JP3907692B1 - Recycled particle paper - Google Patents
Recycled particle paper Download PDFInfo
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- JP3907692B1 JP3907692B1 JP2006240849A JP2006240849A JP3907692B1 JP 3907692 B1 JP3907692 B1 JP 3907692B1 JP 2006240849 A JP2006240849 A JP 2006240849A JP 2006240849 A JP2006240849 A JP 2006240849A JP 3907692 B1 JP3907692 B1 JP 3907692B1
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- paper
- pulp
- silica
- jis
- particle aggregate
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- 239000002245 particle Substances 0.000 title claims abstract description 139
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 105
- 239000000945 filler Substances 0.000 claims abstract description 60
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 239000010893 paper waste Substances 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- 229920001131 Pulp (paper) Polymers 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 24
- 241000628997 Flos Species 0.000 claims abstract description 23
- 238000010304 firing Methods 0.000 claims abstract description 17
- 230000018044 dehydration Effects 0.000 claims abstract description 10
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 59
- 230000008569 process Effects 0.000 claims description 34
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 24
- 229910052791 calcium Inorganic materials 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 229910052782 aluminium Inorganic materials 0.000 claims description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 4
- 230000004931 aggregating effect Effects 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 23
- 239000002761 deinking Substances 0.000 abstract description 16
- 238000010298 pulverizing process Methods 0.000 abstract description 15
- 239000000049 pigment Substances 0.000 abstract description 11
- 239000000123 paper Substances 0.000 description 192
- 238000007639 printing Methods 0.000 description 80
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 48
- 238000004519 manufacturing process Methods 0.000 description 36
- 239000010802 sludge Substances 0.000 description 32
- 229910000019 calcium carbonate Inorganic materials 0.000 description 22
- 238000012360 testing method Methods 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 20
- 238000010521 absorption reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000000428 dust Substances 0.000 description 13
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 238000010998 test method Methods 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 239000010419 fine particle Substances 0.000 description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 9
- 239000012756 surface treatment agent Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000013585 weight reducing agent Substances 0.000 description 9
- 241000519995 Stachys sylvatica Species 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000004115 Sodium Silicate Substances 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052911 sodium silicate Inorganic materials 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 239000004927 clay Substances 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 229910021532 Calcite Inorganic materials 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- -1 silicic acid compound Chemical class 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 3
- 239000004368 Modified starch Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 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 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000011436 cob Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229940097275 indigo Drugs 0.000 description 3
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000002655 kraft paper Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 235000019426 modified starch Nutrition 0.000 description 3
- 238000007645 offset printing Methods 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000003809 water extraction Methods 0.000 description 3
- 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 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 230000002250 progressing effect Effects 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 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 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001248531 Euchloe <genus> Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
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- 239000002283 diesel fuel Substances 0.000 description 1
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- 230000001788 irregular Effects 0.000 description 1
- 238000007644 letterpress printing Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
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- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
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Landscapes
- Paper (AREA)
Abstract
【課題】古紙の主要構成要素であるパルプ繊維と填料・顔料を共に回収して使用する、資源循環型の再生粒子内添新聞用紙の提供。
【解決手段】填料が古紙の処理工程から排出される脱墨フロスを主原料とし、前記主原料を脱水工程、乾燥工程、焼成工程及び粉砕工程を経ることにより得られた再生粒子凝集体の表面がシリカで被覆されたシリカ被覆再生粒子凝集体が前記填料として内添され、前記パルプが、古紙パルプ50〜100質量%からなり、JIS P 8124に準拠した坪量が37〜48g/m2であり、紙中にJIS P 8251に準拠して測定した紙灰分が4〜15質量%含有され、 JIS P 8143に準拠して測定したクラークこわさが30〜55cm3/100である再生粒子内添新聞用紙。
【選択図】なし[PROBLEMS] To provide a resource circulation type recycled particle-added newsprint paper that collects and uses pulp fibers and fillers and pigments, which are main components of waste paper.
A surface of a regenerated particle aggregate obtained by using a deinking floss discharged from a waste paper processing step as a main raw material and subjecting the main raw material to a dehydration step, a drying step, a firing step, and a pulverization step. A silica-coated regenerated particle aggregate coated with silica is internally added as the filler, and the pulp comprises 50 to 100% by weight of waste paper pulp, and the basis weight according to JIS P 8124 is 37 to 48 g / m 2 . There, the paper ash content, as measured in accordance with JIS P 8251 in the paper is contained 4 to 15 wt%, reproducing the particles internally added paper Clark stiffness was measured according to JIS P 8143 is 30~55cm 3/100 Paper.
[Selection figure] None
Description
本発明は、新聞用紙に関するものである。さらに詳しくは、古紙から、新聞用紙の主要構成要素である原料パルプ、填料を回収して再生、再利用する資源循環型の再生粒子内添新聞用紙に関するものである。 The present invention relates to newsprint. More specifically, the present invention relates to a newsprint paper with recycled particles that recovers and recycles raw pulp and filler, which are the main components of newsprint, from used paper.
近年の環境問題から、環境保護、資源保護、ゴミ減少を目的として、最近ではオフィスから発生する廃事務用紙をビル全体で回収しようとする動きも見られ、古紙パルプを使用した再生紙の利用が益々増加すると共に、紙への古紙配合率も増加している。
また、省資源、輸送費の削減、原材料費の削減の観点から、各用紙の軽量化が年々進んでいる。さらに、製紙工場では古紙パルプを使用した再生紙の生産比率の増加と、紙への古紙配合率の増加が進むとともに、紙の生産効率向上のため、紙製造工程の生産スピードが益々高速化している。このような状況下、新聞用紙においても需要は軽量化と古紙の高配合化の方向に進んでいる。例えば、新聞配達時の重量負担を増やすことなく1部当りのページ数を増やすために新聞用紙の軽量化が進み、環境問題に対応するために古紙配合率の増加が進み、また、オフセット輪転印刷機の高速化、紙面のカラー化などが進んでいる。
そのため、新聞用紙には高速オフセット輪転印刷に耐え得る引張り強さなどの強度に対する要求だけでなく、紙面のカラー化や高精細な見栄えのよい印刷仕上り、見開き全面広告などに対応できる、新聞用紙の表面強度やインク吸収性、印刷輪郭や画像が反対面から透けて見える現象、いわゆる裏抜けや隠蔽性の要求レベルが高くなっており、更なる新聞用紙の軽量化、古紙の高配化の妨げとなっている。
Due to environmental problems in recent years, there has been a movement to collect waste office paper generated from offices throughout the building for the purpose of environmental protection, resource protection, and garbage reduction, and the use of recycled paper using waste paper pulp has been seen. Along with the increase, the ratio of used paper to paper is also increasing.
In addition, from the viewpoints of resource saving, transportation cost reduction, and raw material cost reduction, the weight of each paper is increasing year by year. Furthermore, at the paper mill, the production ratio of recycled paper using recycled paper pulp and the ratio of used paper to paper have increased, and the production speed of the paper manufacturing process has increased further in order to improve paper production efficiency. Yes. Under such circumstances, the demand for newsprint is also progressing in the direction of weight reduction and higher blending of used paper. For example, the weight of newspapers has been reduced to increase the number of pages per copy without increasing the weight burden at the time of newspaper delivery, the ratio of used paper has been increased to cope with environmental problems, and offset rotary printing The speed of the machine and the colorization of paper are progressing.
For this reason, newsprint paper can be used not only for strength, such as tensile strength that can withstand high-speed offset rotary printing, but also for colorization of the paper surface, high-definition, good-quality print finish, double-page spread advertisement, etc. The required level of surface strength, ink absorptivity, printing contours and images can be seen through from the opposite side, so-called back-through and concealment, has become higher, hindering further weight reduction of newspapers and higher distribution of used paper It has become.
従来、新聞用紙の不透明度を向上させる為には、原料パルプに機械パルプが多用されてきたが、古紙パルプの高配合が望まれる近年にあっては、新聞用紙を前記機械パルプを主原料に構成することも困難である。また、再生紙の普及に伴って、近年は再生紙である古紙をさらに再利用することになり、すなわちパルプ繊維を繰り返し再利用している状況にあることから、得られる古紙パルプは微細繊維が多く、強度も低下している。この古紙を高配合することは、新聞用紙の強度、不透明度の低下を招き、印刷時の裏抜けや隠蔽性が問題となっている。
前記のごとき新聞用紙の隠蔽性を高め、裏抜けを少なくするためには、ホワイトカーボンや炭酸カルシウムなどの填料を使用して、紙の不透明度、吸油度を向上させることが一般的である。填料の添加方法には、バインダ等と共に填料を表面塗工する外添と、填料をパルプ原料と混合して抄紙する内添とがある。
填料の中でも微細な填料粒子は光の散乱係数と吸収係数とが良好であり不透明度向上効果が高いが、内添填料として利用する場合は歩留が低く、主に外添により塗工される。
しかし、填料を外添塗工する場合は一定以上の塗工層を形成する必要があるため、新聞用紙に要求される軽量化を達成することができない。また、新聞用紙のオフセット印刷機は高速で乾燥設備を持たないため、填料を外添塗工する場合は、インキの乾燥性、表面強度、版汚れなどにおいて、新聞用紙に要求される品質を満足することができないという問題が生じる。
Conventionally, in order to improve the opacity of newsprint, mechanical pulp has been frequently used as raw material pulp. However, in recent years when high blending of used paper pulp is desired, newsprint is used as the main raw material. It is also difficult to configure. Also, with the widespread use of recycled paper, in recent years, recycled paper that is recycled paper has been further reused, that is, because pulp fibers are repeatedly reused, the resulting recycled paper pulp has fine fibers. Many have reduced strength. High blending of this waste paper causes a decrease in the strength and opacity of the newsprint, and there is a problem of show-through and concealment during printing.
In order to improve the concealing property of the newsprint as described above and reduce the back-through, it is common to improve the opacity and oil absorption of the paper by using a filler such as white carbon or calcium carbonate. Methods for adding the filler include an external addition in which a filler is surface-coated with a binder and the like, and an internal addition in which the filler is mixed with a pulp raw material to make paper.
Among the fillers, fine filler particles have good light scattering coefficient and absorption coefficient and high opacity improvement effect, but when used as an internal filler, the yield is low, and it is mainly applied by external addition. .
However, when the filler is externally applied, it is necessary to form a coating layer of a certain level or more, so that the weight reduction required for newsprint cannot be achieved. In addition, newsprint offset printing presses do not have drying equipment at high speed, so when externally applying fillers, the quality required for newsprint is satisfied in terms of ink drying, surface strength, plate stains, etc. The problem of not being able to do arises.
そこで、例えば、パルプと炭酸カルシウムとを含む紙料にホワイトカーボンを添加して抄造し、水和ケイ酸の吸油量、細孔容積、平均粒子径等を特定範囲内に設定した填料内添紙(特許文献1参照)や、ホワイトカーボン及び炭酸カルシウムを主体とし、灰分中のこれらの割合を特定範囲内に設定した新聞用紙(特許文献2参照)が提案されている。
前記填料内添紙や新聞用紙は、特にホワイトカーボンが填料として多用されていることから、確かに従来と比較して不透明度及び吸油性が向上している。
しかしながら、ホワイトカーボンはそもそも高価であり、コスト上昇を招いてしまう。しかもホワイトカーボンを多用した場合には、その粒子特性から紙粉発生や印刷設備汚れの大きな原因となり易いといった問題があるため、その内添量については紙質強度の維持も鑑み、添加量を増やすことにも限界が生じている。
炭酸カルシウムを填料として使用した場合には、カオリンやタルクなどの酸性新聞用填料に比べてその硬度が高いために、製紙用ワイヤーの摩耗が速いことが一般的に言われており、同様に印刷時のオフセット輪転印刷用の版摩耗が懸念されている。したがって、軽量でオフセット輪転印刷に適した新聞用紙は開発されていなかった。
この炭酸カルシウムを新聞用紙に利用しようとした特許文献3には、機械パルプ及び又は脱墨古紙パルプと炭酸カルシウムを含み、クリヤーサイズ剤が塗布された中性新聞用紙が記載されている。しかし、炭酸カルシウムを使用した中性領域での抄紙は、抄紙設備、特にワイヤーが摩耗劣化し易いといった問題と、古紙パルプや木材繊維由来の樹脂成分の溶出によるピッチトラブルや抄紙設備の汚損原因が問題として発現するため、中性またはアルカリ性で抄造するに際し、硫酸アルミニウムを添加して上記パルプ中に含有されている樹脂成分を繊維に定着させた後に、填料として炭酸カルシウムを特定し、抄紙工程の可及的後段に於いて添加し、硫酸アルミニウムのカチオン性が低下しない間に樹脂成分を紙に抄き込むと云う煩雑な操業方法を取らざるを得ない旨が記載されている。
Therefore, for example, a paper containing pulp and calcium carbonate is made by adding white carbon to make a paper, and the filler-added paper in which the oil absorption amount, pore volume, average particle diameter, etc. of hydrated silicic acid are set within specific ranges. (See Patent Document 1) and newspaper paper (see Patent Document 2) in which white carbon and calcium carbonate are mainly used and the ratio of ash in the ash content is set within a specific range.
In the filler-added paper and newsprint, white carbon is often used as a filler, and therefore, the opacity and oil absorption are certainly improved as compared with the conventional one.
However, white carbon is expensive in the first place and causes an increase in cost. In addition, when white carbon is used frequently, there is a problem that due to its particle characteristics, it tends to be a major cause of paper dust generation and printing equipment contamination, so the amount of internal addition should be increased in consideration of maintaining paper quality. There are also limits.
When calcium carbonate is used as a filler, it is generally said that the wear of papermaking wire is fast because of its higher hardness than acidic newspaper fillers such as kaolin and talc. There is concern about plate wear for offset rotary printing. Therefore, a newspaper that is lightweight and suitable for offset rotary printing has not been developed.
Patent Document 3 which attempts to use this calcium carbonate for newsprint describes neutral newsprint that contains mechanical pulp and / or deinked waste paper pulp and calcium carbonate and is coated with a clear sizing agent. However, the papermaking in the neutral region using calcium carbonate has the problems that the papermaking equipment, especially the wire is likely to wear and deteriorate, and the pitch trouble caused by the elution of resin components derived from waste paper pulp and wood fibers and the cause of the papermaking equipment fouling. In order to express as a problem, when making paper in neutral or alkaline, after adding aluminum sulfate and fixing the resin component contained in the pulp to the fiber, specify calcium carbonate as a filler, and in the paper making process It is described that it is necessary to take a complicated operation method in which the resin component is incorporated into paper while the cationic property of aluminum sulfate is not lowered as much as possible after the addition.
