JPWO2018230683A1 - Coated paper for printing - Google Patents
Coated paper for printing Download PDFInfo
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- JPWO2018230683A1 JPWO2018230683A1 JP2019525544A JP2019525544A JPWO2018230683A1 JP WO2018230683 A1 JPWO2018230683 A1 JP WO2018230683A1 JP 2019525544 A JP2019525544 A JP 2019525544A JP 2019525544 A JP2019525544 A JP 2019525544A JP WO2018230683 A1 JPWO2018230683 A1 JP WO2018230683A1
- Authority
- JP
- Japan
- Prior art keywords
- printing
- weight
- paper
- pigment
- coating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007639 printing Methods 0.000 title claims abstract description 100
- 239000000049 pigment Substances 0.000 claims abstract description 136
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 132
- 239000011247 coating layer Substances 0.000 claims abstract description 87
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims description 81
- 239000011248 coating agent Substances 0.000 claims description 78
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 2
- 229940097275 indigo Drugs 0.000 claims description 2
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 19
- 239000000123 paper Substances 0.000 description 149
- 235000010216 calcium carbonate Nutrition 0.000 description 61
- 239000011148 porous material Substances 0.000 description 34
- 239000007788 liquid Substances 0.000 description 27
- 239000000853 adhesive Substances 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 24
- 238000000034 method Methods 0.000 description 21
- 239000007787 solid Substances 0.000 description 21
- 239000004816 latex Substances 0.000 description 20
- 229920000126 latex Polymers 0.000 description 20
- 229920002472 Starch Polymers 0.000 description 17
- 235000019698 starch Nutrition 0.000 description 17
- 239000010410 layer Substances 0.000 description 13
- 239000001254 oxidized starch Substances 0.000 description 13
- 235000013808 oxidized starch Nutrition 0.000 description 13
- 239000008107 starch Substances 0.000 description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910001868 water Inorganic materials 0.000 description 13
- 238000005259 measurement Methods 0.000 description 12
- 229920001131 Pulp (paper) Polymers 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 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 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011146 organic particle Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000012463 white pigment Substances 0.000 description 4
- 229920002261 Corn starch Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000003490 calendering Methods 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- -1 deramikaolin Chemical compound 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 206010016807 Fluid retention Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000009499 grossing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 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
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 238000009993 causticizing Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000962 poly(amidoamine) Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
Landscapes
- Paper (AREA)
Abstract
原紙の少なくとも片面に２層以上の顔料塗工層を備え、最外顔料塗層が０．８０μｍ以下の平均粒子径（Ｄ５０）を有する炭酸カルシウムを含む、印刷用塗工紙。当該印刷用塗工紙は印刷光沢度と優れたインキ乾燥性を両立し、印刷品質に優れる。A coated paper for printing, comprising two or more pigment coating layers on at least one side of a base paper, and the outermost pigment coating layer containing calcium carbonate having an average particle diameter (D50) of 0.80 μm or less. The printing coated paper has both printing glossiness and excellent ink drying property, and is excellent in printing quality.
Description
本発明はインキ乾燥性と印刷光沢度を両立した印刷用塗工紙に関する。 The present invention relates to a coated paper for printing which has both ink dryability and printing glossiness.
塗工紙は光沢塗工紙と艶消し塗工紙に大別される。光沢塗工紙には、従来高級印刷に用いられていたアート紙、スーパーアート紙、あるいはカタログ、パンフレットなどに用いられるコート紙等があり、これらは印刷仕上がりが白紙光沢度も印刷光沢度も高いグロス調となる。 Coated paper is roughly classified into gloss coated paper and matte coated paper. Gloss coated papers include art papers, super art papers, and coated papers used in catalogs, pamphlets, etc., which have been used for high-grade printing, and these have a high finish and high print gloss. It becomes glossy.
艶消し塗工紙とは光沢塗工紙よりも白紙光沢度や印刷光沢度が低い塗工紙であり、ダル調塗工紙、マット調塗工紙がある。特にマット調塗工紙は、光沢塗工紙に比べて白紙光沢度と印刷光沢度の差異が大きく、印刷後の文字部が読みやすいことから、近年需要が増えている。マット調塗工紙を製造する方法としては、粒子径の大きな顔料を塗工用顔料として使用することや、顔料塗工後にカレンダー処理を行わないことで、紙表面の凹凸を大きくするなどの方法が挙げられる。マット調印刷用塗工紙は光沢塗工紙に比べて表面の凹凸が大きく、紙の表面にのったインキが沈み込みやすい。印刷濃度を上げるためにはインキを多めに転移させる必要があるため、マット調印刷用塗工紙はインキの転移量が多くなりインキ乾燥性が低下する傾向にある。インキ乾燥性が劣ると、印刷後の印字物を重ねた際にインキが他方に転移する裏移りや印刷面の擦れ汚れ、また作業が次工程に進めず作業効率が低下するなどの問題が発生する。そのため、特にマット調印刷用塗工紙においては高いインキ乾燥性が求められる。 The matte coated paper is a coated paper having a lower whiteness or printing gloss than the glossy coated paper, and includes dull-like coated paper and matte-like coated paper. In particular, matte coated paper has a large difference between the white paper glossiness and the printing glossiness as compared with glossy coated paper, and the character portion after printing is easy to read, so that the demand has increased in recent years. As a method for producing a matte coated paper, a method such as using a pigment having a large particle size as a coating pigment or not performing calendar treatment after coating the pigment to increase the unevenness of the paper surface, etc. Is mentioned. The matte printing coated paper has larger surface irregularities than the gloss coated paper, and the ink on the surface of the paper easily sinks. Since it is necessary to transfer a large amount of ink in order to increase the printing density, the amount of transferred ink in the matte printing paper tends to increase and the ink drying property tends to decrease. If the ink dryness is inferior, there will be problems such as ink transfer to the other side when printing after printing, set-off and rubbing stains on the printed surface, and work efficiency declines because the work does not proceed to the next process. To do. Therefore, high ink drying property is required especially for coated paper for matte printing.
