006-03-23 | Kyushu Institute Of Technology | Composite of calcium carbonate of vaterite crystal system and starch, recording medium, printed article, inkjet recording method and method for producing recording medium |
| JP2006169706A (en) * | 2004-12-20 | 2006-06-29 | Oji Paper Co Ltd | Paper used for newspaper for offset printing |
| JP2006327914A (en) * | 2005-05-30 | 2006-12-07 | Nippon Paper Industries Co Ltd | Manufacturing method of calcium carbonate and coated paper using the same |
| JP2007186408A (en) * | 2005-12-15 | 2007-07-26 | Oji Paper Co Ltd | Calcium carbonate particle and their manufacturing method, and newsprint paper for cold offset printing |
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| WO2004108597A1 (en) * | 2003-06-05 | 2004-12-16 | Okutama Kogyo Co., Ltd. | Light calcium carbonate, method for production thereof and loading material for loading into paper |
| JP2006076828A (en) * | 2004-09-09 | 2006-03-23 | Kyushu Institute Of Technology | Composite of calcium carbonate of vaterite crystal system and starch, recording medium, printed article, inkjet recording method and method for producing recording medium |
| JP2006169706A (en) * | 2004-12-20 | 2006-06-29 | Oji Paper Co Ltd | Paper used for newspaper for offset printing |
| JP2006327914A (en) * | 2005-05-30 | 2006-12-07 | Nippon Paper Industries Co Ltd | Manufacturing method of calcium carbonate and coated paper using the same |
| JP2007186408A (en) * | 2005-12-15 | 2007-07-26 | Oji Paper Co Ltd | Calcium carbonate particle and their manufacturing method, and newsprint paper for cold offset printing |
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