一方、製紙工場においては、近年の微細繊維の多い古紙パルプの高配合化と用紙の軽量化、抄紙機の高速化に伴うワイヤーパートでの急激なそして強制的な脱水により、微細繊維の歩留まりや灰分の歩留まりが極めて低い状況下になっており、各製紙工程から排出される排水・脱水スラッジ等の製紙スラッジが増加している。
すなわち、古紙パルプを使用した再生紙の生産比率の増加と古紙パルプの高配合化により、多くの古紙パルプが必要となり、古紙の使用量が増大している。この新聞古紙や雑誌古紙をはじめとした古紙には、非塗工紙に使用された填料や塗工紙に使用された填料・顔料に由来する無機物が多く含まれているため、古紙処理工程からは、パルプ繊維と分離され、填料・顔料の無機物が多量に含まれた脱墨フロスの発生量が増大している。
これら填料・顔料の無機物を多量に含む古紙処理工程から排出される脱墨フロス、各製紙工程から排出される排水・脱水スラッジ等の製紙スラッジは、従来は燃焼し減容化を図った上で、多くは埋立処分されてきた。
しかしながら、前記背景技術により、環境保護、資源保護、ゴミ減少に貢献できる再生紙の品質を維持、向上しながら継続的に製造するためには、製紙工場にとって、この製紙スラッジの再資源化、有効利用が重大な課題となっている。
前記製紙スラッジは、多量の無機物を含有するため、燃焼しても多量の燃焼灰(無機物)が残り、減容化の効果は低い。そこで、この燃焼灰をセメント原料や土壌改良材として活用する等の努力もなされているが、これらの方法において燃焼灰は助剤として使用されており、多量に使用されるわけではないため、結局、大部分の燃焼灰は埋立処分されることになる。
On the other hand, in paper mills, the yield of fine fibers has increased due to the rapid and forced dehydration at the wire part due to the high blending of waste paper pulp with a lot of fine fibers, the weight reduction of paper, and the speedup of paper machines in recent years. The yield of ash is extremely low, and paper sludge such as drainage and dewatered sludge discharged from each paper making process is increasing.
That is, due to the increase in the production ratio of recycled paper using waste paper pulp and the high blending of waste paper pulp, a lot of waste paper pulp is required, and the amount of waste paper used is increasing. Waste paper such as newspaper and magazine waste paper contains a lot of inorganic substances derived from fillers used in uncoated paper and fillers and pigments used in coated paper. The amount of deinking floss that is separated from pulp fibers and contains a large amount of inorganic fillers and pigments is increasing.
Paper sludges such as deinking floss discharged from waste paper processing processes that contain a large amount of inorganic fillers and pigments, and wastewater and dewatered sludge discharged from each paper manufacturing process have been conventionally burned and reduced in volume. Many have been landfilled.
However, in order to continuously manufacture while maintaining and improving the quality of recycled paper that can contribute to environmental protection, resource protection, and dust reduction by the above-mentioned background technology, the paper mill can recycle and effectively use this paper sludge. Usage is a major issue.
Since the papermaking sludge contains a large amount of inorganic matter, a large amount of combustion ash (inorganic matter) remains even after combustion, and the effect of volume reduction is low. Therefore, efforts such as utilizing this combustion ash as a raw material for cement and soil improvement have been made, but in these methods, combustion ash is used as an auxiliary agent and is not used in large quantities. Most of the combustion ash will be landfilled.
燃焼灰を有効に活用する方法として、紙の内添填料として使用することも考えられるが、燃焼灰は白色度が低いため、そのままの状態では紙の内添填料として使用するのに適していない。
そこで、燃焼灰(焼却灰)を再燃焼し、スラリー化及び湿式分散を行って白色度を向上させ、白色顔料とする方法が提案されている(特許文献4参照)。
しかしながら、この焼却灰を再燃焼する方法の場合、未燃焼カーボンを完全に燃焼させるためには、再燃焼温度を500〜900℃に設定する必要があり、しかも焼却灰の白色度は50%程度にまでしか向上せず、紙の填料としての使用に適したものではないことが知見された。また、再燃焼温度を900℃超に設定すると、燃焼灰(無機物)が焼結、溶融し、極めて硬くなることも知見された。さらに、再燃焼灰を紙の填料として使用した場合、この再燃焼灰は非常に硬い性質を有することから、抄紙ワイヤーの摩耗進行が早く、寿命が非常に短くなるため、実操業に使用することができなかった。
このような抄紙ワイヤーの摩耗については、再燃焼灰を粉砕し、その粒子径を小さくして摩耗の低減、平滑性の向上を図ることも考えられるが、紙の内添填料として使用する場合には、抄紙時における歩留まりが低くなり、また、再燃焼灰自体が極めて硬いことから、粉砕のためのエネルギーコストが極めて高くなるといった問題がある。
また、製紙スラッジの利用方法として、紙繊維からの有機物を含む含水の製紙工場廃棄スラッジを、酸素含有ガスを注入した反応器内に供給し、250〜300℃、3000psig(プサイグ)程度の加温加圧下で0.25〜5時間酸化して、該廃棄スラッジ中の無機物を製紙用の顔料(無機填料)として再生する方法が提案されている(特許文献5参照)。
しかしながら、前記方法は、製紙スラッジの湿式空気酸化処理によるものであることから、有機物除去が充分ではなく、また得られた顔料の白色度が低く、粒子径も不揃いで、製紙用の填料として使用するには不適切であり、しかも反応操作が複雑でコストが高いとう問題がある。
これらのほかにも、製紙スラッジをいぶし焼きしてPS炭とした後、さらにこれをキルンで焼却して製紙用原料となる白土を生成させる方法が提案されている(特許文献6参照)。
しかしながら、この方法では製紙スラッジをいぶし焼きするため、製紙スラッジからエネルギーを有効に取り出すことができないばかりか、逆に投入エネルギーが必要になるという大きなデメリットがある。さらに、生成した白土も粒子径が不揃いで大きく、製紙用填料としては使用することができないという問題がある。
さらに、排水に凝集剤を添加して造粒し、得られる成形汚泥をロータリーキルン内で連続して乾燥、炭化、焼成して製紙用填料を製造する方法も提案されている(特許文献7参照)。この方法において、焼成に先立って造粒、成形するのは、焼成を均一に行うためである。
ところが、例えば固形分濃度が40〜60%(換言すれば水分率が60〜40%)の成形汚泥をロータリーキルン内で連続して乾燥、炭化、焼成した場合、乾燥状態、炭化状態の如何にかかわらず、キルンの回転によって汚泥粒子の処理は強制的に進行する。したがって、乾燥が不充分であると粒子内部に未燃分が多く残留し、その結果、焼成が不完全となって白色度の低下が生じる。逆に過乾燥になると、焼成は完全であるが過焼成を招き、得られる再生粒子の硬度が高くなる。この再生粒子を使用すると、抄紙機でのワイヤー摩耗や紙を断裁する場合のカッター刃摩耗が生じ易くなるという問題を惹き起こす。
前記特許文献4〜7に記載の、製紙スラッジを原料として紙の填料を製造する従来の方法の最も大きな問題点は、原料とする製紙スラッジには、抄紙工程でワイヤーを通過して流出したもの、パルプ化工程での洗浄過程で発生した固形分を含む排水から回収したもの、排水処理工程において、沈殿あるいは浮上などを利用した固形分分離装置によりその固形分を分離、回収したもの、古紙処理工程での混入異物除去したもの等の各種スラッジが混在している点である。
前記各種スラッジのうち、例えば抄紙工程でワイヤーを通過して流出したスラッジには、紙力剤等が混入しており、また抄紙工程における抄造物の変更によってスラッジの品質に変動が生じる。
また、排水から回収したスラッジには、凝集剤が混入しており、さらに工場全体の抄造物、生産量の変動や生産設備の工程内洗浄などにより、スラッジの品質に大きな変動が生じる。
パルプ化工程での洗浄過程から生じるスラッジには、紙用填料、顔料に適さない物質が混入していたり、チップ水分やパルプ製造条件の変動により品質に変動が生じたりする。
したがって、種々の製紙スラッジを無選別に用いて製紙用の填料、顔料を得ようとすると、その品質は低いものとなり、しかも品質の変動が極めて大きく、不安定なものとなる。
It is conceivable to use the combustion ash as an internal filler for paper, but the combustion ash is not suitable for use as an internal paper filler because it has low whiteness. .
Therefore, a method has been proposed in which combustion ash (incineration ash) is reburned, and the whiteness is improved by slurrying and wet dispersion (see Patent Document 4).
However, in the case of the method of reburning the incinerated ash, in order to completely burn the unburned carbon, it is necessary to set the reburning temperature to 500 to 900 ° C., and the whiteness of the incinerated ash is about 50%. It has been found that it is not suitable for use as a paper filler. It has also been found that when the re-combustion temperature is set to over 900 ° C., the combustion ash (inorganic material) is sintered and melted and becomes extremely hard. In addition, when reburned ash is used as a filler for paper, the reburned ash has very hard properties, so the papermaking wire wears quickly and its life is very short. I could not.
For such papermaking wire wear, it is conceivable that the reburned ash is crushed and its particle size is reduced to reduce wear and improve smoothness, but when used as an internal filler for paper. However, there is a problem that the yield during paper making is low and the reburned ash itself is extremely hard, so that the energy cost for pulverization becomes extremely high.
Also, as a method of using paper sludge, water-containing paper mill waste sludge containing organic matter from paper fibers is supplied into a reactor into which oxygen-containing gas has been injected, and is heated to about 250 to 300 ° C. and 3000 psig (psig). There has been proposed a method of regenerating the inorganic substance in the waste sludge as a papermaking pigment (inorganic filler) by oxidation under pressure for 0.25 to 5 hours (see Patent Document 5).
However, since the above method is based on wet air oxidation treatment of papermaking sludge, organic matter removal is not sufficient, and the obtained pigment has low whiteness and irregular particle sizes, and is used as a filler for papermaking. However, there is a problem that the reaction operation is complicated and expensive.
In addition to these, a method has been proposed in which papermaking sludge is baked into PS charcoal and then incinerated with a kiln to produce white clay as a papermaking raw material (see Patent Document 6).
However, in this method, since the papermaking sludge is fried, not only energy cannot be effectively extracted from the papermaking sludge, but also there is a great demerit that input energy is required. Furthermore, the generated white clay also has a problem that the particle size is uneven and large, and cannot be used as a papermaking filler.
Furthermore, a method for producing a papermaking filler by adding a flocculant to the waste water and granulating the resulting sludge and drying, carbonizing, and firing continuously in a rotary kiln has also been proposed (see Patent Document 7). . In this method, the granulation and shaping are performed prior to firing in order to perform firing uniformly.
However, for example, when formed sludge having a solid content concentration of 40 to 60% (in other words, moisture content of 60 to 40%) is continuously dried, carbonized, and calcined in a rotary kiln, it depends on the dry state and carbonized state. First, the treatment of sludge particles is forced to proceed by the rotation of the kiln. Therefore, if the drying is insufficient, a large amount of unburned matter remains inside the particles, and as a result, the firing becomes incomplete and the whiteness is lowered. On the other hand, when overdried, the firing is complete but overfired and the hardness of the obtained regenerated particles is increased. Use of the recycled particles causes a problem that wire wear in a paper machine and cutter blade wear when cutting paper are likely to occur.
The biggest problem of the conventional methods of manufacturing paper fillers using papermaking sludge as a raw material described in Patent Documents 4 to 7 is that the papermaking sludge used as a raw material flows out through a wire in the papermaking process. , Collected from wastewater containing solids generated in the washing process in the pulping process, separated and recovered by solids separation equipment using precipitation or floating in the wastewater treatment process, waste paper treatment Various sludges such as those from which foreign substances are removed in the process are mixed.
Among the various sludges, for example, a paper strength agent or the like is mixed in sludge that has flowed out through the wire in the papermaking process, and the quality of the sludge varies due to changes in the papermaking process.
Moreover, flocculant is mixed in the sludge collected from the waste water, and the quality of the sludge varies greatly due to papermaking, production volume fluctuations, and in-process washing of the production equipment.
The sludge generated from the washing process in the pulping process contains substances that are not suitable for paper fillers and pigments, and the quality may vary due to fluctuations in chip moisture and pulp production conditions.
Therefore, when various papermaking sludges are used without selection, the quality and quality of the papermaking fillers and pigments are low, and the quality is extremely variable and unstable.
このように、従来の製紙スラッジを利用した方法は、いずれも単なる製紙用粒子の回収に終始し、これらの方法で得られる製紙スラッジからの再生粒子は、製紙用の顔料、填料としては品質が適さず、品質安定性に欠けるものであった。
したがって、新聞用紙の主要構成要素である原料パルプは、古紙パルプの多用が進むものの、填料としては従来のホワイトカーボンや炭酸カルシウムを多用せざるを得ず、例えば製紙工程での不要物を有効利用するなどして、コストダウンと抄紙設備の摩耗問題の改善とを図りながら、しかも不透明度及び紙力を向上させ得る技術の開発が待ち望まれている。
Therefore, although raw paper pulp, which is a major component of newsprint, is increasingly used as waste paper pulp, conventional white carbon and calcium carbonate must be used as a filler. Therefore, development of a technique capable of improving the opacity and paper strength while reducing costs and improving the wear problem of the papermaking equipment is desired.
本発明は前記背景技術に鑑みてなされたものであり、古紙から、古紙(紙)の主要構成要素であるパルプ繊維、填料・顔料を共に回収して使用する、資源循環型の再生粒子内添新聞用紙を提供することを課題とする。
より詳しくは、古紙(紙)の主要構成要素であるパルプ繊維と填料・顔料を共に回収し、資源を循環使用して低コストで製造され、さらに、中性又はアルカリ領域で抄紙することで、優れた紙力が維持されて断紙が少ないだけでなく、樹脂分や紙粉によるブランケット汚れ、印刷白抜け等も少なく、しかもインク吸収性にも優れ、不透明度に優れて裏抜けが少なく、高速オフセット輪転印刷における印刷に好適に使用し得る再生粒子内添新聞用紙を提供することを課題とする。
The present invention has been made in view of the above-mentioned background art, and from recycled paper, pulp fibers, fillers and pigments, which are main components of waste paper (paper), are recovered and used together. The issue is to provide newspaper.
More specifically, the pulp fibers and fillers / pigments that are the main components of waste paper (paper) are collected together, recycled at low cost by using resources, and papermaking in the neutral or alkaline region. Not only is excellent paper strength maintained and there are few paper breaks, but there are also little blanket stains due to resin and paper dust, printing white spots, etc., and excellent ink absorption, excellent opacity and little show through. It is an object to provide a recycled particle-added newsprint that can be suitably used for printing in high-speed offset rotary printing.
この課題を解決した本発明は、次のとおりである。
〔請求項1記載の発明〕
パルプに填料を内添した新聞用紙であって、
前記填料が古紙の処理工程から排出される脱墨フロスを主原料とし、
前記主原料を脱水工程、乾燥工程、焼成工程及び粉砕工程を経て、前記焼成工程において凝集させて得られた再生粒子凝集体の表面がシリカで被覆され、下記組成のシリカ被覆再生粒子凝集体が前記填料として内添され、
前記パルプが、古紙パルプ50〜100質量%からなり、
JIS P 8124に準拠した坪量が37〜48g/m2であり、
紙中にJIS P 8251に準拠して測定した紙灰分が4〜15質量%含有され、
JIS P 8143に準拠して測定したクラークこわさが30〜55cm3/100である、
ことを特徴とする再生粒子内添新聞用紙。
(組成)
前記シリカ被覆再生粒子凝集体は、シリカ被覆再生粒子凝集体の構成成分がカルシウム、ケイ素及びアルミニウムを、酸化物換算で30〜62:29〜55:9〜35の質量割合で含有したシリカ被覆再生粒子凝集体。
The present invention that has solved this problem is as follows.