一方で、インキ乾燥性が高いと、印刷されたインキ面のレベリングが進まずに印刷面に凹凸ができてしまい印刷光沢度は低くなる場合が多い。印刷光沢度を高める手法として、カレンダー処理で平滑性を追求する方法がある。しかし、印刷光沢度とともに白紙光沢度も高くなってしまうため、マット調印刷用塗工紙には不向きである。高いインキ乾燥性と高い印刷光沢を両立するために、特許文献１には顔料塗工層に特定の接着剤を特定量用いることが開示されている。 On the other hand, when the ink drying property is high, the leveling of the printed ink surface does not proceed and unevenness is formed on the printing surface, and the printing glossiness is often low. As a method of increasing the printing glossiness, there is a method of pursuing smoothness by calendar processing. However, it is not suitable for coated paper for matte tone printing because the glossiness of white paper increases with the glossiness of printing. In order to achieve both high ink drying property and high print gloss, Patent Document 1 discloses that a specific amount of a specific adhesive is used in the pigment coating layer.
本発明は、印刷光沢度と優れたインキ乾燥性を両立し、印刷品質に優れた印刷用塗工紙、特にマット調印刷用塗工紙を提供することを課題とする。 An object of the present invention is to provide a coated paper for printing, which has both printing glossiness and excellent ink drying property, and is excellent in printing quality, particularly a matte printing coated paper.
本発明者は上記課題に鑑み、誠意検討を重ねた結果、特定の微粒炭酸カルシウムを含む顔料塗工層を備える印刷用塗工紙が上記課題を解決することを見出した。すなわち、前記課題は以下の本発明によって解決される。
（態様１）原紙の少なくとも片面に２層以上の顔料塗工層を備え、
最外顔料塗層が０．８０μｍ以下の平均粒子径（Ｄ５０）を有する炭酸カルシウムを含む、印刷用塗工紙。
（態様２）前記最外顔料塗工層における顔料１００重量部中に、前記炭酸カルシウムを４０重量部以上含む、態様１に記載の印刷用塗工紙。
（態様３）前記炭酸カルシウムの平均粒子径（Ｄ５０）が０．５０〜０．７５μｍである、態様１または２に記載の印刷用塗工紙。
（態様４）白紙光沢度が４０％以下であり、藍紅印刷部の印刷光沢度が５８〜７５％である態様１に記載の印刷用塗工紙。
（態様５）前記最外顔料塗工層における顔料１００重量部中に、前記炭酸カルシウムを７５重量部以上含む、態様２に記載の印刷用塗工紙。
（態様６）最外顔料塗工層の塗工量が最内顔料塗工層の塗工量より多い、態様１〜５のいずれかに記載の印刷用塗工紙。
（態様７）白紙光沢度が４０％以下である態様１〜６のいずれかに記載の印刷用塗工紙。In view of the above problems, the present inventor has conducted sincerity studies, and as a result, found that a printing coated paper having a pigment coating layer containing specific fine calcium carbonate solves the above problems. That is, the said subject is solved by the following this invention.
(Aspect 1) Two or more pigment coating layers are provided on at least one side of the base paper,
A coated paper for printing, wherein the outermost pigment coating layer contains calcium carbonate having an average particle diameter (D50) of 0.80 μm or less.
(Aspect 2) The coated printing paper according to Aspect 1, wherein 40 parts by weight or more of the calcium carbonate is contained in 100 parts by weight of the pigment in the outermost pigment coating layer.
(Aspect 3) The printing coated paper according to Aspect 1 or 2, wherein the calcium carbonate has an average particle diameter (D50) of 0.50 to 0.75 μm.
(Aspect 4) The coated paper for printing according to Aspect 1, wherein the glossiness of white paper is 40% or less, and the glossiness of the deep red printing portion is 58 to 75%.
(Aspect 5) The coated printing paper according to aspect 2, wherein the calcium carbonate is contained in an amount of 75 parts by weight or more in 100 parts by weight of the pigment in the outermost pigment coating layer.
(Aspect 6) The printing coated paper according to any one of Aspects 1 to 5, wherein the coating amount of the outermost pigment coating layer is larger than the coating amount of the innermost pigment coating layer.
(Aspect 7) The coated paper for printing according to any one of Aspects 1 to 6, which has a white paper gloss of 40% or less.
本発明により、優れた印刷光沢度と優れたインキ乾燥性を両立し、印刷品質に優れた印刷用塗工紙、特にマット調印刷用塗工紙を提供できる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a coated paper for printing which has both excellent printing glossiness and excellent ink drying property and is excellent in printing quality, particularly a coated paper for matte printing.
以下、本発明を詳細に説明する。本発明において「〜」はその端点を含む。すなわち「Ｘ〜Ｙ」はＸおよびＹの値を含む。また、「ＸまたはＹ」はＸ、Ｙのいずれか一つ、あるいは双方を意味する。 Hereinafter, the present invention will be described in detail. In the present invention, “to” includes its endpoints. That is, “X to Y” includes X and Y values. Further, “X or Y” means either one or both of X and Y.
１．印刷用塗工紙
印刷用塗工紙とは原紙の上に設けられた顔料塗工層を備える印刷用の紙である。顔料塗工層とは白色顔料を主成分とする層である。本発明の印刷用塗工紙は、顔料塗工層が２層以上で、かつ最外顔料塗工層が０．８０μｍ以下の平均粒子径（Ｄ５０）を有する炭酸カルシウムを含有する。本発明の印刷用塗工紙は、用紙表面にオフセット印刷、グラビア印刷、オンデマンド印刷（レーザー方式、インクジェット方式、電子写真方式）、などの商業印刷を施すことができ、用途しては書籍、雑誌、ポスター、封筒、カレンダーなどが挙げられるが、これらに限定されない。1. Coated paper for printing Coated paper for printing is a paper for printing having a pigment coating layer provided on a base paper. The pigment coating layer is a layer containing a white pigment as a main component. The printing coated paper of the present invention contains two or more pigment coating layers, and the outermost pigment coating layer contains calcium carbonate having an average particle diameter (D50) of 0.80 μm or less. The printing coated paper of the present invention can be subjected to commercial printing such as offset printing, gravure printing, on-demand printing (laser system, ink jet system, electrophotographic system) on the surface of the paper, and is used as a book, Examples include, but are not limited to magazines, posters, envelopes, calendars, and the like.