[Invention of Claim 1]
Newspaper with internal filler in pulp,
The main material is deinked floss discharged from the waste paper processing process,
The surface of the regenerated particle aggregate obtained by aggregating the main raw material through the dehydration step, drying step, firing step and grinding step in the firing step is coated with silica, and the silica-coated regenerated particle aggregate having the following composition Is internally added as the filler,
The pulp comprises 50-100% by weight of waste paper pulp,
The basis weight according to JIS P 8124 is 37 to 48 g / m 2 ,
The paper ash content measured according to JIS P 8251 is contained in the paper in an amount of 4 to 15% by mass,
Clark stiffness was measured according to JIS P 8143 is 30~55cm 3/100,
Recycled particle-attached newsprint.
(composition)
The silica-coated regenerated particle aggregate is a silica-coated regenerated particle whose constituent components of the silica-coated regenerated particle aggregate contain calcium, silicon, and aluminum in a mass ratio of 30 to 62:29 to 55: 9 to 35 in terms of oxides. Particle aggregate.
〔請求項2記載の発明〕
JIS P 8138に準拠して測定した白紙不透明度が、91〜95%である、請求項1記載の再生粒子内添新聞用紙。
[Invention of Claim 2]
Renewed particle-added newsprint according to claim 1, wherein the blank paper opacity measured in accordance with JIS P 8138 is 91 to 95%.
〔請求項3記載の発明〕
JIS P 8140に基づく10秒コブサイズ度が30〜300g/m2である、請求項1または請求項2記載の再生粒子内添新聞用紙。
[Invention of Claim 3]
Renewable particle-added newsprint according to claim 1 or 2 , wherein the 10-second bump size based on JIS P 8140 is 30 to 300 g / m2.
本発明の再生粒子内添新聞用紙は、産業廃棄物として焼却や埋立処分されていた脱墨フロスを製紙用填料資源として活用すると共に、古紙からなる古紙パルプを主たる原料パルプとして使用することで、資源を循環使用して低コストで製造され、抄造時の灰分歩留まりが高く、ワイヤー摩耗等の抄紙設備の摩耗劣化や樹脂成分の溶出による印刷設備汚れを殆ど起こすことなく、優れた紙力が維持されて断紙が少ないだけでなく、紙粉によるブランケット汚れ、印刷白抜け等も少なく、しかもインク吸収性にも優れ、不透明度に優れて裏抜けが少ない再生粒子内添新聞用紙として、高速オフセット輪転印刷、オフセット輪転カラー印刷・高精細印刷に好適に使用し得るものとなる。 The recycled particle-added newsprint of the present invention utilizes deinking floss that has been incinerated or landfilled as industrial waste as a filler material for papermaking, and by using wastepaper pulp made of wastepaper as the main raw material pulp, It is manufactured at low cost by recycling resources, has a high ash yield at the time of paper making, and maintains excellent paper strength with little deterioration of wear of the paper making equipment such as wire wear and contamination of the printing equipment due to elution of resin components. In addition to low paper breakage, there are few blanket stains due to paper dust, printed white spots, etc., and excellent ink absorption, high opacity and low back-through. It can be suitably used for rotary printing, offset rotary color printing and high-definition printing.
次に、本発明の実施の形態を説明する。
本形態の再生粒子内添新聞用紙は、パルプに填料を内添した新聞用紙であって、前記填料が古紙の処理工程から排出される脱墨フロスを主原料とし、前記主原料を脱水工程、乾燥工程、焼成工程及び粉砕工程を経ることにより得られた(粉砕工程後に粒子を凝集させる工程を付加することなく得られた)、再生粒子凝集体の表面がシリカで被覆され、下記組成に調整したシリカ被覆再生粒子凝集体が前記填料として内添され、
前記パルプが、古紙パルプ50〜100質量%からなり、
JIS P 8124に準拠した坪量が37〜48g/m2であり、
紙中にJIS P 8251に準拠して測定した紙灰分が4〜15質量%含有され、
JIS P 8143に準拠して測定したクラークこわさが30〜55cm3/100である、
ことを特徴とするものである。
(組成)
前記再生粒子凝集体は、再生粒子凝集体の構成成分がカルシウム、ケイ素及びアルミニウムを、酸化物換算で30〜62:29〜55:9〜35の質量割合で含有した再生粒子凝集体。
Next, an embodiment of the present invention will be described.
The recycled particle-added newsprint of this embodiment is newsprint with a filler added to pulp, the filler being a deinking floss discharged from a used paper processing step as a main raw material, and the main raw material being a dehydrating step, The surface of the regenerated particle aggregate obtained by passing through the drying step, firing step and pulverization step (obtained without adding the step of aggregating particles after the pulverization step) is coated with silica and adjusted to the following composition The silica-coated regenerated particle aggregate is internally added as the filler,
The pulp comprises 50-100% by weight of waste paper pulp,
The basis weight according to JIS P 8124 is 37 to 48 g / m 2 ,
The paper ash content measured according to JIS P 8251 is contained in the paper in an amount of 4 to 15% by mass,
Clark stiffness was measured according to JIS P 8143 is 30~55cm 3/100,
It is characterized by this.
(composition)
The regenerated particle aggregate is a regenerated particle aggregate in which the components of the regenerated particle aggregate contain calcium, silicon, and aluminum in a mass ratio of 30 to 62:29 to 55: 9 to 35 in terms of oxides.
なお、紙の主要構成要素であるパルプ繊維、填料が、いずれも回収、再生、再利用されたものであることから、本発明によって提供することができる紙を、従来の新聞用紙に対し、完全再生新聞用紙と定義する。 Since pulp fibers and fillers, which are the main components of paper, are all collected, recycled and reused, the paper that can be provided by the present invention is completely different from conventional newsprint paper. Defined as recycled newspaper.
まず、本実施形態に用いられる原料パルプについて説明する。係る原料パルプは、例えば新聞古紙、雑誌古紙、模造・色上古紙、OA古紙等の古紙を原料とする古紙パルプ50〜100質量%から構成される。このように本実施形態においては古紙パルプが50質量%以上も用いられるので、資源の有効利用に大きく寄与し、低コスト化を図ることができる。特に新聞用紙は古紙としての回収率が高く、再資源化の優等生といわれるものであり、その用途に本発明に基づく完全再生紙からなる新聞用紙を用いることで、新聞用紙の循環使用をより進めることが可能となる。
古紙パルプの種類には特に限定がなく、例えばディインキングパルプ(DIP)、ウェストパルプ(WP)などがあげられ、これらは単独で又は同時に用いることができる。
原料パルプとして、前記古紙パルプ以外にも通常の紙に用いられるパルプを適宜使用することができる。古紙パルプ以外のほかの原料パルプとしては、例えばストーングランドパルプ(SGP)、加圧ストーングランドパルプ(PGW)、リファイナーグランドパルプ(RGP)、ケミグランドパルプ(CGP)、サーモグランドパルプ(TGP)、砕木パルプ(GP)、サーモメカニカルパルプ(TMP)、ケミサーモメカニカルパルプ(CTMP)、リファイナーメカニカルパルプ(RMP)などの機械パルプ;針葉樹クラフトパルプ(NBKP)、広葉樹クラフトパルプ(LBKP)などの化学パルプや、これらを漂白したパルプなどがあげられ、これらの中から1種又は2種以上を選択して用いることができる。
原料パルプ中の古紙パルプの割合は、前記したように、50〜100質量%であるが、より省資源化及び低コスト化が実現される点から、さらには60〜100質量%、特に70〜100質量%とすることができる。
First, the raw material pulp used for this embodiment is demonstrated. Such raw material pulp is composed of 50 to 100% by weight of waste paper pulp made from waste paper such as newspaper waste paper, magazine waste paper, imitation / colored waste paper, and OA waste paper. Thus, in this embodiment, since used paper pulp is 50 mass% or more, it contributes greatly to the effective use of resources and can achieve cost reduction. In particular, newsprint paper has a high recovery rate as waste paper, and is said to be an excellent student of recycling. Newspaper paper made of completely recycled paper based on the present invention is used for its use, thereby further promoting the circulation of newsprint paper. It becomes possible.
There is no limitation in particular in the kind of used paper pulp, For example, a diinking pulp (DIP), a waist pulp (WP) etc. are mention | raise | lifted, These can be used individually or simultaneously.
As the raw material pulp, pulp used for ordinary paper can be used as appropriate in addition to the waste paper pulp. Examples of raw material pulp other than waste paper pulp include Stone Grand Pulp (SGP), Pressurized Stone Grand Pulp (PGW), Refiner Grand Pulp (RGP), Chemi Grand Pulp (CGP), Thermo Grand Pulp (TGP), and ground wood. Pulp (GP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), refiner mechanical pulp (RMP) and other mechanical pulp; softwood kraft pulp (NBKP), hardwood kraft pulp (LBKP) and other chemical pulp; The pulp etc. which bleached these are mention | raise | lifted and it can select and use 1 type (s) or 2 or more types from these.
As described above, the ratio of the waste paper pulp in the raw material pulp is 50 to 100% by mass. However, 60 to 100% by mass, particularly 70 to 100% by mass, is achieved from the point of realizing resource saving and cost reduction. It can be 100 mass%.
次に本実施形態に用いられる填料について説明する。係る填料としては、脱墨フロスを主原料とし、脱水工程、乾燥工程、焼成工程及び粉砕工程を経て得られた、カルシウム、ケイ素及びアルミニウムを特定量含有する再生粒子凝集体が少なくとも用いられる。
少なくとも前記再生粒子凝集体の表面をシリカで被覆し、上記組成に調整したシリカ被覆再生粒子凝集体が前記填料として用い、古紙パルプを50〜100質量%含んだ原料パルプに特定量内添することが本実施形態の大きな特徴の1つである。前記再生粒子凝集体は、脱墨フロスを焼成して得られる循環使用が可能なものであるので、廃棄物としての埋立等の処分が不要であり、環境負荷の低減と、省資源化に大きく貢献するものである。また、原料が古紙処理工程で生じる脱墨フロスであるので、安価であり、新たな無機粒子の使用量を抑えることができ、製造コストが充分に削減されるという利点がある。さらに係る再生粒子凝集体を用いることで、抄造時の灰分歩留まりが高く、例えば炭酸カルシウムと異なり、ワイヤー摩耗等の抄紙設備の摩耗劣化を来たすことが無く、更に樹脂成分が微細な状態下で再生粒子に吸着することで、樹脂分の凝集によるピッチトラブルを防ぎ印刷設備汚れを殆ど起こすことがなく、低コストで高い操業性で紙を製造することができ、しかも従来と同等以上の優れた不透明度や紙力が紙に付与され、裏抜け、断紙も少なくなる。
Next, the filler used in this embodiment will be described. As such a filler, at least a regenerated particle aggregate containing a specific amount of calcium, silicon and aluminum, which is obtained by using deinked floss as a main raw material and undergoing a dehydration step, a drying step, a firing step and a pulverization step, is used.
At least the surface of the regenerated particle aggregate is coated with silica, and the silica-coated regenerated particle aggregate adjusted to the above composition is used as the filler, and a specific amount is internally added to the raw material pulp containing 50 to 100% by weight of waste paper pulp. This is one of the major features of this embodiment. Since the recycled particle aggregate can be recycled by baking deinked froth, it does not require disposal such as landfill as waste, greatly reducing the environmental burden and saving resources. It contributes. Further, since the raw material is deinking floss generated in the waste paper processing step, there is an advantage that it is inexpensive, the amount of new inorganic particles used can be suppressed, and the manufacturing cost is sufficiently reduced. Furthermore, by using the recycled particle aggregate, the ash yield during paper making is high. Unlike calcium carbonate, for example, there is no wear deterioration of paper making equipment such as wire wear, and the resin component is regenerated in a fine state. By adsorbing to the particles, pitch troubles caused by resin agglomeration can be prevented, printing equipment can be hardly contaminated, and paper can be manufactured at low cost and high operability. Transparency and paper strength are imparted to the paper, and there are fewer breakthroughs and paper breaks.
本実施形態に用いられる再生粒子凝集体は、脱墨フロスを原料とし、脱水工程、乾燥工程、焼成工程及び粉砕工程を経て得られるものである。なおさらに、後述するように、脱墨フロスの凝集工程、造粒工程、各工程間に設けられる分級工程等を経てもよい。また再生粒子の製造設備には、各種センサーを設け、被処理物や設備の状態、処理速度のコントロール等を行うことが望ましい。 The regenerated particle aggregate used in the present embodiment is obtained by using deinked floss as a raw material and passing through a dehydration step, a drying step, a firing step, and a pulverization step. Furthermore, as will be described later, a deinking floss aggregation process, a granulation process, a classification process provided between the processes, and the like may be performed. In addition, it is desirable to provide various sensors in the production facility for regenerated particles to control the state of the object to be processed and the equipment, the processing speed, and the like.
さらに本実施形態においては、原料パルプに内添する再生粒子凝集体として、前記のごとき工程を経て得られた粒子の表面をシリカで被覆した、シリカ被覆再生粒子凝集体を特に好適に用いることができるのである。 Furthermore, in the present embodiment, as the regenerated particle aggregate internally added to the raw material pulp, it is particularly preferable to use a silica-coated regenerated particle aggregate in which the surface of the particles obtained through the above-described steps is coated with silica. It can be done.
前記再生粒子凝集体の表面にさらにシリカを析出させ、シリカ被覆再生粒子凝集体とすることで、循環使用における古紙処理工程において、水酸化ナトリウムと反応させて緩衝剤や漂白助剤として製紙用原料、無機粒子の循環使用にも寄与させることができる。またかかるシリカ被覆再生粒子凝集体を填料として原料パルプに内添した場合には、シリカで被覆していない再生粒子凝集体を用いた場合よりもさらに、紙の白色度、不透明度、表面強度、インク乾燥性、インク吸収ムラ、嵩高といった各効果を向上することができる。 Silica is further precipitated on the surface of the regenerated particle aggregate to form a silica-coated regenerated particle agglomerate, so that it is reacted with sodium hydroxide in the used paper processing step in circulation use and used as a buffering agent or bleaching aid as a papermaking raw material. In addition, it can contribute to the recycling of inorganic particles. Further, when such a silica-coated regenerated particle aggregate is internally added to the raw material pulp as a filler, the whiteness of the paper, opacity, surface strength, and more than when using a regenerated particle aggregate not coated with silica, Each effect such as ink drying property, ink absorption unevenness and bulkiness can be improved.
なお、本実施形態に用いられる古紙処理工程にて生じる脱墨フロスは、近年の中性抄紙化に伴い、炭酸カルシウムの含有量が増加傾向にあり、得られる再生粒子凝集体中のカルシウムの割合も高くなる傾向がある。このようにカルシウムの割合が高い再生粒子凝集体を原料パルプに内添すると、紙の不透明度がやや低下する場合があるが、表面にシリカを析出させたシリカ被覆再生粒子凝集体は、製紙用途の再生粒子凝集体としての機能が非常に高く、該シリカ被覆再生粒子凝集体を原料パルプに内添して得られる紙の不透明度は、著しく向上する。 In addition, the deinking floss produced in the used paper processing step used in the present embodiment has a tendency to increase the content of calcium carbonate with the recent neutral paper making, the proportion of calcium in the obtained regenerated particle aggregate Tend to be higher. When regenerated particle agglomerates with a high calcium content are added internally to the raw material pulp, the opacity of the paper may be slightly reduced, but the silica-coated regenerated particle agglomerates with silica precipitated on the surface are used for papermaking. The regenerated particle aggregate has a very high function, and the opacity of the paper obtained by internally adding the silica-coated regenerated particle aggregate to the raw material pulp is remarkably improved.
再生粒子凝集体の表面を被覆するシリカについては、天然に産出するシリカではなく、何らかの化学反応による合成シリカであれば特に制限なく使用することが可能である。具体的には、例えばコロイダルシリカ、シリカゲル、無水シリカなどがあげられる。これらの合成シリカは、高比表面積、ガス吸着能の高さ、微細性、細孔への浸透力や吸着力の大きさ、付着性の高さ、高吸油性などの優れた特性を活かして、幅広い分野で利用されているものである。これらのうち、コロイダルシリカは、ケイ酸化合物から不純分を除去して無水ケイ酸ゾルとし、pH及び濃度を調整してゾルを安定化させた、球状、連鎖状、不定形等の形状を有する非晶質シリカである。シリカゲルは、ケイ酸ナトリウムを無機酸で分解することによって得られる含水ケイ酸である。また無水シリカは、四塩化ケイ素の加水分解によって得られるものである。 The silica covering the surface of the regenerated particle aggregate can be used without particular limitation as long as it is not naturally produced silica but synthetic silica by some chemical reaction. Specific examples include colloidal silica, silica gel, and anhydrous silica. These synthetic silicas make use of excellent properties such as high specific surface area, high gas adsorbing capacity, fineness, permeability to pores and large adsorbing power, high adhesion, and high oil absorption. It is used in a wide range of fields. Among these, colloidal silica has a shape such as a spherical shape, a chain shape, and an amorphous shape, in which impurities are removed from a silicic acid compound to form an anhydrous silicic acid sol, and the sol is stabilized by adjusting pH and concentration. Amorphous silica. Silica gel is hydrous silicic acid obtained by decomposing sodium silicate with an inorganic acid. Anhydrous silica is obtained by hydrolysis of silicon tetrachloride.
再生粒子凝集体の表面にシリカを析出させ、シリカ被覆再生粒子凝集体を得る方法には特に限定がないが、例えば以下の方法を好適に採用することができる。まず、再生粒子凝集体をケイ酸アルカリ溶液に添加、分散させ、スラリーを調製した後に加熱攪拌しながら、液温を70〜100℃程度に保持して酸を添加し、シリカゾルを生成させる。次いで最終反応液のpHを8〜11の範囲に調整することにより、再生粒子凝集体の表面にシリカを析出させることができる。このようにして再生粒子凝集体の表面に析出されるシリカは、ケイ酸アルカリ(例えばケイ酸ナトリウム:水ガラス)を原料として、硫酸、塩酸、硝酸等の鉱酸の希釈液と高温下で反応し、加水分解反応とケイ酸の重合化により得られる、粒子径が10〜20nm程度のシリカゾル粒子である。 There is no particular limitation on the method for obtaining silica-coated regenerated particle aggregates by precipitating silica on the surface of the regenerated particle aggregates. For example, the following methods can be suitably employed. First, regenerated particle aggregates are added and dispersed in an alkali silicate solution, and after preparing a slurry, while heating and stirring, an acid is added while maintaining the liquid temperature at about 70 to 100 ° C. to produce a silica sol. Subsequently, silica can be deposited on the surface of the regenerated particle aggregate by adjusting the pH of the final reaction solution to a range of 8-11. Silica deposited on the surface of the regenerated particle aggregate in this way reacts at a high temperature with a dilute solution of mineral acid such as sulfuric acid, hydrochloric acid, nitric acid, etc., using alkali silicate (eg, sodium silicate: water glass) as a raw material. And silica sol particles having a particle size of about 10 to 20 nm, which are obtained by hydrolysis reaction and polymerization of silicic acid.
また、ケイ酸ナトリウム溶液等のケイ酸アルカリ溶液に希硫酸等の酸を添加することによって生成する、粒子径が数nm程度のシリカゾル微粒子を、再生粒子凝集体の多孔性を有する表面全体を被覆するように付着させ、このシリカゾル微粒子の結晶成長に伴う、無機微粒子表面上のシリカゾル微粒子と再生粒子凝集体に包含されるケイ素やカルシウム、アルミニウムとの間で生じる結合により、再生粒子凝集体の表面にシリカを析出させることもできる。この場合、ケイ酸アルカリ溶液に酸を添加する際のpHは、中性〜弱アルカリ性の範囲とし、好ましくはpHを8〜11の範囲に調整する。これは、pHが7未満の酸性条件になるまで酸を添加してしまうと、シリカゾル粒子ではなくホワイトカーボンが生成する恐れが生じるからである。 In addition, silica sol fine particles with a particle size of several nanometers, which are generated by adding an acid such as dilute sulfuric acid to an alkali silicate solution such as sodium silicate solution, cover the entire porous surface of the regenerated particle aggregate. The surface of the regenerated particle aggregate is caused by the bond between the silica sol fine particle on the surface of the inorganic fine particle and the silicon, calcium, or aluminum included in the regenerated particle aggregate accompanying the crystal growth of the silica sol fine particle. Silica can also be deposited on the substrate. In this case, the pH when adding the acid to the alkali silicate solution is in a neutral to weakly alkaline range, and the pH is preferably adjusted in the range of 8-11. This is because if the acid is added until the pH reaches an acidic condition of less than 7, white carbon may be generated instead of silica sol particles.
なお、前記ケイ酸アルカリ溶液の種類には特に限定がないが、入手が容易である点からケイ酸ナトリウム溶液(3号水ガラス)が特に望ましい。このケイ酸アルカリ溶液の濃度としては、再生粒子凝集体中のシリカ成分が低下し、再生粒子凝集体の表面にシリカが析出し難くならないようにするには、溶液中のケイ酸分(SiO2換算)が3質量%以上であることが好ましく、再生粒子凝集体の表面に析出されるシリカが、シリカゾルの形態からホワイトカーボンになり、再生粒子凝集体の多孔性が阻害され、不透明度やトナー定着性の向上効果が不充分になる恐れをなくすには、係るケイ酸分(SiO2換算)が10質量%以下であることが好ましい。 The type of the alkali silicate solution is not particularly limited, but a sodium silicate solution (No. 3 water glass) is particularly desirable from the viewpoint of easy availability. The concentration of the alkali silicate solution is such that the silica component in the regenerated particle aggregate decreases and the silica content (SiO 2) in the solution does not become difficult to precipitate on the surface of the regenerated particle aggregate. (Converted) is preferably 3% by mass or more, and the silica deposited on the surface of the regenerated particle aggregate becomes white carbon from the form of the silica sol, and the porosity of the regenerated particle aggregate is hindered. In order to eliminate the possibility that the effect of improving the fixability will be insufficient, the silicic acid content (in terms of SiO 2 ) is preferably 10% by mass or less.
再生粒子凝集体の粒度を各工程で均一に揃えるためには、分級を行うことが好ましく、粗大粒子や微小粒子を前工程にフィードバックすることでより品質の安定化を図ることができる。 In order to make the particle size of the regenerated particle aggregate uniform in each step, classification is preferably performed, and the quality can be further stabilized by feeding back coarse particles and fine particles to the previous step.
また乾燥工程の前段階において、脱水処理を行った脱墨フロスを造粒することが好ましく、さらには造粒物の粒度を均一に揃えるための分級を行うことがより好ましく、粗大や微小の造粒粒子を前工程にフィードバックすることでより品質の安定化を図ることができる。なお造粒においては、通常の造粒設備を使用することができ、回転式、攪拌式、押出式等の設備が好適である。 In addition, it is preferable to granulate the deinked floss that has been dehydrated in the previous stage of the drying process, and more preferably to classify the granulated product uniformly so that coarse or fine particles are formed. The quality can be further stabilized by feeding back the grains to the previous process. In granulation, ordinary granulation equipment can be used, and equipment such as a rotary type, a stirring type, and an extrusion type is preferable.
製造設備において、再生粒子以外の異物を除去することが好ましく、例えば古紙パルプ製造工程の脱墨工程に至る前段階のパルパーやスクリーン、クリーナー等で砂、プラスチック、金属等の異物を除去することが、除去効率の点で好ましい。特に鉄分は、酸化により再生粒子凝集体の白色度低下の起因物質を生成するため、鉄分の混入を避け、選択的に除去することが好ましい。したがって、各工程を鉄以外の素材で設計又はライニングし、磨滅等により鉄分が系内に混入することを防止すると共に、さらに乾燥・分級設備内等に磁石等の高磁性体を設置し、選択的に鉄分を除去することが好ましい。 It is preferable to remove foreign substances other than regenerated particles in the production facility. For example, it is possible to remove foreign substances such as sand, plastic, metal, etc. with a pulper, screen, cleaner, etc. before reaching the deinking process of the used paper pulp manufacturing process. From the viewpoint of removal efficiency. In particular, the iron content is preferably removed by avoiding the mixing of iron content, since it causes a substance that causes a decrease in whiteness of the regenerated particle aggregate by oxidation. Therefore, each process is designed or lined with materials other than iron, and iron is prevented from being mixed into the system due to wear, etc., and a high magnetic material such as a magnet is installed and selected in the drying / classifying equipment. It is preferable to remove iron.
なお本実施形態においては、前記乾燥工程や焼成工程、及び必要に応じて分級工程において、粉砕工程前にあらかじめ、粒子径が40μm以下の粒子が90質量%以上となるように処理しておくことが好ましい。これにより、通常行われている乾式粉砕による粗大粒子の粉砕及び湿式粉砕による微粒子化といった複数段の粉砕処理を行うことなく、湿式粉砕による一段粉砕処理も可能となる。またこれにより、コールターカウンター法による粒度分布の微分曲線における平均粒子径のピーク高さを30%以上とすることができる。さらには原料である脱墨フロス中のカルシウム、ケイ素及びアルミニウムを、あらかじめ、例えば後述する質量割合に調整することで、再生粒子凝集体の細孔容積を0.15〜0.60cc/g、細孔表面積を10〜25m2/g、細孔半径を30〜100nmとすることもできる。 In the present embodiment, in the drying step, the firing step, and the classification step as necessary, the particles having a particle size of 40 μm or less are preliminarily processed to 90% by mass or more before the pulverization step. Is preferred. Accordingly, a single-stage pulverization process by wet pulverization can be performed without performing a multistage pulverization process such as pulverization of coarse particles by dry pulverization and fine particle formation by wet pulverization. Thereby, the peak height of the average particle diameter in the differential curve of the particle size distribution by the Coulter counter method can be set to 30% or more. Furthermore, by adjusting calcium, silicon, and aluminum in the deinking floss as a raw material in advance to a mass ratio described later, for example, the pore volume of the regenerated particle aggregate is 0.15 to 0.60 cc / g, fine. The pore surface area may be 10 to 25 m 2 / g, and the pore radius may be 30 to 100 nm.
かくして得られる再生粒子凝集体は、カルシウム、ケイ素及びアルミニウムを含有している。再生粒子凝集体中のこれらカルシウム、ケイ素及びアルミニウムの割合は、X線マイクロアナライザー(型番:E−MAX・S−2150、(株)日立製作所/(株)堀場製作所製)にて元素分析を行い、酸化物換算で、カルシウム:ケイ素:アルミニウムが30〜62:29〜55:9〜35であることが好ましい。また同時に、これらカルシウム、ケイ素及びアルミニウムの元素分析における酸化物換算の合計含有割合は、90質量%以上、好ましくは93質量%以上である。 The regenerated particle aggregate thus obtained contains calcium, silicon and aluminum. The ratio of these calcium, silicon, and aluminum in the regenerated particle aggregate is subjected to elemental analysis using an X-ray microanalyzer (model number: E-MAX S-2150, Hitachi, Ltd./Horiba, Ltd.). In terms of oxide, calcium: silicon: aluminum is preferably 30 to 62:29 to 55: 9 to 35. At the same time, the total content in terms of oxides in the elemental analysis of calcium, silicon and aluminum is 90% by mass or more, preferably 93% by mass or more.
このように、例えばカルシウムが酸化物換算で30質量割合以上含有された再生粒子凝集体を填料として原料パルプに内添した場合には、特に得られる紙の白色度を向上させることができる。 Thus, for example, when a regenerated particle aggregate containing 30 mass% or more of calcium in terms of oxide is internally added to the raw material pulp as a filler, the whiteness of the obtained paper can be improved.
再生粒子凝集体中のカルシウム、ケイ素及びアルミニウムの割合を、例えば酸化物換算で前記範囲内に調整するには、本来、脱墨フロスにおける原料構成を調整することが好ましいが、乾燥工程や焼成工程、さらには必要に応じて分級工程において、由来が明確な塗工フロスや調整工程フロスをスプレー等で含有させる方法や、焼却炉スクラバー石灰を含有させる方法を採用することも可能である。 In order to adjust the ratio of calcium, silicon, and aluminum in the regenerated particle aggregate within the above range, for example, in terms of oxide, it is originally preferable to adjust the raw material composition in the deinking floss, but the drying step and the firing step Further, if necessary, in the classification step, it is also possible to employ a method in which a coating floss having a clear origin or an adjustment step floss is contained by spraying or a method in which incinerator scrubber lime is contained.
例えば、再生粒子凝集体中のカルシウムの調整には中性抄紙系の排水スラッジや、塗工紙製造工程の排水スラッジを、ケイ素の調整には不透明度向上剤として多量添加されている新聞用紙製造系の排水スラッジを、アルミニウムの調整には酸性抄紙系等の硫酸バンドが使用された抄紙系の排水スラッジや、クレーの使用量が多い上質紙抄造工程の排水スラッジを適宜用いることができる。 For example, neutral paper-making wastewater sludge for the adjustment of calcium in recycled particle aggregates and wastewater sludge from the coated paper manufacturing process, and newsprint manufacturing with a large amount added as an opacity improver for silicon adjustment For the adjustment of aluminum, a papermaking wastewater sludge using an acid papermaking system or other sulfuric acid band or a high quality papermaking process wastewater sludge using a large amount of clay can be used as appropriate.