（１）顔料塗工層
１）顔料
顔料塗工層は平均粒子径（Ｄ５０）が０．８０μｍ以下の炭酸カルシウム（以下、「第１の炭酸カルシウム」ともいう）を含む。Ｄ５０は体積５０％平均粒子径である。沈降法による顔料の粒度分布およびＤ５０は、Ｍａｌｖｅｒｎ社製、マスターサイザー３０００等により測定可能である。炭酸カルシウムのＤ５０の上限は０．７５μｍ以下であることが好ましく、０．７０μｍ以下であることが好ましい。下限は０．５０μｍ以上であることが好ましい。(1) Pigment coating layer 1) Pigment The pigment coating layer contains calcium carbonate having an average particle diameter (D50) of 0.80 μm or less (hereinafter, also referred to as “first calcium carbonate”). D50 is a volume 50% average particle diameter. The particle size distribution and D50 of the pigment by the sedimentation method can be measured with a Mastersizer 3000 manufactured by Malvern. The upper limit of D50 of calcium carbonate is preferably 0.75 μm or less, and more preferably 0.70 μm or less. The lower limit is preferably 0.50 μm or more.
顔料塗工層が原紙の両面に存在する場合は、少なくとも一方の面の最外顔料塗工層が第１の炭酸カルシウムを含めばよい。 When the pigment coating layer is present on both sides of the base paper, the outermost pigment coating layer on at least one side may contain the first calcium carbonate.
最外顔料塗工層における第１の炭酸カルシウムの配合量の下限は、当該顔料塗工層中の顔料１００重量部中、４０重量部以上であることが好ましく、４５重量部以上であることが好ましい。しかしながら最外顔料塗工層の第１の炭酸カルシウムの配合量が多すぎると白紙光沢度が過度に上昇してマット調が損なわれるのでその上限は当該顔料塗工層中の顔料１００重量部中、７０重量部以下であることが好ましく、６０重量部以下であることがより好ましく、５５重量部以下であることがさらに好ましい。最外塗工層以外の顔料塗工層は第１の炭酸カルシウムを含有しなくてもよいが、含有する場合、当該量は前記範囲であることが好ましい。第１の炭酸カルシウムは、重質炭酸カルシウムまたはパルプ製造工程の苛性化工程で製造された軽質炭酸カルシウム（苛性化軽質炭酸カルシウム、特許５２７４０７７号公報参照）であることが好ましい。 The lower limit of the blending amount of the first calcium carbonate in the outermost pigment coating layer is preferably 40 parts by weight or more, and more preferably 45 parts by weight or more, with respect to 100 parts by weight of the pigment in the pigment coating layer. preferable. However, if the blending amount of the first calcium carbonate in the outermost pigment coating layer is too large, the glossiness of the white paper increases excessively and the matteness is impaired. Therefore, the upper limit is 100 parts by weight of the pigment in the pigment coating layer. It is preferably 70 parts by weight or less, more preferably 60 parts by weight or less, and further preferably 55 parts by weight or less. The pigment coating layers other than the outermost coating layer may not contain the first calcium carbonate, but when it is contained, the amount is preferably within the above range. The first calcium carbonate is preferably heavy calcium carbonate or light calcium carbonate manufactured in the causticizing step of the pulp manufacturing step (causticized light calcium carbonate, see Japanese Patent No. 5274077).
顔料塗工層中の第１の炭酸カルシウム以外の白色顔料として、当該分野で通常使用されている顔料を用いることができる。その例としては、カオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコアーシェル型などの有機顔料が挙げられる。これらの顔料は複数種を組合せて使用してもよい。 As the white pigment other than the first calcium carbonate in the pigment coating layer, a pigment usually used in this field can be used. Examples thereof include kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin. Inorganic pigments such as white and organic pigments such as solid type, hollow type, or core-shell type are mentioned. You may use these pigments in combination of multiple types.
第１の炭酸カルシウム以外の白色顔料として、Ｄ５０が０．８０μｍを超える重質炭酸カルシウムまたは軽質炭酸カルシウム（以下、「第２の炭酸カルシウム」ともいう）を用いることが好ましい。炭酸カルシウムは接着剤（バインダー）との結着性に優れかつ白色度を向上するので、インキ乾燥性を向上し、さらに高い白色度および印刷適性を達成できる。最外顔料塗工層中の顔料１００重量部中、第１および第２の炭酸カルシウムの合計量は９０重量部以上が好ましく、１００重量部がより好ましい。それ以外の顔料塗工層中の第１および第２の炭酸カルシウムの合計量は限定されないが前記範囲であることが好ましい。第２の炭酸カルシウムは、重質炭酸カルシウムまたは苛性化軽質炭酸カルシウムであることが好ましい。 As the white pigment other than the first calcium carbonate, it is preferable to use heavy calcium carbonate or light calcium carbonate having a D50 of more than 0.80 μm (hereinafter, also referred to as “second calcium carbonate”). Since calcium carbonate has excellent binding properties with an adhesive (binder) and improves whiteness, it improves ink drying properties and can achieve higher whiteness and printability. In 100 parts by weight of the pigment in the outermost pigment coating layer, the total amount of the first and second calcium carbonates is preferably 90 parts by weight or more, and more preferably 100 parts by weight. The total amount of the first and second calcium carbonates in the other pigment coating layers is not limited, but is preferably within the above range. The second calcium carbonate is preferably ground calcium carbonate or causticized light calcium carbonate.
２）接着剤
顔料塗工層はマトリックスとして接着剤（バインダー）を含む。接着剤は限定されず、公知の接着剤を使用できる。その例としては、スチレン・ブタジエン系共重合体、スチレン・アクリル系共重合体、エチレン・酢酸ビニル系共重合体、ブタジエン・メチルメタクリレート系共重合体、酢酸ビニル・ブチルアクリレート系共重合体、無水マレイン酸共重合体、アクリル酸・メチルメタクリレート系共重合体等のラテックス；完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、アセトアセチル変性ポリビニルアルコール等のポリビニルアルコール類；カゼイン、大豆蛋白、合成蛋白等の蛋白質類；酸化澱粉、陽性澱粉、尿素燐酸エステル化澱粉、ヒドロキシエチルエーテル化澱粉などのエーテル化澱粉、デキストリン等の澱粉類；カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシメチルセルロース等のセルロース誘導体等が挙げられる。これらの複数種を組合せて使用できる。2) Adhesive The pigment coating layer contains an adhesive (binder) as a matrix. The adhesive is not limited, and known adhesives can be used. Examples thereof include styrene / butadiene type copolymers, styrene / acrylic type copolymers, ethylene / vinyl acetate type copolymers, butadiene / methyl methacrylate type copolymers, vinyl acetate / butyl acrylate type copolymers, anhydrous Latex of maleic acid copolymer, acrylic acid / methyl methacrylate copolymer, etc .; polyvinyl alcohol such as fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol; casein, soybean Proteins such as proteins and synthetic proteins; oxidized starch, positive starch, urea phosphate esterified starch, etherified starch such as hydroxyethyl etherified starch, starches such as dextrin; carboxymethyl cellulose, hydroxyethyl cellulose, hydrid Cellulose derivatives such as carboxymethyl cellulose and the like. These plural types can be used in combination.