またカルシウム、ケイ素及びアルミニウムの合計含有割合を、酸化物換算で90質量%以上に調整するには、例えば排水スラッジの凝集処理に鉄分を含有しない凝集剤を使用する手段、製造設備工程を鉄以外の素材で設計又はライニングし、磨滅等により鉄分が系内に混入するのを防止したり、さらには乾燥・分級設備内に磁石等の高い磁性体を設置して鉄分を除去する手段等を採用することが可能である。特に鉄分は、酸化により白色度を低下させる起因物質になるため、選択的に除去することが好ましい。 Moreover, in order to adjust the total content of calcium, silicon and aluminum to 90% by mass or more in terms of oxides, for example, means for using a flocculant containing no iron in the agglomeration treatment of drainage sludge, and manufacturing equipment processes other than iron Designed or lined with other materials to prevent iron from being mixed into the system due to wear, etc., and further adopting means to remove iron by installing high magnetic materials such as magnets in the drying and classification equipment Is possible. In particular, iron content is preferably a causative substance that lowers the whiteness by oxidation, and thus is preferably removed selectively.
ところで、炭酸カルシウムには、六方結晶系のカルサイト結晶(方解石)や、斜方結晶系のアラゴナイト結晶(あられ石)などの同質異像が存在する。天然に産する石灰石はその殆どがカルサイト結晶であり、貝殻類にはカルサイト結晶のほか、アラゴナイト結晶も存在する。さらに炭酸カルシウムには、天然ではないが、バテライト結晶も存在する。前記脱墨フロスから得られるカルシウムは多種多様であるが、焼成凝集化することでほぼ均一の炭酸カルシウム性状となる。したがって、係るカルシウムは再生粒子凝集体そのものの品質安定性に寄与し、該再生粒子凝集体は、カルシウム、ケイ素、アルミニウムといった異なる成分で構成される凝集体でありながら、安定した性状を示す。 By the way, calcium carbonate has homogeneous images such as hexagonal calcite crystals (calcite) and orthorhombic aragonite crystals (aragonite). Most limestones produced in nature are calcite crystals, and shellfish contain aragonite crystals in addition to calcite crystals. Furthermore, although not natural, calcium carbonate also has vaterite crystals. There are various kinds of calcium obtained from the deinking floss, but it becomes a substantially uniform calcium carbonate property by calcination and aggregation. Accordingly, the calcium contributes to the quality stability of the regenerated particle aggregate itself, and the regenerated particle aggregate exhibits stable properties while being an aggregate composed of different components such as calcium, silicon, and aluminum.
また再生粒子凝集体にはケイ素が含まれるが、該ケイ素からなるシリカの一次粒子は微細であるので、光学的屈折率が高い。したがって、例えばケイ素が酸化物換算で9質量割合以上含有された再生粒子凝集体を填料として原料パルプに内添した場合には、特に得られる紙の不透明度を向上させることができる。 The regenerated particle aggregate contains silicon, but since the primary particles of silica composed of silicon are fine, the optical refractive index is high. Therefore, for example, when a regenerated particle aggregate containing 9 mass% or more of silicon in terms of oxide is internally added to the raw material pulp as a filler, the opacity of the obtained paper can be improved.
さらに本実施形態に用いられる再生粒子凝集体は、微細な粒子が二次凝集した柔軟かつポーラスな性状を有するので、嵩高な紙層形成に寄与し、該再生粒子凝集体を填料として原料パルプに内添して得られる新聞用紙は、密度が低く、取りまわしが良好な剛度を有する。 Furthermore, since the regenerated particle aggregate used in the present embodiment has a flexible and porous property in which fine particles are secondarily aggregated, it contributes to the formation of a bulky paper layer, and the regenerated particle aggregate is used as a filler in raw pulp. Newspaper paper obtained by internal addition has a low density and a high rigidity for handling.
本実施形態に用いられる再生粒子凝集体の粒子径は、例えば一次粒子が凝集した二次粒子として、原料パルプ中への歩留まりや再生粒子凝集体の白水中への流失防止という点から、そのメタノール分散溶液をコールターカウンター粒度分布測定装置(TA−II型、COULTER ELECTRONICS社製)にて測定して、平均粒子径が0.05μm以上、さらには0.1μm以上であることが好ましく、また印刷適正の維持と剣先詰まりの防止という点から、平均粒子径が16μm以下、さらには15μm以下であることが好ましい。 The particle diameter of the regenerated particle aggregate used in the present embodiment is, for example, as a secondary particle in which primary particles are aggregated, in terms of yield in raw pulp and prevention of loss of regenerated particle aggregate into white water. The dispersion is measured with a Coulter counter particle size distribution analyzer (TA-II type, manufactured by COULTER ELECTRONICS), and the average particle size is preferably 0.05 μm or more, more preferably 0.1 μm or more, and printing is suitable. The average particle size is preferably 16 μm or less, more preferably 15 μm or less, from the viewpoint of maintaining the thickness and preventing clogging of the blade tip.
前記再生粒子凝集体の含有量があまりにも少ない場合には、例えば抄紙機でのカレンダー処理において、平滑化の効果が発現されにくくなり、紙の不透明性が低下して印刷後の不透明度が低下したり、新聞用紙の剛直度が高くなり、輪転機上での走行性が低下したりする恐れがあるので、原料パルプに対して2質量%以上、さらには5質量%以上であることが好ましい。逆に再生粒子凝集体の含有量があまりにも多い場合には、表面性や剛度の点では望ましいものの、印刷機内での搬送に伴って灰分が脱落し易くなり、表面強度の低下や、剥け・ケバ立ち、印刷白抜け、紙粉が発生する恐れがあるので、原料パルプに対して20質量%以下、さらには15質量%以下であることが好ましい。 When the content of the regenerated particle aggregate is too small, for example, in a calendar process on a paper machine, a smoothing effect is hardly exhibited, and the opacity after printing is lowered due to a decrease in paper opacity. Or the rigidity of the newsprint is increased, and the running performance on a rotary press may be reduced. Therefore, the content is preferably 2% by mass or more, more preferably 5% by mass or more based on the raw material pulp. . Conversely, if the content of regenerated particle aggregates is too high, it is desirable in terms of surface properties and rigidity, but ash tends to fall off during transport in the printing press, resulting in reduced surface strength, Since there is a possibility that fluffing, printing white spots, and paper dust may occur, the content is preferably 20% by mass or less, more preferably 15% by mass or less, based on the raw material pulp.
本実施形態において、填料として前記再生粒子凝集体を単独で用いることもできるが、このほかに、内添用填料として通常使用される、例えば重質炭酸カルシウム、軽質炭酸カルシウム等の炭酸カルシウム、タルク、カオリンクレー、デラミネーテッドクレー等のクレー、二酸化チタン、合成シリカ、水酸化アルミニウム等の無機填料、ポリスチレン樹脂、尿素ホルムアルデヒド樹脂等の合成高分子微粒子等から選ばれた少なくとも1種の填料を併用することもできる。 In the present embodiment, the regenerated particle aggregate can be used alone as a filler, but in addition to this, calcium carbonate such as heavy calcium carbonate and light calcium carbonate, talc, etc. And at least one filler selected from clays such as kaolin clay and delaminated clay, inorganic fillers such as titanium dioxide, synthetic silica and aluminum hydroxide, and synthetic polymer fine particles such as polystyrene resin and urea formaldehyde resin You can also
なお再生粒子凝集体を含む填料の添加率があまりにも少ない場合には、填料を用いる効果が充分に発現されず、逆にあまりにも多い場合には、紙力が低下する恐れがあるので、該填料は、紙中に紙灰分として4〜15質量%、さらには5〜10質量%含まれることが好ましい。 In addition, when the addition rate of the filler containing the regenerated particle agglomerates is too small, the effect of using the filler is not sufficiently expressed, and conversely, when it is too large, the paper strength may be reduced. The filler is preferably contained in the paper in an amount of 4 to 15% by mass, more preferably 5 to 10% by mass, as paper ash.
また原料パルプ及び填料から得られた紙料スラリーに添加する添加剤としては、通常の紙に配合されるものを用いることができ、例えば澱粉類、植物性ガム、水性セルロース誘導体、ケイ酸ソーダ等の紙力増強剤;ロジン、澱粉、CMC(カルボキシルメチルセルロース)、ポリビニルアルコール、アルキルケテンダイマー、ASA(アルケニル無水コハク酸)、中性ロジン等の内添サイズ剤;ポリアクリルアミドやその共重合体、ケイ酸ナトリウム等の歩留まり向上剤などがあげられる。 In addition, as additives to be added to the paper slurry obtained from raw pulp and filler, those added to ordinary paper can be used, such as starches, vegetable gums, aqueous cellulose derivatives, sodium silicate, etc. Paper strength enhancers: rosin, starch, CMC (carboxyl methylcellulose), polyvinyl alcohol, alkyl ketene dimer, ASA (alkenyl succinic anhydride), neutral rosin and other internal sizing agents; polyacrylamide and copolymers thereof, silica Examples thereof include a yield improving agent such as sodium acid.
さらに本実施形態においては、原料パルプから紙料スラリーを調製して抄紙した後、表面に例えば澱粉、変性澱粉、PVA(ポリビニルアルコール)、ポリアクリルアミド等の高分子材料を成分とする表面処理剤を塗布したり、紙料スラリーに染料、顔料等の色料を添加したりしてもよい。 Furthermore, in this embodiment, after preparing a paper slurry from raw material pulp and making paper, a surface treatment agent containing, as a component, a polymer material such as starch, modified starch, PVA (polyvinyl alcohol), or polyacrylamide is formed on the surface. You may apply | coat or color materials, such as dye and a pigment, may be added to paper stock slurry.
前記変性澱粉としては、特に限定されるものではなく、通常の澱粉原料が用いられ、例えばトウモロコシ、馬鈴薯、タピオカ、小麦、米等に酸化処理、酵素処理等が施された澱粉があげられる。この変性澱粉を用いる場合、表面処理剤中の量は、所望の効果を得るためには、全固形分中40質量%以上となるように調整することが好ましい。 The modified starch is not particularly limited, and ordinary starch raw materials are used. Examples thereof include starch obtained by subjecting corn, potato, tapioca, wheat, rice, etc. to oxidation treatment, enzyme treatment, and the like. When this modified starch is used, the amount in the surface treatment agent is preferably adjusted so as to be 40% by mass or more in the total solid content in order to obtain a desired effect.
表面処理剤には、適宜他の接着剤、例えばスチレン−ブタジエン共重合体等のラテックス類、ポリビニルアルコールやポリアクリルアミド、さらにはカオリンや炭酸カルシウム等の顔料、消泡剤、耐水化剤、表面サイズ剤、防腐剤等の各種助剤を添加することもできる。また表面処理剤の固形分濃度は特に限定されるものではなく、塗布装置や塗布量に応じて、例えば2〜25質量%程度に調整することが好ましい。 As the surface treatment agent, other adhesives as appropriate, for example, latexes such as styrene-butadiene copolymer, polyvinyl alcohol and polyacrylamide, and pigments such as kaolin and calcium carbonate, antifoaming agents, water-proofing agents, surface size, etc. Various auxiliaries such as agents and preservatives can also be added. Moreover, the solid content concentration of the surface treatment agent is not particularly limited, and is preferably adjusted to, for example, about 2 to 25% by mass according to the coating apparatus and the coating amount.
なお、表面処理剤をあまりにも多量に使用すると、コスト高となるだけでなく、紙表面が湿った状態でネッパリ性と呼ばれる紙表面の粘着性が発現される傾向がある。このネッパリ性が大きくなると、特に非画線部におけるブランケットパイリングを逆に増大させたり、また印刷時に紙面がブランケットに貼り付き、結果的にシワや断紙といった走行性トラブルを誘発したりする恐れがあるので、好ましくない。また、表面処理剤の使用量が増加すると、目的とする紙の透明性が上昇、すなわち不透明度が低下したり、インクの乾燥性が悪化したりする場合もある。これらの表面処理剤のうち、澱粉やポリアクリルアミドは比較的ネッパリ性が低いので広く使用されているが、いずれも水への溶解性が高いため、印刷時に湿し水中に容易に溶出して填料と共にブランケットに堆積し、ブランケットパイリングが発生し易い。また溶出した表面処理剤がブランケットを介して刷版に転移、蓄積することで刷版の非画線部が感脂化し、非画線部のインク汚れ、すなわち地汚れと呼ばれる紙面の汚れを誘発し易くなることから、多量に用いることは好ましくない。 If the surface treatment agent is used in an excessively large amount, not only the cost is increased, but also the adhesiveness of the paper surface called “Nepari” property tends to be expressed when the paper surface is wet. If this sharpness increases, there is a risk that blanket piling, especially in non-image areas, will increase and the paper surface will stick to the blanket during printing, resulting in running problems such as wrinkles and paper breaks. Because there is, it is not preferable. Further, when the amount of the surface treatment agent used is increased, the transparency of the target paper may be increased, that is, the opacity may be decreased, or the ink drying property may be deteriorated. Of these surface treatments, starch and polyacrylamide are widely used because of their relatively low nepariness, but they are both highly soluble in water, so that they can be easily eluted in dampening water during printing. At the same time, it is deposited on the blanket, and blanket piling is likely to occur. Also, the eluted surface treatment agent is transferred to and accumulated on the printing plate via the blanket, so that the non-image area of the printing plate becomes sensitized, and ink stains on the non-image area, that is, paper contamination called background contamination, is induced. Therefore, it is not preferable to use a large amount.
前記表面処理剤は、製紙分野で一般に使用されている塗布装置、例えばサイズプレス、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、ブレードコータ、バーコータ、ロッドコータ、エアナイフコータ等を用いて塗布すればよい。 The surface treatment agent is a coating apparatus commonly used in the papermaking field, such as a size press, a blade metering size press, a rod metalling size press, a gate roll coater, a blade coater, a bar coater, a rod coater, an air knife coater, etc. And apply.
表面処理剤の塗布量は、紙の表面強度を充分に向上させるには、乾燥重量で0.4g/m2以上となるように調整することが好ましく、またコスト高となったり、不透明度やインク乾燥性の低下を招いたりしないようにするには、乾燥重質量で3.0g/m2以下となるように、より好ましくは、0.7〜2.5g/m2以下に調整することが好ましい。 The coating amount of the surface treating agent, in order to sufficiently improve the surface strength of the paper is preferably adjusted so that 0.4 g / m 2 or more by dry weight, also may become a cost, Ya opacity to prevent or cause a reduction in the ink drying property is dried as heavy weight becomes 3.0 g / m 2 or less, more preferably, it is adjusted to below 0.7 to 2.5 g / m 2 Is preferred.
かくして紙料スラリー及び必要に応じて添加剤から調製された紙料は、公知の抄紙機によって抄造することができ、さらに必要に応じてカレンダー装置に通紙し、加圧、平滑化処理を施して新聞用紙に仕上げることができる。該カレンダー装置としては、通常の金属ロールと金属ロールとの組み合わせによるマシンカレンダーよりも、金属ロールと樹脂ロールとの組み合わせによるソフトカレンダーを使用するほうが、紙層を強く加圧せずに平滑化することができ、さらに紙層強度の低下を充分に抑制することができるのでより好ましい。 Thus, the stock prepared from the stock slurry and, if necessary, the additive can be made by a known paper machine, and further passed through a calender device as necessary, followed by pressurization and smoothing treatment. Can be finished into newspaper. As the calendering device, a soft calender using a combination of a metal roll and a resin roll is used to smooth the paper layer without pressing strongly, rather than a machine calender using a combination of a normal metal roll and a metal roll. Further, it is more preferable because a decrease in paper layer strength can be sufficiently suppressed.