接着剤の量は、印刷適性、塗工適性の点から、全顔料塗工層中の顔料１００重量部に対して５〜３０重量部であることが好ましく、８〜２５重量部であることがより好ましい。接着剤の総量が２５重量部を越える場合、顔料塗工液の粘度が高くなり塗工時に操業トラブルが生じ易い。さらに、インキの乾燥性が低下する傾向が見られる。一方、接着剤の総量が５重量部未満であると十分な表面強度を得にくくなる。 From the viewpoints of printability and coating suitability, the amount of the adhesive is preferably 5 to 30 parts by weight, and preferably 8 to 25 parts by weight, based on 100 parts by weight of the pigment in the entire pigment coating layer. More preferable. When the total amount of the adhesive exceeds 25 parts by weight, the viscosity of the pigment coating solution becomes high and operating troubles are likely to occur during coating. Further, there is a tendency that the drying property of the ink is lowered. On the other hand, if the total amount of the adhesive is less than 5 parts by weight, it becomes difficult to obtain sufficient surface strength.
本発明の印刷用塗工紙は、全接着剤中１０〜８０重量％の、エマルションの形態であるスチレン・ブタジエン系共重合体ラテックスを含むことが好ましく、１５〜７０重量％のラテックスを含むことが好ましく、ラテックスとしてはスチレン・ブタジエン系ラテックスを含有することが好ましい。本発明の印刷用塗工紙は２層以上顔料塗工層を備えるが、原紙に最も近い層は全接着剤中１０〜８０重量％のラテックスを含むことが好ましく、原紙に遠い層は３０〜６０重量％のラテックスを含むことが好ましい。他の接着剤としては澱粉類を用いることが特に好ましく、その量は原紙に最も近い層では全接着剤中３０〜９０重量％であることが好ましく、原紙に遠い層では４０〜７０重量％であることが好ましい。ラテックスと比較して澱粉類は顔料塗工液の保水性を高めるため、原紙への塗工液の沈み込みが生じにくく、顔料塗工層で原紙を効果的に被覆することができる。言い換えれば、澱粉類を使用すると、顔料塗工層による原紙の被覆性が良好となる。その結果、印刷品質、特に印刷光沢度の向上と、インキ乾燥性の向上が期待できる。本発明においては、ラテックスと澱粉類の割合が、３：５〜５：７であることが好ましい。 The coated paper for printing of the present invention preferably contains 10 to 80% by weight of the styrene / butadiene copolymer latex in the form of an emulsion in the total adhesive, and preferably 15 to 70% by weight of the latex. Is preferred, and the latex preferably contains a styrene-butadiene-based latex. The coating paper for printing of the present invention comprises two or more pigment coating layers, but the layer closest to the base paper preferably contains 10 to 80% by weight of latex in the total adhesive, and the layer far from the base paper is 30 to 30% by weight. It preferably comprises 60% by weight of latex. It is particularly preferable to use starches as the other adhesive, and the amount thereof is preferably 30 to 90% by weight in the total adhesive in the layer closest to the base paper and 40 to 70% by weight in the layer far from the base paper. Preferably there is. Since starches increase the water retention of the pigment coating liquid as compared with latex, it is difficult for the coating liquid to sink into the base paper, and the pigment coating layer can effectively coat the base paper. In other words, the use of starch improves the coverage of the base paper with the pigment coating layer. As a result, it can be expected that the printing quality, especially the printing glossiness, and the ink drying property are improved. In the present invention, the ratio of latex to starch is preferably 3: 5 to 5: 7.
３）他の添加剤
顔料塗工層は、必要に応じて、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、染料、着色用顔料等、通常の塗工紙用顔料に配合される各種助剤を含んでいてもよい。本発明においては、前述の白色顔料より大きな粒子径を有する有機物粒子を用いることが好ましい。当該有機物粒子を原紙から最も遠い最外塗工層に含有することで、印刷後の紙同士の擦れによる紙面汚れが低減し、印刷適性を向上させることができる。有機物粒子としては蒸煮をしていない澱粉粒が好ましく、前述の顔料に対し０．５〜１０重量％含有させることで、上記効果を得ることができる。有機物粒子の粒子径は、レーザー回析式粒度分布測定機で測定した平均粒子径（Ｄ５０）が８〜２５μｍであることが好ましい。3) Other additives The pigment coating layer can be used as a pigment for ordinary coated paper such as a dispersant, a thickener, a water retention agent, a defoaming agent, a water resistant agent, a dye, a coloring pigment, etc., if necessary. It may contain various auxiliary agents to be blended. In the present invention, it is preferable to use organic particles having a particle size larger than that of the above white pigment. By including the organic particles in the outermost coating layer farthest from the base paper, paper stains due to rubbing between the printed papers can be reduced, and printability can be improved. As the organic particles, starch granules that have not been steamed are preferable, and the above effects can be obtained by containing 0.5 to 10% by weight of the above-mentioned pigment. Regarding the particle size of the organic particles, the average particle size (D50) measured by a laser diffraction type particle size distribution measuring device is preferably 8 to 25 μm.
４）塗工量
顔料塗工層の塗工量は、片面あたり固形分で２ｇ／ｍ２以上が好ましく、５ｇ／ｍ２以上がより好ましく、１０ｇ／ｍ２以上がさらに好ましい。塗工量が５ｇ／ｍ２未満では、紙基材表面の凹凸を十分に覆うことができないため、印刷インキの受理性が著しく低下することがある。一方、顔料塗工層の塗工量は、５０ｇ／ｍ２以下が好ましく、４０ｇ／ｍ２以下がより好ましく、３５ｇ／ｍ２以下がさらに好ましい。当該塗工量は片面あたりの全顔料塗工層の合計の値であるが、最内顔料塗工層（原紙に隣接する顔料塗工層）の塗工量は２〜１５ｇ／ｍ２が好ましく、より好ましくは５〜１２ｇ／ｍ２である。また、最外顔料塗工層の塗工量は６〜２０ｇ／ｍ２が好ましく、より好ましくは８〜１５ｇ／ｍ２である。インキ乾燥性には、最外塗工層の影響が大きいため、最外塗工層の塗工量は最内顔料塗工層の塗工量よりも多いことが好ましい。4) Coating amount The coating amount of the pigment coating layer is preferably 2 g / m 2 or more, more preferably 5 g / m 2 or more, and further preferably 10 g / m 2 or more in terms of solid content per one surface. If the coating amount is less than 5 g / m 2 , the irregularities on the surface of the paper substrate cannot be sufficiently covered, so that the acceptability of the printing ink may be significantly reduced. On the other hand, the coating amount of the pigment coating layer is preferably 50 g / m 2 or less, more preferably 40g / m 2, 35g / m 2 or less is more preferred. The coating amount is the total value of all the pigment coating layers on one side, but the coating amount of the innermost pigment coating layer (pigment coating layer adjacent to the base paper) is preferably 2 to 15 g / m 2. , And more preferably 5 to 12 g / m 2 . Further, the coating amount of the outermost pigment coating layer is preferably 6 to 20 g / m 2 , and more preferably 8 to 15 g / m 2 . Since the outermost coating layer has a great influence on the ink drying property, it is preferable that the outermost coating layer is coated more than the innermost pigment coating layer.
（２）原紙
１）パルプ
原紙には公知のパルプを使用できる。公知のパルプとしては、化学パルプ、砕木パルプ（ＧＰ）、リファイナー砕木パルプ（ＲＧＰ）、サーモメカニカルパルプ（ＴＭＰ）、ケモサーモメカニカルパルプ（ＣＴＭＰ）、ケミグランドパルプ（ＣＧＰ）、セミケミカルパルプ（ＳＣＰ）、古紙パルプなどが挙げられる。本発明においては、化学パルプを使用することが好ましい。化学パルプには、クラフトパルプ法により製造したものと、亜硫酸パルプ法により製造されたものがあり、本発明においてはその両方を使用することができるが、クラフト法により製造した化学パルプが生産コストの面から好適である。原料パルプに占める化学パルプの含有量は、白色度等の観点から、全パルプ中６０重量％以上が好ましく、８０重量％以上がより好ましく、９０重量％以上がさらに好ましく、９５重量％以上が特に好ましい。(2) Base paper 1) Pulp As the base paper, known pulp can be used. Known pulps include chemical pulp, groundwood pulp (GP), refiner groundwood pulp (RGP), thermomechanical pulp (TMP), chemothermomechanical pulp (CTMP), chemigrand pulp (CGP), semi-chemical pulp (SCP). , Waste paper pulp and the like. In the present invention, it is preferable to use chemical pulp. There are two types of chemical pulp, one produced by the kraft pulp method and the other produced by the sulfite pulp method. In the present invention, both of them can be used. It is preferable from the aspect. From the viewpoint of whiteness and the like, the content of the chemical pulp in the raw material pulp is preferably 60% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, particularly preferably 95% by weight or more, based on the total pulp. preferable.
２）填料
原紙には公知の填料を用いてよい。公知の填料としては、重質炭酸カルシム、軽質炭酸カルシウム、クレー、シリカ、軽質炭酸カルシウム−シリカ複合物、カオリン、焼成カオリン、デラミカオリン、ホワイトカーボン、タルク、炭酸マグネシウム、炭酸バリウム、硫酸バリウム、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、水酸化亜鉛、酸化亜鉛、酸化チタン、ケイ酸ナトリウムの鉱酸による中和で製造される非晶質シリカ等の無機填料や、尿素−ホルマリン樹脂、メラミン系樹脂、ポリスチレン樹脂、フェノール樹脂などの有機填料が挙げられる。この中でも、中性抄紙やアルカリ抄紙における代表的な填料である重質炭酸カルシウムや軽質炭酸カルシウムが不透明度向上のためにも好ましく使用される。填料として使用する炭酸カルシウムは前述の第１の炭酸カルシウムであってもよいし第２の炭酸カルシウムであってもよいが、軽質炭酸カルシウムが好ましい。紙中填料率は特に制限されないが、１〜４０重量％が好ましく、１０〜３５重量％がさらに好ましい。原紙の強度等を考慮すると、より好ましくは１０〜２０重量％である。2) Filler A known filler may be used for the base paper. Known fillers include heavy calcium carbonate, light calcium carbonate, clay, silica, light calcium carbonate-silica composite, kaolin, calcined kaolin, deramikaolin, white carbon, talc, magnesium carbonate, barium carbonate, barium sulfate, water. Inorganic fillers such as aluminum oxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, zinc oxide, titanium oxide, and amorphous silica produced by neutralization of sodium silicate with a mineral acid, urea-formalin resin, melamine Examples include organic fillers such as system resins, polystyrene resins, and phenol resins. Among these, heavy calcium carbonate and light calcium carbonate, which are typical fillers in neutral papermaking and alkaline papermaking, are preferably used for improving opacity. The calcium carbonate used as the filler may be the above-mentioned first calcium carbonate or second calcium carbonate, but light calcium carbonate is preferable. The filler content in the paper is not particularly limited, but is preferably 1 to 40% by weight, more preferably 10 to 35% by weight. Considering the strength of the base paper and the like, it is more preferably 10 to 20% by weight.
３）その他
公知の製紙用添加剤も使用できる。例えば、硫酸バンドや各種のアニオン性、カチオン性、ノニオン性あるいは、両性の歩留まり向上剤、濾水性向上剤、各種紙力増強剤や内添サイズ剤等の抄紙用内添助剤を必要に応じて使用することができる。乾燥紙力向上剤としてはポリアクリルアミド、カチオン化澱粉などが挙げられ、湿潤紙力向上剤としてはポリアミドアミンエピクロロヒドリンなどが挙げられる。これらの薬品は地合や操業性などの影響の無い範囲で添加される。内添サイズ剤としてはアルキルケテンダイマーやアルケニル無水コハク酸、ロジンサイズ剤などが挙げられる。更に、染料、顔料、蛍光増白剤、ｐＨ調整剤、消泡剤、ピッチコントロール剤、スライムコントロール剤等も必要に応じて添加することができる。3) Others Known additives for papermaking can also be used. For example, a sulfuric acid band and various anionic, cationic, nonionic or amphoteric retention improvers, drainage improvers, various paper strength enhancers and internal additives for papermaking such as internal sizing agents are added as necessary. Can be used. Examples of the dry paper strength improver include polyacrylamide and cationized starch, and examples of the wet paper strength improver include polyamidoamine epichlorohydrin. These chemicals are added within a range that does not affect formation and operability. Examples of the internally added sizing agent include alkyl ketene dimer, alkenyl succinic anhydride, and rosin sizing agent. Further, dyes, pigments, optical brighteners, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as required.