ソフトカレンダーの使用においては、新聞用紙の粗面側に当たる裏面側がソフトカレンダーの金属ロール面に先に接触するように通紙することで、より平坦性及び嵩高性の向上をより図ることができ、1500m/分以上の高速抄紙において高い平坦性と表裏差の少ない新聞用紙を得ることができる。 In the use of the soft calendar, the flatness and bulkiness can be further improved by passing the paper so that the back side, which is the rough side of the newspaper, contacts the metal roll surface of the soft calendar first, Newspaper paper with high flatness and little difference in front and back can be obtained in high-speed papermaking at 1500 m / min or more.
さらに好ましくは、表裏面に設ける表面処理剤の塗布量を表面側より裏面側を多くすることにより、より良好な平坦性と嵩高性とが得られ、腰のある新聞用紙を得ることができる。 More preferably, by increasing the coating amount of the surface treatment agent provided on the front and back sides on the back side from the front side, better flatness and bulkiness can be obtained, and it is possible to obtain a newsprint with a waist.
なお前記抄造の際の新聞用紙のpHは、硫酸アルミニウム(硫酸バンド)を添加し、アルミニウムを介して樹脂成分を繊維に定着させるか、あるいは樹脂成分の凝集体を形成させることにより、樹脂成分を紙支持体に取り込むことによって製造工程での樹脂成分の付着を防ぐため、アルミニウムイオン種のカチオン性が最も活性なpH4〜6未満の範囲内で新聞用紙を抄造するのが一般的であるが、本発明にて使用する古紙パルプは、古紙から脱インクして製造されるためpHが6以上と高く、高pH化による安定性やpH調整という点、補助的な使用が考えられる炭酸カルシウムの使用に際しては、該炭酸カルシウムが溶解して歩留まりが低下したり、抄紙工程の汚れの原因になったりする恐れをなくすほか、理由は不明確ながらpH6未満で抄紙するよりも、6以上で抄紙することによって紙力の向上が図られる事由から、6〜9.5程度となるように調整することが好ましい。 The pH of the newsprint at the time of papermaking is determined by adding aluminum sulfate (sulfuric acid band) and fixing the resin component to the fiber through aluminum or forming an aggregate of the resin component. In order to prevent adhesion of the resin component in the manufacturing process by incorporating it into the paper support, it is common to make newsprint within the range of pH 4 to less than 6 where the cationicity of the aluminum ion species is most active, The waste paper pulp used in the present invention is manufactured by deinking from waste paper, so that the pH is as high as 6 or more, and the use of calcium carbonate, which is considered to be auxiliary use in terms of stability and pH adjustment due to high pH. At this time, the calcium carbonate dissolves to eliminate the risk of yield loss and the cause of soiling in the papermaking process. In than paper, the grounds improvement in paper strength is achieved by paper with 6 or more, it is preferable to adjust such that the order of 6 to 9.5.
また再生粒子凝集体の添加は、従来のいずれの段階でも行うことが可能であるが、原料配合チェストからインレットの間で行うことが好ましい。この間に添加することにより、再生粒子凝集体が分散し易くなり、パルプ繊維への定着性が向上し、その結果、填料の歩留まりが向上する。また再生粒子凝集体がパルプ繊維間の結合を阻害しないので、紙の剛度が低下することもない。再生粒子凝集体をより均一に分散させ、パルプ繊維への定着性を向上させるためには、できる限りインレットの近傍工程で該再生粒子凝集体を添加することが特に好ましい。 Addition of the regenerated particle agglomerates can be performed at any stage of the prior art, but is preferably performed between the raw material blending chest and the inlet. Addition during this time makes it easy to disperse the regenerated particle aggregates, improving the fixability to pulp fibers, and as a result, improving the yield of the filler. Further, since the regenerated particle aggregate does not inhibit the binding between the pulp fibers, the rigidity of the paper is not lowered. In order to disperse the regenerated particle aggregate more uniformly and to improve the fixability to the pulp fiber, it is particularly preferable to add the regenerated particle aggregate as close as possible to the inlet.
かくして得られる新聞用紙は、JIS P 8251に準拠した灰分が4〜15%で、JIS P 8133に記載の「紙、板紙及びパルプ−水抽出液pHの試験方法」に準拠して測定した熱水抽出pHが、6.0以上、さらには6.1以上であることが好ましく、また9.5以下、さらには8.5以下であることが好ましい。熱水抽出pHがこのような範囲の場合には、補助的な使用が考えられる炭酸カルシウムや、僅かとは考えられるが、再生粒子凝集体中に内在する炭酸カルシウムの溶出が防止されて再生粒子凝集体の形状が安定し、また水酸化カルシウムの生成が防止され、抄紙工程系内の汚れやスケールの発生を抑制し、紙の劣化抑制や資源循環を図ることができる。また、紙のインク乾燥性を向上させ、インク吸収ムラを少なくしたり、劣化を充分に抑制し、保存性や助剤の定着性をさらに向上させることもできる。 The newsprint thus obtained has an ash content of 4 to 15% in accordance with JIS P 8251, and hot water measured in accordance with “Test method for pH of paper, paperboard and pulp-water extract” described in JIS P 8133. The extraction pH is preferably 6.0 or more, more preferably 6.1 or more, and is preferably 9.5 or less, more preferably 8.5 or less. When the hot water extraction pH is in such a range, calcium carbonate, which is considered to be an auxiliary use, or a little, but it is considered that the elution of calcium carbonate contained in the regenerated particle aggregate is prevented, and regenerated particles are used. The shape of the aggregate is stable, the formation of calcium hydroxide is prevented, the occurrence of dirt and scale in the papermaking process system is suppressed, paper deterioration can be suppressed, and resource circulation can be achieved. In addition, the ink drying property of paper can be improved, the ink absorption unevenness can be reduced, the deterioration can be sufficiently suppressed, and the storage stability and the fixing property of the auxiliary agent can be further improved.
さらに本実施形態に係る紙の坪量は、軽量化、例えば高速輪転印刷における紙質強度の確保、印刷不透明度の確保という点から、JIS P 8124に記載の「坪量測定方法」に準拠して測定して、37g/m2以上、さらには40g/m2以上であることが好ましく、またその軽量化の点から、係る坪量は48g/m2以下、さらには46g/m2以下であることが好ましい。37g/m2未満では、例えば高速オフセット輪転印刷機における強度確保が困難であり、48g/m2を超えると、近年の軽量化、省資源に逆行することとなる。 Further, the basis weight of the paper according to the present embodiment is based on the “basis weight measurement method” described in JIS P 8124 from the viewpoint of weight reduction, for example, ensuring the paper quality strength in high-speed rotary printing and ensuring the printing opacity. Measured, it is preferably 37 g / m 2 or more, more preferably 40 g / m 2 or more, and the basis weight is 48 g / m 2 or less, further 46 g / m 2 or less from the viewpoint of weight reduction. It is preferable. If it is less than 37 g / m 2 , for example, it is difficult to ensure the strength in a high-speed offset rotary printing press, and if it exceeds 48 g / m 2 , it goes against the recent weight saving and resource saving.
紙の白色度は、その用途に応じて異なるが、新聞用紙においては購読者の眼精疲労をきたさないように、JIS P 8123に記載の「紙及びパルプのハンター白色度試験方法」に準拠して測定して、少なくとも50%以上が好ましく、白色度は52〜56%、さらには53〜55%であることが好ましい。 The whiteness of paper varies depending on the application, but in order to prevent eye strain of subscribers in newspapers, it conforms to the “Testing Method for Hunter Whiteness of Paper and Pulp” described in JIS P 8123. Measured at least 50% or more, and the whiteness is preferably 52 to 56%, more preferably 53 to 55%.
新聞用紙の白紙不透明度は、印刷時の裏抜けが発生し難いという点から不透明度は高いものが求められるが、JIS P 8138に記載の「紙の不透明度試験方法」に準拠して測定して、91〜95%、さらには92〜94%であることが好ましい。 Newspaper paper opacity is required to have high opacity because it is difficult to see through during printing, but it is measured in accordance with “Paper Opacity Test Method” described in JIS P 8138. Thus, it is preferably 91 to 95%, more preferably 92 to 94%.
また新聞用紙の密度は、近年の軽量化や軽量化に伴う強度維持の点から、JIS P 8118に記載の「紙及び板紙−厚さ及び密度の試験方法」に準拠して測定して、0.55〜0.60g/cm3、さらには0.56〜0.59g/cm3であることが好ましい。 Further, the density of newsprint is measured in accordance with “Paper and paperboard—Test method of thickness and density” described in JIS P 8118 from the viewpoint of maintaining the strength accompanying weight reduction and weight reduction in recent years. .55~0.60g / cm 3, preferably further it is 0.56~0.59g / cm 3.
また紙のMD方向の剛度は、例えば高速輪転印刷に適した腰を付与するという点から、JIS P 8143に記載の「紙のクラークこわさ試験機によるこわさ試験方法」に準拠して測定して、30〜55cm3/100、さらには32〜50cm3/100であることが好ましい。 In addition, the stiffness in the MD direction of the paper is measured in accordance with “a stiffness test method using a paper Clark stiffness tester” described in JIS P 8143, for example, in order to give a waist suitable for high-speed rotary printing. It is preferable that it is 30-55 cm < 3 > / 100, Furthermore, it is 32-50 cm < 3 > / 100.
新聞用紙において用いられるオフセト輪転印刷は、刷版に湿し水と印刷インキとを供給し、次いでブランケットと呼ばれるゴム版にインキを転移させた後、紙に転移させて印刷を行う方法であり、従来の凸版印刷方式に比べて、比較的粘度の高いインキを使用するため、インキの紙層内部への浸透が少なく、インキの着肉性が良好となると共に、印刷後のインキ裏抜けの少ない(不透明度の大きい)利点を有している。 Offset rotary printing used in newsprint is a method in which dampening water and printing ink are supplied to a printing plate, then the ink is transferred to a rubber plate called a blanket, and then transferred to paper for printing. Compared to the conventional letterpress printing method, ink with relatively high viscosity is used, so that the ink does not penetrate into the paper layer, the ink is well-positioned, and there is little ink penetration after printing. It has the advantage (high opacity).
さらに近年では、新聞用紙のカラー化や軽量化に伴い、良好なインキの着肉性や印刷後の高い不透明性が一層求められている。このうち、インキ着肉性を高める手段としては、先に述べたソフトカレンダー等による平坦化処理により新聞用紙を平滑化することが広く行われている。しかし、カレンダー処理のニップ圧力を高くしたり、ニップ数を増やすことで平滑化すれば、インキ着肉性は高まるが、紙の嵩高さが損なわれるために、印刷後の不透明度が低下や、剛度が低くなるため、印刷時の皺発生など走行性不良トラブルの原因となる恐れがある。 Further, in recent years, with the colorization and weight reduction of newsprint, there is a further demand for good ink fillability and high opacity after printing. Of these, as a means for improving ink fillability, it is widely practiced to smooth newspaper paper by the above-described flattening process using a soft calendar or the like. However, if the nip pressure in the calendar process is increased or smoothed by increasing the number of nips, the ink inking property is increased, but the bulkiness of the paper is impaired, so the opacity after printing decreases, Since the rigidity becomes low, it may cause troubles such as poor running performance during printing.
一方で、カレンダー処理を軽減すれば嵩高な紙を得ることはできるが、紙面の着肉性の表裏差が増大し、特に平滑度が低い側の紙面で着肉性が悪くなるため、表と裏とで画像の濃度が著しく異なるという問題が発生する。これは、抄紙工程中、ワイヤーパート、プレスパートでの脱水条件が表面と裏面とで微妙に異なるため、用紙の平滑性に表裏差ができたり、厚さ方向での填料、微細繊維の分布状態が異なったりするために、インキの転移性に表裏差がでるためと考えられている。 On the other hand, if the calendar process is reduced, a bulky paper can be obtained, but the difference in front and back of the paper surface is increased. There arises a problem that the density of the image is significantly different from the back. This is because the dehydration conditions in the wire part and press part are slightly different between the front and back sides during the paper making process, so there is a difference in the smoothness of the paper, and the distribution of filler and fine fibers in the thickness direction. It is considered that there is a difference between the front and the back of the ink transferability.
本発明者らは、JIS P 8124に準拠した坪量が、37〜48g/m2である新聞用紙における湿し水と印刷インキの転写において、該新聞用紙のJIS P 8140に基づく10秒コブサイズ度が30〜300g/m2であり、かつJIS P 3001に基づく吸油度が50〜150秒である関係を有することが好ましいことを知見している。いわゆる親水性と親油性の関係を所定の範囲内に抑えることで、平坦化処理と相俟ってよりオフセット輪転印刷適正を向上させることが可能となる。 In the transfer of dampening water and printing ink on newsprint paper having a basis weight of 37 to 48 g / m 2 according to JIS P 8124, the inventors have a 10 second Cobb sizing degree based on JIS P 8140 of the newsprint paper. Is 30 to 300 g / m 2 , and the oil absorption based on JIS P 3001 is preferably 50 to 150 seconds. By suppressing the relationship between so-called hydrophilicity and lipophilicity within a predetermined range, it is possible to improve the appropriateness of offset rotary printing in combination with the flattening process.
さらに紙の表面強度は、やはり高速輪転印刷における紙質強度を考慮すると、後述するRIテスター((株)明製作所製)による測定において最低限度グレード3以上であることが好ましい。 Furthermore, considering the paper quality strength in high-speed rotary printing, the surface strength of the paper is preferably at least grade 3 or higher as measured by an RI tester (manufactured by Akira Seisakusho Co., Ltd.) described later.
このように、本実施形態に係る新聞用紙は、古紙パルプを50質量%以上も含有した原料パルプに、古紙処理工程にて生じる脱墨フロスを主原料とし、カルシウム、ケイ素及びアルミニウムを合計90質量%以上も含有した再生粒子凝集体を填料として内添して抄造したものである。したがって、本実施形態に係る新聞用紙は、抄造時の灰分歩留まりが高く、ワイヤー摩耗等の抄紙設備の摩耗劣化や印刷設備汚れを殆ど起こすことなく、資源を循環使用して低コストで製造され、優れた紙力が維持されて断紙がないだけでなく、紙粉によるブランケット汚れ、剣先詰まり、色ズレ等もなく、不透明度に優れて裏抜けが少ない。しかも本実施形態に係る新聞用紙は、印刷時、特にカラー印刷時の各種特性にも優れ、例えば12〜17万部/時程度といった高速オフセット輪転カラー印刷等に好適に使用することができる。 As described above, the newsprint according to the present embodiment uses, as a main raw material, deinking floss generated in the waste paper processing step in raw pulp containing 50% by mass or more of waste paper pulp, and a total of 90 masses of calcium, silicon, and aluminum. % Of the regenerated particle agglomerates also contained as a filler. Therefore, the newsprint according to the present embodiment has a high ash yield at the time of papermaking, and is produced at low cost by reusing resources without causing wear deterioration of the papermaking equipment such as wire wear and printing equipment contamination. Excellent paper strength is maintained and there is no paper breakage, and there is no blanket stains due to paper dust, clogging of the sword, color misalignment, etc. Moreover, the newsprint according to the present embodiment is excellent in various characteristics during printing, particularly color printing, and can be suitably used for high-speed offset rotary color printing such as about 1 to 170,000 copies / hour.
次に本発明の新聞用紙を、以下の実施例に基づいてさらに詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。
〔再生粒子凝集体の製造(製造例1〜19及び比較例1〜4)〕
原料として、表1に示すように、脱墨フロス(古紙パルプを製造する古紙処理工程より得られた脱墨フロス、製造例1〜19)又は製紙スラッジ(主に製紙工程から排出される排水・脱水スラッジ、比較(製造)例1〜4)を用い、表1に示す条件の脱水工程、乾燥工程及び焼成工程を経た後、湿式粉砕処理を施して再生粒子凝集体を得た。
さらに製造例15〜17においては、再生粒子をケイ酸ナトリウム溶液(水ガラス)に添加、分散させてスラリーを調製した後、加熱攪拌しながら、液温を約85℃に保持して希硫酸を添加し、シリカゾルを生成させた。次いで反応液のpHを8〜11に調整し、再生粒子の表面にシリカを析出させて、本発明に係るシリカ被覆再生粒子凝集体を得た。
得られた再生粒子凝集体及びシリカ被覆再生粒子凝集体について、カルシウム、ケイ素及びアルミニウムの含有量をそれぞれ酸化物換算で求め、カルシウム、ケイ素及びアルミニウムの合計含有割合を算出した。その結果を表2に示す。また平均粒子径も併せて表2に示す。さらにワイヤー摩耗度、生産性、品質安定性及び外観についても調べた。これらの結果も併せて表2に示す。
Next, the newspaper of the present invention will be described in more detail based on the following examples, but the present invention is not limited to these examples.
[Production of regenerated particle aggregates (Production Examples 1 to 19 and Comparative Examples 1 to 4)]
As shown in Table 1, as a raw material, deinking floss (deinking floss obtained from a waste paper treatment process for producing waste paper pulp, Production Examples 1 to 19) or paper sludge (mainly drainage / drainage discharged from the paper making process) Using dehydrated sludge and comparative (manufacturing) Examples 1 to 4), after undergoing a dehydration step, a drying step and a firing step under the conditions shown in Table 1, a wet pulverization treatment was performed to obtain a regenerated particle aggregate.
Furthermore, in Production Examples 15 to 17, after the regenerated particles were added to and dispersed in a sodium silicate solution (water glass) to prepare a slurry, the liquid temperature was maintained at about 85 ° C. while stirring with heating, and diluted sulfuric acid was added. Addition to produce a silica sol. Subsequently, the pH of the reaction solution was adjusted to 8 to 11, and silica was precipitated on the surface of the regenerated particles to obtain a silica-coated regenerated particle aggregate according to the present invention.
With respect to the obtained regenerated particle aggregate and silica-coated regenerated particle aggregate, the contents of calcium, silicon and aluminum were determined in terms of oxides, respectively, and the total content ratio of calcium, silicon and aluminum was calculated. The results are shown in Table 2. The average particle size is also shown in Table 2. Furthermore, the wire wear degree, productivity, quality stability and appearance were also examined. These results are also shown in Table 2.
なお、表1及び2に示す各種測定値は、以下の方法にて測定した。
(ア)乾燥工程後(焼成工程入口)の乾燥物の平均粒子径
X線マイクロアナライザー(型番:EMAX2770、(株)日立製作所/(株)堀場製作所製)を加速電圧15kVで用い、白黒ポラロイドフィルム(ポラロイド社製、8.5cm×10.8cm)にて、X線マイクロアナライザーディスプレーのX線像を20枚撮影して実測した。
(イ)乾燥工程後(焼成工程入口)の粒子径355〜2000μmの粒子の割合
4.7メッシュの篩にて、粒子径が2000μmを超える乾燥物粒子の質量割合を、42メッシュの篩にて、粒子径が355μm未満の乾燥物粒子の質量割合を、それぞれ測定し、質量割合を算出した。
(ウ)再生粒子凝集体中のカルシウム、ケイ素及びアルミニウムの含有量(酸化物換算)
X線マイクロアナライザー(型番:E−MAX・S−2150、(株)日立製作所/(株)堀場製作所製)にて元素分析を行った。
(エ)再生粒子凝集体の平均粒子径
再生粒子凝集体サンプル10mgをメタノール溶液8mLに添加し、超音波分散機(出力:80W)で3分間分散させた。この溶液をコールターカウンター粒度分布測定装置(TA−II型、COULTER ELECTRONICS社製)にて、50μmのアパチャーを用いて測定した。ただし、50μmのアパチャーで測定不可能なものについては、200μmのアパチャーを使用した。また電解液として、ISOTON II(商品名、COULTER ELECTRONICS社製、0.7%の高純度NaCl水溶液)を用いた。
(オ)ワイヤー摩耗度
摩耗度試験装置(日本フィルコン(株)製)を用い、スラリー濃度2質量%にて3時間
(カ)生産性
原料の脱水効率、生産性及び粉砕に必要な電力を各々4段階評価し、以下の評価基準に基づいて評価した。
(評価基準)
◎:いずれも高い評価でバランスが最もよかった。
○:平均してよい評価であった。
△:脱水効率、生産性及び粉砕に必要な電力のいずれかに問題があった。
×:実操業が困難であった。
(キ)品質安定性
白色度、粒子径、一定時間間隔における生産量の各項目について、変動程度を測定し、変動が少ない順にランク付けを行い、以下の評価基準に基づいて評価した。
(評価基準)
◎:上位10位まで
○:11〜22位
△:23〜25位
×:26位以下
(ク)外観
目視にて再生粒子凝集体の色を観察し、白色と灰色とに区分した。
Various measured values shown in Tables 1 and 2 were measured by the following methods.
(A) Average particle diameter of dried product after drying process (firing process inlet) X-ray microanalyzer (model number: EMAX2770, Hitachi, Ltd./Horiba, Ltd.) at an acceleration voltage of 15 kV, black and white polaroid film Twenty X-ray images of the X-ray microanalyzer display were taken and measured at Polaroid (8.5 cm × 10.8 cm).
(A) Ratio of particles having a particle size of 355 to 2000 μm after the drying step (calcination step inlet) The mass ratio of dry matter particles having a particle size of more than 2000 μm is obtained with a 42 mesh sieve. The mass ratio of dried particles having a particle diameter of less than 355 μm was measured, and the mass ratio was calculated.
(C) Content of calcium, silicon and aluminum in the regenerated particle aggregate (as oxide)
Elemental analysis was performed with an X-ray microanalyzer (model number: E-MAX · S-2150, Hitachi, Ltd./Horiba, Ltd.).
(D) Average particle diameter of regenerated particle aggregate 10 mg of the regenerated particle aggregate sample was added to 8 mL of a methanol solution and dispersed with an ultrasonic disperser (output: 80 W) for 3 minutes. This solution was measured with a Coulter counter particle size distribution measuring apparatus (TA-II type, manufactured by COULTER ELECTRONICS) using an aperture of 50 μm. However, for a 50 μm aperture that cannot be measured, a 200 μm aperture was used. Moreover, ISOTON II (trade name, manufactured by COULTER ELECTRONICS, 0.7% high-purity NaCl aqueous solution) was used as the electrolytic solution.
(E) Degree of wire wear Using an abrasion degree tester (manufactured by Nippon Filcon Co., Ltd.) for 3 hours at a slurry concentration of 2% by mass (F) Productivity Dehydration efficiency of raw materials, productivity and power required for grinding The evaluation was made on a four-point scale and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: All were highly evaluated and the balance was the best.
○: The evaluation may be averaged.
(Triangle | delta): There existed a problem in either the dehydration efficiency, productivity, and the electric power required for a grinding | pulverization.
X: Actual operation was difficult.
(G) Quality stability The degree of variation was measured for each item of whiteness, particle size, and production volume at a fixed time interval, ranked in ascending order of variation, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Up to the top 10 O: 11-22, Δ: 23-25, X: 26 or less (K) Appearance The color of the regenerated particle aggregate was visually observed and classified into white and gray.
表2中のCaO、SiO2、Al2O3は、粒子構成成分中の酸化物換算における3成分の含有比率を、表2中の「合計含有割合」は、粒子中の3成分の合計含有割合を示す。
表2に示された結果から、製造例1〜19の再生粒子凝集体は、いずれもワイヤー摩耗度が低く、生産性及び品質安定性にも優れたものであることがわかる。これに対して比較例1〜4の再生粒子は、いずれもワイヤー摩耗度が高く、生産性及び品質安定性にも劣るものであることがわかる。
CaO, SiO2, and Al2O3 in Table 2 indicate the content ratios of the three components in terms of oxides in the particle constituents, and "Total content ratio" in Table 2 indicates the total content ratio of the three components in the particles.
From the results shown in Table 2, it can be seen that the regenerated particle aggregates of Production Examples 1 to 19 each have a low degree of wire wear and excellent productivity and quality stability. On the other hand, it can be seen that the regenerated particles of Comparative Examples 1 to 4 have a high degree of wire wear and are inferior in productivity and quality stability.
〔新聞用紙の作製(製造例1〜19及び比較例1〜7)〕
表3に示す割合でディンキングパルプ(DIP)、加圧ストーングランドパルプ(PGW)及び針葉樹クラフトパルプ(NBKP)を配合し、レファイナーでフリーネスを120mL C.S.F(JIS P 8121に準拠)に調整したパルプスラリーを得た。このパルプスラリーに対し、絶乾パルプ100質量部あたりカチオン化澱粉を0.5質量部添加し、さらに、填料として前述した製造例1〜19及び比較製造例1〜4で得られた再生粒子を表3に示す割合で添加し、硫酸バンドでpHを調整後、ツインワイヤー抄紙機で表4に示す坪量の新聞用紙を抄造した。また表面サイズ剤として酸化澱粉を両面で1g/m2塗布した。
得られた新聞用紙について、各種物性を調べた。これらの結果を表4に示す。また、市販の新聞用紙を試験紙A〜Cとして準備し、製造例1〜19及び比較例1〜4の新聞用紙と同様に各種物性を調べた。その結果を、比較例5〜7として併せて表4に示す。
[Production of Newspaper (Production Examples 1-19 and Comparative Examples 1-7)]
Dinking pulp (DIP), pressed stone ground pulp (PGW), and softwood kraft pulp (NBKP) were blended in the proportions shown in Table 3, and the freeness was 120 mL with a refiner. S. A pulp slurry adjusted to F (based on JIS P 8121) was obtained. To this pulp slurry, 0.5 part by mass of cationized starch is added per 100 parts by mass of absolutely dry pulp, and the regenerated particles obtained in Production Examples 1 to 19 and Comparative Production Examples 1 to 4 are used as fillers. After adding at the ratio shown in Table 3 and adjusting the pH with a sulfuric acid band, newspaper paper having the basis weight shown in Table 4 was made with a twin wire paper machine. Further, 1 g / m 2 of oxidized starch was applied on both sides as a surface sizing agent.
Various physical properties of the obtained newspaper were examined. These results are shown in Table 4. Moreover, commercially available newsprint was prepared as test papers A to C, and various physical properties were examined in the same manner as the newsprints of Production Examples 1 to 19 and Comparative Examples 1 to 4. The results are shown in Table 4 together as Comparative Examples 5 to 7.
なお、表3及び4に示す各種測定値は、以下の方法にて測定した。
(a)原料パルプ中の各パルプの割合
JIS P 8120に記載の「繊維組成試験方法」に準拠して測定した。
(b)坪量
JIS P 8124に記載の「坪量測定方法」に準拠して測定した。
(c)密度
JIS P 8118に記載の「紙及び板紙−厚さ及び密度の試験方法」に準拠して測定した。
(d)熱水抽出pH
JIS P 8133に記載の「紙、板紙及びパルプ−水抽出液pHの試験方法」に準拠して測定した。
(e)灰分
JIS P 8251に記載の「紙、板紙及びパルプ−灰分試験方法」に準拠して測定した。
(f)コッブ吸水度(サイズ度)
JIS P 8140に記載の「紙及び板紙―吸水度試験方法−コッブ法」に準拠し、測定時間10秒にて測定した。
(g)吸油度
JIS P 3001−1976に記載の、「吸油度試験方法」に準拠し、軽油1号にて測定した。
(h)白色度
JIS P 8123に記載の「紙及びパルプのハンター白色度試験方法」に準拠して測定した。
(i)白紙不透明度
JIS P 8138に記載の「紙の不透明度試験方法」に準拠して測定した。
(j)剛度(MD方向)
JIS P 8143に記載の「紙のクラークこわさ試験機によるこわさ試験方法」に準拠して測定した。
(k)表面強度
紙試料を、実験室の金属ロールからなるカレンダーに、線圧40kg/cmで2回通した後、この紙試料の表面に、RIテスター((株)明製作所製)で、インキタック6(東洋インキ製造(株)製)を用いて印刷した。10cm2あたりの繊維が剥がれた状態を目視にて観察し、以下の評価基準(グレード)に基づいて評価した。
(評価基準)
1:繊維の剥がれかなりあり
2:繊維の剥がれあり
3:繊維の剥がれややあり
4:繊維の剥がれ僅かあり
5:繊維の剥がれ殆どなし
なお実用上は、最低限度グレード3である。
The various measured values shown in Tables 3 and 4 were measured by the following methods.
(A) The ratio of each pulp in raw material pulp It measured based on the "fiber composition test method" of JISP8120.
(B) Basis weight It measured based on the "basis weight measuring method" as described in JISP8124.
(C) Density Measured according to “Paper and paperboard—Test method for thickness and density” described in JIS P 8118.
(D) Hot water extraction pH
It was measured according to “Test method for pH of paper, paperboard and pulp-water extract” described in JIS P 8133.
(E) Ash content Measured according to “Paper, paperboard and pulp-ash content test method” described in JIS P 8251.
(F) Cobb water absorption (size)
In accordance with “paper and paperboard—water absorption test method—Cobb method” described in JIS P 8140, the measurement was performed at a measurement time of 10 seconds.
(G) Oil Absorbance Measured with diesel oil No. 1 in accordance with “Oil Absorbency Test Method” described in JIS P 3001-1976.
(H) Whiteness The whiteness was measured in accordance with “Testing Method for Hunter Whiteness of Paper and Pulp” described in JIS P 8123.
(I) White paper opacity It was measured in accordance with “Paper Opacity Test Method” described in JIS P 8138.
(J) Stiffness (MD direction)
It was measured in accordance with “A stiffness test method using a paper Clark stiffness tester” described in JIS P 8143.
(K) Surface strength After passing a paper sample twice through a calendar made of a metal roll in a laboratory at a linear pressure of 40 kg / cm, the surface of the paper sample was subjected to RI tester (manufactured by Akira Seisakusho). Printing was performed using Ink Tack 6 (manufactured by Toyo Ink Manufacturing Co., Ltd.). The state where the fibers per 10 cm 2 were peeled off was visually observed and evaluated based on the following evaluation criteria (grade).