４）原紙の坪量
本発明の印刷用塗工紙の原紙の坪量は４０〜１６０ｇ／ｍ２が好ましく、４５〜１５０ｇ／ｍ２がより好ましく、５０〜１４０ｇ／ｍ２がさらに好ましい。4) The basis weight of base paper coated printing paper having a basis weight of the present invention of the base paper is preferably 40~160g / m 2, more preferably 45~150g / m 2, more preferably 50~140g / m 2.
５）クリア塗工層
本発明の印刷用塗工紙は、上述した原紙の片面または両面にクリア（透明）塗工層を有していてもよい。原紙上にクリア塗工を施すことにより、原紙の表面強度や平滑性を向上させることができ、また、顔料塗工をする際の塗工適性を向上させることができる。クリア塗工の量は、片面あたり固形分で０．１〜３．０ｇ／ｍ２が好ましく、０．２〜２．０ｇ／ｍ２がより好ましく、さらに好ましくは０．５〜２．０ｇ／ｍ２である。5) Clear coating layer The printing coated paper of the present invention may have a clear (transparent) coating layer on one side or both sides of the above-mentioned base paper. By applying a clear coating on the base paper, it is possible to improve the surface strength and smoothness of the base paper, and it is also possible to improve the coating suitability for pigment coating. The amount of clear coating is preferably 0.1 to 3.0 g / m 2 in terms of solid content on one side, more preferably 0.2 to 2.0 g / m 2 , and even more preferably 0.5 to 2.0 g / m 2. m 2 .
本発明においてクリア塗工とは、例えば、２ロールポンドサイズプレス、ゲートロールコーター、プレメタリングサイズプレス、カーテンコーター、スプレーコーターなどのコータ（塗工機）を使用して、澱粉、酸化澱粉、各種変性澱粉（自家変性、カチオン変性等）などの澱粉類、ポリアクリルアミド、ポリビニルアルコールなどの水溶性高分子を主成分とする塗布塗工液（表面処理液）を、原紙上に塗布塗工（サイズプレス）することをいう。クリア塗工液にサイズ剤を含有させて塗工することもできる。本発明においては澱粉を塗工することが好ましい。 In the present invention, the clear coating means, for example, using a coater (coating machine) such as a 2-roll pond size press, a gate roll coater, a premetering size press, a curtain coater, a spray coater, starch, oxidized starch, A coating solution (surface treatment solution) containing starches such as various modified starches (self-modified, cation-modified, etc.) and water-soluble polymers such as polyacrylamide and polyvinyl alcohol as a main component is applied and coated on the base paper ( Size press). It is also possible to coat the clear coating liquid with a sizing agent. In the present invention, it is preferable to apply starch.
２．製造方法
本発明の印刷用塗工紙は公知の方法で製造できるが、原紙上に、顔料と接着剤を含む顔料塗工液を塗工することにより製造することが好ましい。
（１）原紙の調製
本発明で用いられる原紙に使用される原料についてはすでに述べたとおりである。原紙は公知の抄紙方法で製造される。例えば、トップワイヤー等を含む長網抄紙機、オントップフォーマー、ギャップフォーマ、丸網抄紙機、長網抄紙機と丸網抄紙機を併用した板紙抄紙機、ヤンキードライヤーマシン等を用いて行うことができる。抄紙時のｐＨは、酸性、中性、アルカリ性のいずれでもよいが、中性またはアルカリ性が好ましい。抄紙速度も特に限定されない。本発明で用いられる原紙は、単層でも多層でもよいが、単層の原紙が好適に使用される。2. Manufacturing Method The coated paper for printing of the present invention can be manufactured by a known method, but it is preferably manufactured by coating a base paper with a pigment coating liquid containing a pigment and an adhesive.
(1) Preparation of base paper The raw materials used for the base paper used in the present invention are as described above. The base paper is manufactured by a known papermaking method. For example, use a Fourdrinier paper machine including top wire, an on-top former, a gap former, a reticulated paper machine, a paperboard machine that combines a fourdrinier paper machine and a reticulated paper machine, a Yankee dryer machine, etc. You can The pH during papermaking may be acidic, neutral or alkaline, but is preferably neutral or alkaline. The papermaking speed is also not particularly limited. The base paper used in the present invention may be a single layer or a multilayer, but a single layer base paper is preferably used.
（２）原紙の平滑化処理
得られた原紙に顔料塗工液を塗工する前に、各種カレンダー装置により原紙に平滑化処理を施すことが好ましい。かかるカレンダー装置としては、スーパーカレンダー、ソフトカレンダー等の一般に使用されているカレンダー装置が適宜使用できる。カレンダー仕上げ条件としては、剛性ロールの温度、カレンダー圧力、ニップ数、ロール速度、カレンダー前の紙水分等が、要求される品質に応じて適宜選択される。本発明においては、マット調の風合いを維持したまま平滑性を付与するために原紙にカレンダー処理を施すことが好ましい。原紙にカレンダー処理を施すことで、原紙の平滑性が向上し、顔料塗工適性が向上する。(2) Smoothing Treatment of Base Paper Before applying the pigment coating liquid to the obtained base paper, it is preferable to perform smoothing treatment on the base paper with various calendering devices. As such a calendar device, a commonly used calendar device such as a super calendar or a soft calendar can be appropriately used. As calender finishing conditions, the temperature of the rigid roll, the calender pressure, the number of nips, the roll speed, the paper moisture before the calender, etc. are appropriately selected according to the required quality. In the present invention, the base paper is preferably subjected to a calendering treatment in order to impart smoothness while maintaining the matte texture. By subjecting the base paper to a calendar treatment, the smoothness of the base paper is improved and the pigment coating suitability is improved.
（３）顔料塗工液の調製
顔料塗工液は顔料、接着剤、および必要に応じて添加剤を水に分散または溶解することで調製できる。前述顔料塗工層を形成できるように各成分の配合は調整される。ブレード塗工を行う場合は、顔料塗工液の固形分濃度は４０〜７０重量％が好ましく、より好ましくは６０〜７０重量％である。顔料塗工液の粘度は室温にて６０ｒｐｍで測定したＢ型粘度が５００〜５０００ｍＰａ・ｓの範囲であることが好ましい。また、ロールコーターで塗工を行う場合は、顔料塗工液の固形分は５０〜７０重量％が好ましく、より好ましくは６０〜７０重量％である。固形分重量が低すぎるとバックフロー等が起きてしまい、高すぎるとブレード負荷が大きくなりブレードの摩耗が進むなど、操業性に影響が出る。(3) Preparation of Pigment Coating Liquid The pigment coating liquid can be prepared by dispersing or dissolving a pigment, an adhesive and, if necessary, an additive in water. The composition of each component is adjusted so that the pigment coating layer can be formed. When blade coating is performed, the solid content concentration of the pigment coating liquid is preferably 40 to 70% by weight, more preferably 60 to 70% by weight. The viscosity of the pigment coating liquid is preferably such that the B-type viscosity measured at 60 rpm at room temperature is in the range of 500 to 5000 mPa · s. When coating with a roll coater, the solid content of the pigment coating liquid is preferably 50 to 70% by weight, more preferably 60 to 70% by weight. If the solid content weight is too low, backflow or the like will occur, and if it is too high, the blade load will increase and the blade will wear more, which will affect the operability.
（４）塗工方法
塗工方法は限定されず、ロールコーター、ブレードコーター等の公知の塗工方法を用いることができる。塗工速度も特に限定されないが、ブレードコーターの場合は４００〜１８００ｍ／分、ロールコーターの場合は４００〜２０００ｍ／分が好ましい。本発明においては、顔料塗工層を１層ブレードコーターで塗工してもよく、ロールコーターで塗工した後にブレードコーターで塗工してもよいし、ブレードコーターで塗工した後にブレードコーターで塗工してもよいが、表面の平滑性を向上させることができるため、最外塗工層の塗工にブレードコーターを用いることが好ましい。(4) Coating Method The coating method is not limited, and a known coating method such as a roll coater or a blade coater can be used. The coating speed is not particularly limited, but is preferably 400 to 1800 m / min in the case of a blade coater and 400 to 2000 m / min in the case of a roll coater. In the present invention, the pigment coating layer may be coated with a single layer blade coater, may be coated with a roll coater and then with a blade coater, or may be coated with a blade coater and then with a blade coater. Although coating may be performed, it is preferable to use a blade coater for coating the outermost coating layer because the surface smoothness can be improved.
本発明の印刷用塗工紙は印刷光沢度を上げるため２層以上の顔料塗工層を設けることが必要である。顔料塗工層を２層以上とすることで繊維被覆性が向上し、平滑度も高くなる。３層以上とすると塗工量を増やすことができるため塗工紙の品質は向上するが、コストや操業性の点から層数は２層であることが好ましい。前述のとおり原紙の上にクリア塗工層を設け、その上に２層以上の顔料塗工層を設けてもよい。 The coated paper for printing of the present invention needs to have two or more pigment coating layers in order to increase the printing gloss. By using two or more pigment coating layers, the fiber coverage is improved and the smoothness is also increased. When the number of layers is 3 or more, the amount of coating can be increased and thus the quality of the coated paper is improved, but the number of layers is preferably 2 from the viewpoint of cost and operability. As described above, a clear coating layer may be provided on the base paper, and two or more pigment coating layers may be provided thereon.
（５）その他の工程
湿潤状態の塗工層を乾燥させる方法は限定されず、例えば蒸気加熱シリンダ、加熱熱風エアドライヤ、ガスヒータードライヤ、電気ヒータードライヤ、赤外線ヒータードライヤ等を用いることができる。(5) Other Steps The method for drying the wet coating layer is not limited, and for example, a steam heating cylinder, a heated hot air dryer, a gas heater dryer, an electric heater dryer, an infrared heater dryer or the like can be used.
本発明印刷用塗工紙は、以上のように製造した塗工紙を必要に応じて表面処理してもよいが、本発明のマット調の風合が得にくくなるため、カレンダー処理を行わないことが望ましい。カレンダー処理を行う場合には、スーパーカレンダー、ソフトカレンダー等の一般に使用されているカレンダー装置が適宜使用できる。カレンダー仕上げ条件としては、剛性ロールの温度、カレンダー圧力、ニップ数、ロール速度、カレンダー前の紙水分等が、要求される品質に応じて適宜選択されるが、本発明の印刷用塗工紙においては、マット調の風合いを出すために低圧でのカレンダー処理が好ましい。 The coated paper for printing of the present invention may be subjected to a surface treatment on the coated paper produced as described above, but the matte texture of the present invention becomes difficult to obtain, so calendar treatment is not performed. Is desirable. When carrying out the calendar treatment, a generally used calendar device such as a super calendar or a soft calendar can be appropriately used. As the calender finishing conditions, the temperature of the rigid roll, the calender pressure, the nip number, the roll speed, the paper moisture before the calender, etc. are appropriately selected according to the required quality. In the coated paper for printing of the present invention, Is preferred to be calendered at a low pressure to give a matte texture.
３．紙質
（１）白紙光沢度
白紙光沢度は白紙での光沢度合いを示す指標であり、本発明においてはＪＩＳ−Ｐ８１４２に従い測定される。本発明の印刷用塗工紙は、一態様において白紙光沢と印刷光沢の差異が大きなマット調の印刷用塗工紙である。この場合、白紙光沢度は４０％以下が好ましく、３６％以下がさらに好ましく、３２％未満がより好ましい。白紙光沢度の下限は限定されないが、１５％以上が好ましい。3. Paper quality (1) White paper glossiness The white paper glossiness is an index indicating the glossiness of a white paper, and is measured according to JIS-P8142 in the present invention. The printing coated paper of the present invention is a matte printing coated paper having a large difference between white gloss and printing gloss in one embodiment. In this case, the white paper glossiness is preferably 40% or less, more preferably 36% or less, and further preferably less than 32%. The lower limit of the white paper glossiness is not limited, but is preferably 15% or more.
（２）印刷光沢度（光沢度差）
印刷光沢度は、印刷後の印刷物の光沢度合を示す指標であり、本発明においては後述の方法で測定される。マット調の印刷用塗工紙において、印刷光沢度（ＣＭ）は５７以上が好ましく、５８％以上が好ましい。この場合の印刷光沢度の上限は限定されないが、７５％以下が好ましい。本発明においては、印刷光沢度から白紙光沢度を差し引いた光沢度差は、１５以上であれば印刷部と白紙部の光沢の差異が十分に得られており、より鮮明な印刷物であるといえる。(2) Print glossiness (difference in glossiness)
The print glossiness is an index showing the glossiness of the printed matter after printing, and is measured by the method described later in the present invention. In the matte coated paper for printing, the printing glossiness (CM) is preferably 57 or more, and more preferably 58% or more. The upper limit of the printing glossiness in this case is not limited, but is preferably 75% or less. In the present invention, if the gloss difference obtained by subtracting the blank gloss from the print gloss is 15 or more, the gloss difference between the printed portion and the blank portion is sufficiently obtained, and it can be said that the printed matter is clearer. .