(Evaluation criteria)
1: There is considerable peeling of the fiber 2: There is peeling of the fiber 3: Slightly peeling of the fiber 4: Slightly peeling of the fiber 5: Little peeling of the fiber In practice, it is grade 3 at the minimum.
次に、製造例1〜19及び比較例1〜7の新聞用紙について、以下の試験例1〜9に基づいて各特性を調べた。その結果を表5に示す。
〔試験例1(ケバ立ち)〕
RI印刷適正試験機((株)明製作所製)にて、試験インクを付与しないゴムロールのままで新聞用紙表面を繰り返し5回印刷した。ルーペを用い、100mm×100mmの範囲で紙ウェブ表面を目視にて観察し、以下の評価基準に基づいて評価した。
(評価基準)
◎:ケバ立ちが非常に少ない。
○:ケバ立ちが少ない。
△:ケバ立ちがやや多い。
×:ケバ立ちが非常に多い。
〔試験例2(インク吸収ムラ)〕
オフセットカラー印刷機(型番:SYSTEM C−20、(株)小森コーポレーション製)を使用し、16万部/時の印刷速度で、藍、赤、黄、墨の順に4色カラー印刷を行った。藍/赤の重色部分のインク濃度ムラを目視にて観察し、以下の評価基準に基づいて評価した。
(評価基準)
◎:インク濃度ムラが全く認められず、均一で鮮明な画像である。
○:インク濃度ムラが殆ど認められず、均一な画像である。
△:インク濃度ムラが認められ、やや不均一な画像である。
×:インク濃度ムラが明らかであり、不均一な画像である。
〔試験例3(ブランケットへの紙粉堆積)〕
(1)前記試験例2と同じオフセットカラー印刷機を使用し、同じ印刷速度で藍、赤、黄、墨の順に4色カラー印刷を行った。10000部の印刷を行った後、ブランケット非画線部への紙粉の堆積度合いを目視にて観察し、以下の評価基準に基づいて評価した。
(評価基準)
◎:紙粉の発生が認められない。
○:紙粉の発生が僅かに認められるが、実用上問題がない。
△:紙粉の発生が明確に認められる。
×:ブランケット上に紙粉が多く堆積し、ブランケットが白くなっている。
(2)オフセット輪転機(東芝オフセット輪転機、(株)東芝製)を使用し、900rpmの印刷速度で墨色単色印刷を行った。6万部印刷後、ブランケット上に堆積している紙粉をかき取り、その質量を測定して100cm2あたりの質量で表した。なお湿し水の膜厚は0.9μmとした。
〔試験例4(印刷後不透明度)〕
前記試験例1と同じRI印刷適正試験機を使用し、墨色インクのインク量を変えて印刷を行った。印刷面の反射率が9%のときの、印刷前の裏面反射率(印刷面の反対面)に対する印刷後の裏面反射率を求めた。なお反射率の測定には、分光白色度測色機(スガ試験機(株)製)を使用した。
〔試験例5(印刷白抜け)〕
前記試験例2と同じオフセットカラー印刷機を使用し、網点面積率30〜100%でオフセット輪転印刷用インク(墨)の単色印刷を行った。網点面積率100%ベタ部について、印刷面の白抜けの程度を目視にて観察し、以下の評価基準に基づいて評価した。
(評価基準)
◎:白抜けが殆ど認められない。
○:白抜けが少ししか認められない。
△:白抜けが認められる。
×:白抜けが著しい。
〔試験例6(ネッパリ性)〕
新聞用紙サンプル2枚を適当な大きさに切断して水に10秒間浸漬した後、2枚を素早く密着させ、線圧100kg/cmでカレンダーに通紙した。24時間室温乾燥した後、引張り試験機(型番:オートグラフAGS−500NG、(株)島津製作所製)を用いて2枚の剥離強度を測定した。なお、数値が大きい程ネッパリ性(粘着性)が高い。
〔試験例7(インク乾燥性)〕
前記試験例2と同じオフセットカラー印刷機を使用し、同じ印刷速度で、植物油含有量が45%の新聞印刷用インクにて藍、赤、黄、墨の順に4色カラー印刷を行った。印刷面と白紙面とが重なるように印刷物500部を重ね合わせ、5kgf(約49N)の荷重で1日間放置した後、白紙面の汚れの程度を目視にて観察し、以下の評価基準に基づいて評価した。
(評価基準)
◎:汚れが殆ど認められない。
○:汚れが少ししか認められない。
△:汚れが認められる。
×:汚れが著しい。
〔試験例8(断紙回数)〕
オフセット輪転機(東芝オフセット輪転機、(株)東芝製)を使用し、900rpmの印刷速度で墨色単色印刷を行い、6万部の印刷の間に、断紙が発生する回数を測定した。
〔試験例9(裏抜け)〕
前記試験例8と同じオフセット輪転機を使用し、同じ印刷速度で墨色単色印刷を行った。6万部印刷後、墨ベタ面を裏面から目視にて観察し、以下の評価基準に基づいて評価した。
(評価基準)
◎:裏抜けが殆ど認められない。
○:裏抜けが少ししか認められない。
△:裏抜けが認められる。
×:裏抜けが著しい。
Next, each characteristic was investigated based on the following test examples 1-9 about the newspapers of manufacture examples 1-19 and comparative examples 1-7. The results are shown in Table 5.
[Test Example 1 (Stuffing)]
Using an RI printing suitability tester (manufactured by Akira Seisakusho Co., Ltd.), the newspaper paper surface was repeatedly printed five times with the rubber roll not applied with the test ink. Using a loupe, the surface of the paper web was visually observed in the range of 100 mm × 100 mm, and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Very little standing
○: Little standing.
(Triangle | delta): There is a little bit of standing.
×: There are very many standing spots.
[Test example 2 (ink absorption unevenness)]
Using an offset color printer (model number: SYSTEM C-20, manufactured by Komori Corporation), four-color printing was performed in the order of indigo, red, yellow, and black at a printing speed of 160,000 copies / hour. The ink density unevenness of the deep blue / red color portion was visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Ink density unevenness is not recognized at all, and the image is uniform and clear.
○: Ink density unevenness is hardly recognized, and the image is uniform.
Δ: Ink density unevenness is recognized and the image is slightly non-uniform.
X: Ink density unevenness is obvious and the image is non-uniform.
[Test Example 3 (Paper dust accumulation on blanket)]
(1) Using the same offset color printer as in Test Example 2, four-color printing was performed in the order of indigo, red, yellow, and black at the same printing speed. After printing 10,000 copies, the degree of paper powder accumulation on the blanket non-image area was visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Generation of paper dust is not recognized.
○: Slight generation of paper dust is observed, but there is no practical problem.
Δ: The occurrence of paper dust is clearly recognized.
X: A lot of paper dust is accumulated on the blanket, and the blanket is white.
(2) Using a web offset press (Toshiba web offset press, manufactured by Toshiba Corp.), black monochrome printing was performed at a printing speed of 900 rpm. After printing 60,000 copies, the paper dust deposited on the blanket was scraped off, and the mass was measured and expressed as the mass per 100 cm 2 . The film thickness of the fountain solution was 0.9 μm.
[Test Example 4 (Opacity after printing)]
Using the same RI printing suitability testing machine as in Test Example 1, printing was performed while changing the ink amount of black ink. The back surface reflectance after printing with respect to the back surface reflectance before printing (opposite surface of the printing surface) when the reflectance of the printing surface was 9% was determined. A spectral whiteness colorimeter (manufactured by Suga Test Instruments Co., Ltd.) was used for the reflectance measurement.
[Test Example 5 (Printing White)]
The same offset color printing machine as in Test Example 2 was used, and single-color printing of offset rotary printing ink (black) was performed at a dot area ratio of 30 to 100%. About a solid part with a halftone dot area ratio of 100%, the degree of white spots on the printed surface was visually observed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Almost no white spots are observed.
○: Little white spots are observed.
Δ: White spots are observed.
X: White spots are remarkable.
[Test Example 6 (Nepari property)]
Two newspaper paper samples were cut to a suitable size and immersed in water for 10 seconds, and then the two sheets were quickly brought into close contact and passed through a calendar at a linear pressure of 100 kg / cm. After drying at room temperature for 24 hours, the peel strength of the two sheets was measured using a tensile tester (model number: Autograph AGS-500NG, manufactured by Shimadzu Corporation). In addition, the larger the numerical value, the higher the Nepari property (adhesiveness).
[Test Example 7 (ink drying property)]
Using the same offset color printing machine as in Test Example 2, four-color printing was performed in the order of indigo, red, yellow, and black with newspaper printing ink having a vegetable oil content of 45% at the same printing speed. Overlap the 500 copies of the printed material so that the printed surface and the white paper surface overlap, and leave it for 1 day under a load of 5 kgf (about 49 N), and then visually observe the degree of dirt on the white paper surface based on the following evaluation criteria: And evaluated.
(Evaluation criteria)
(Double-circle): Dirt is hardly recognized.
○: Only a small amount of dirt is observed.
Δ: Dirt is observed.
X: Dirt is remarkable.
[Test Example 8 (Number of sheet breaks)]
Using an offset rotary press (Toshiba offset rotary press, manufactured by Toshiba Corporation), black monochrome printing was performed at a printing speed of 900 rpm, and the number of occurrences of sheet breakage was measured during 60,000 copies.
[Test Example 9 (Back-through)]
Using the same web offset press as in Test Example 8, black single color printing was performed at the same printing speed. After printing 60,000 copies, the black solid surface was visually observed from the back side and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: Almost no see-through is observed.
○: Only a small amount of strikethrough is recognized.
(Triangle | delta): See-through is recognized.
X: The showthrough is remarkable.
以上の結果から、製造例1〜19の新聞用紙は、カルシウム、ケイ素及びアルミニウムを90質量%以上も含む、脱墨フロスが原料の再生粒子凝集体を填料として、古紙パルプを50質量%以上も含む原料パルプに内添して抄造したものであるので、資源を循環使用して低コストで得られるだけでなく、適度の坪量、密度及び熱水抽出pH、白色度、剛度及び表面強度を有し、また、優れた不透明度と紙力とを兼備したものであることがわかる。しかもこれら製造例1〜19の新聞用紙は、ケバ立ち、インク吸収ムラ、ブランケットへの紙粉の堆積及び断紙が全く又は殆どなく、さらに印刷後不透明度も高く、印刷白抜けや裏抜けも全く又は殆どないので、例えば高速オフセット輪転印刷に非常に適した特性を具備していることがわかる。
これに対して比較例1〜4の新聞用紙は、脱墨フロスではなく、製紙スラッジを原料とした再生粒子が填料として用いられており、しかも原料パルプとして古紙パルプの使用量が少ないものであるので、省資源化や低コスト化が図られず、しかもケバ立ち、インク吸収ムラ、ブランケットへの紙粉の堆積、断紙に加え、印刷後不透明度、印刷白抜けや裏抜けの殆どが悪い結果で、高速オフセット印刷に適した特性を具備していないことがわかる。
また比較例5〜7の市販の新聞用紙も、製造例1〜19と比較し、ケバ立ち、インク吸収ムラ、ブランケットへの紙粉の堆積、断紙に加え、印刷後不透明度、印刷白抜けや裏抜けの殆どが悪い結果で、本発明が高速、カラー、高精細オフセット輪転印刷により適した特性を具備していることがわかる。
From the above results, the newspapers of Production Examples 1 to 19 contain calcium, silicon, and aluminum in an amount of 90% by mass or more, and the deinked floss is made of recycled particle aggregates as raw materials, and the waste paper pulp is in an amount of 50% by mass or more. Since it is made by adding paper to the raw material pulp that contains it, not only can it be obtained at low cost by recycling resources, but it also has an appropriate basis weight, density and hot water extraction pH, whiteness, stiffness and surface strength. It can also be seen that it has both excellent opacity and paper strength. Moreover, these newsprints of Production Examples 1 to 19 have no or little fluffing, ink absorption unevenness, accumulation of paper dust on the blanket and paper breakage, and high opacity after printing. It can be seen that it has characteristics that are very suitable for, for example, high speed web offset printing because there is little or no.
On the other hand, the newspapers of Comparative Examples 1 to 4 are not deinked floss, but regenerated particles made from paper sludge are used as fillers, and the amount of used paper pulp is small as raw material pulp. Therefore, resource saving and cost reduction are not achieved, and in addition to eruption, ink absorption unevenness, paper powder accumulation on the blanket, and paper breakage, most of opacity after printing, white spots on prints and back-through are bad. As a result, it is understood that the characteristics suitable for high-speed offset printing are not provided.
In addition, the commercially available newsprint of Comparative Examples 5 to 7 is also less crisp, ink absorption unevenness, paper powder accumulation on the blanket, paper breakage, opacity after printing, and printing blank compared to Production Examples 1 to 19. It can be seen that the present invention has characteristics more suitable for high-speed, color, and high-definition offset rotary printing, with almost no result of bad show-through and show-through.
本発明の新聞用紙は、例えばサテライト型やタワープレス型のオフセットカラー印刷機等における高速オフセットカラー印刷に特に好適な新聞用紙として使用することができる。 The newsprint of the present invention can be used as newsprint particularly suitable for high-speed offset color printing in, for example, satellite-type or tower press-type offset color printing machines.
Claims (3)
前記填料が古紙の処理工程から排出される脱墨フロスを主原料とし、
前記主原料を脱水工程、乾燥工程、焼成工程及び粉砕工程を経て、前記焼成工程において凝集させて得られた再生粒子凝集体の表面がシリカで被覆され、下記組成のシリカ被覆再生粒子凝集体が前記填料として内添され、
前記パルプが、古紙パルプ50〜100質量%からなり、
JIS P 8124に準拠した坪量が37〜48g/m2であり、
紙中にJIS P 8251に準拠して測定した紙灰分が4〜15質量%含有され、
JIS P 8143に準拠して測定したクラークこわさが30〜55cm3/100である、
ことを特徴とする再生粒子内添新聞用紙。
(組成)
前記シリカ被覆再生粒子凝集体は、シリカ被覆再生粒子凝集体の構成成分がカルシウム、ケイ素及びアルミニウムを、酸化物換算で30〜62:29〜55:9〜35の質量割合で含有したシリカ被覆再生粒子凝集体。 Newspaper with internal filler in pulp,
The main material is deinked floss discharged from the waste paper processing process,
The surface of the regenerated particle aggregate obtained by aggregating the main raw material through the dehydration step, drying step, firing step and grinding step in the firing step is coated with silica, and the silica-coated regenerated particle aggregate having the following composition Is internally added as the filler,
The pulp comprises 50-100% by weight of waste paper pulp,
The basis weight according to JIS P 8124 is 37 to 48 g / m 2 ,
The paper ash content measured according to JIS P 8251 is contained in the paper in an amount of 4 to 15% by mass,
Clark stiffness was measured according to JIS P 8143 is 30~55cm 3/100,
Recycled particle-attached newsprint.
(composition)
The silica-coated regenerated particle aggregate is a silica-coated regenerated particle whose constituent components of the silica-coated regenerated particle aggregate contain calcium, silicon, and aluminum in a mass ratio of 30 to 62:29 to 55: 9 to 35 in terms of oxides. Particle aggregate.
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