（３）インキ乾燥性
本発明の印刷用塗工紙は、印刷光沢度が高いにもかかわらずインキ乾燥性に優れる。印刷用塗工紙のインキ乾燥性の優劣は、一般的に印刷後の印字物を重ねた際にインキが他方に転移する裏移りや印刷面の擦れ汚れなどを確認することで識別される。(3) Ink Dryability The coated paper for printing of the present invention is excellent in ink dryness even though the printing glossiness is high. The superiority or inferiority of the ink drying property of the coated paper for printing is generally identified by confirming the set-off that the ink is transferred to the other when the printed matters are piled up on the other side after printing and the rubbing stain on the printed surface.
（３−１）窒素吸着法（紙の全細孔容積）による評価
本発明においては、低圧条件下で測定できる窒素吸着法を用いて顔料塗工層の細孔構造を定評的に評価することで、本発明の印刷用塗工紙のインキ乾燥性を評価できる。顔料塗工層と溶剤吸収性との関係については、顔料塗工層中に存在する多数の微細な孔を毛細管の集合体として捉えた（１）式に示すＬｕｃａｓ−Ｗａｓｈｂｕｒｎの式が広く用いられている。ここで、Ｌは溶剤の浸透深さ、ｒは毛細管の平均半径、ｔは時間、γは溶剤の表面張力、θは毛細管壁と溶剤の接触角、ηは溶剤の粘度である。そして、顔料塗工層の細孔構造を平均半径ｒの円筒菅がｎ個並んだものと仮定すると、顔料塗工層へのインキ溶剤浸透量νは式（２）で表されるから、式（１）は式（３）のように変形できる。ｄは顔料塗工層の厚さ、Ｖは顔料塗工層の細孔容積、ｋはインキの粘度である。つまり、顔料塗工層中の細孔直径、細孔容積が大きいほど、また顔料塗工層厚さが小さいほど一定時間あたりの溶剤浸透量は多くなり、インキ乾燥性は向上すると考えられる。本発明においては、トライスター３０００によって得られた細孔容積を、顔料塗工層の細孔容積とみなし、平均細孔直径を、顔料塗工層の平均細孔直径とみなす。(3-1) Evaluation by Nitrogen Adsorption Method (Total Pore Volume of Paper) In the present invention, the pore structure of the pigment coating layer is evaluated remarkably by using the nitrogen adsorption method which can be measured under low pressure conditions. Thus, the ink drying property of the printing coated paper of the present invention can be evaluated. Regarding the relationship between the pigment coating layer and the solvent absorbability, the Lucas-Washburn equation shown in the equation (1) in which a large number of fine pores existing in the pigment coating layer are regarded as an assembly of capillaries is widely used. ing. Here, L is the penetration depth of the solvent, r is the average radius of the capillary, t is time, γ is the surface tension of the solvent, θ is the contact angle between the capillary wall and the solvent, and η is the viscosity of the solvent. Assuming that the cylindrical structure of the pigment coating layer has n cylindrical tubes with an average radius r, the ink solvent penetration amount ν into the pigment coating layer is expressed by equation (2). Equation (1) can be transformed into equation (3). d is the thickness of the pigment coating layer, V is the pore volume of the pigment coating layer, and k is the viscosity of the ink. That is, it is considered that the larger the pore diameter and the pore volume in the pigment coating layer, and the smaller the pigment coating layer thickness, the larger the solvent permeation amount per constant time and the ink drying property is improved. In the present invention, the pore volume obtained by Tristar 3000 is regarded as the pore volume of the pigment coating layer, and the average pore diameter is regarded as the average pore diameter of the pigment coating layer.
本発明の印刷用塗工紙の細孔容積Ｖは、０．０４ｃｍ３／ｇ超であることが好ましく、は０．０４５ｃｍ３／ｇ以上であることがより好ましい。上限は０．０９ｃｍ３／ｇ以下であることが好ましく、０．０８５ｃｍ３／ｇ以下であることがより好ましく、０．０８ｃｍ３／ｇ以下であることがさらに好ましい。細孔容積Ｖが０．０４ｃｍ３／ｇより高い印刷用塗工紙はインキ乾燥性に優れる。Pore volume V of the coated printing paper of the present invention is preferably 0.04 cm 3 / g greater, is more preferably 0.045 cm 3 / g or more. Preferably the upper limit is less than 0.09 cm 3 / g, more preferably 0.085cm 3 / g or less, and more preferably not more than 0.08 cm 3 / g. The coated paper for printing having a pore volume V higher than 0.04 cm 3 / g is excellent in ink drying property.
本発明の印刷用塗工紙の全細孔容積（ｃｍ３／ｍ２）は、細孔容積Ｖ（ｃｍ３／ｇ）×塗工量ｃ（ｇ／ｍ２）により定義され、その値は０．５５ｃｍ３／ｍ２以上が好ましく、０．６０ｃｍ３／ｍ２以上がより好ましく、０．８０ｃｍ３／ｍ２以上がさらに好ましい。全細孔容積の上限は、１．００ｃｍ３／ｍ２以下が好ましく、０．９５ｃｍ３／ｍ２以下がより好ましい。The total pore volume (cm 3 / m 2 ) of the coated paper for printing of the present invention is defined by the pore volume V (cm 3 / g) × the coating amount c (g / m 2 ), and the value is 0.55 cm 3 / m 2 or more, more preferably 0.60 cm 3 / m 2 or more, more preferably 0.80 cm 3 / m 2 or more. The upper limit of the total pore volume is preferably 1.00 cm 3 / m 2 or less, more preferably 0.95cm 3 / m 2.
本発明の印刷用塗工紙の平均細孔直径ｍは３０ｎｍ以上が好ましい。平均細孔直径ｍの上限は６０ｎｍ以下であることが好ましい。具体的に本発明において平均細孔直径は、窒素吸着法によって得られた脱着等温線より求められる。本願では、トライスター３０００によって得られた平均細孔直径を、顔料塗工層の平均細孔直径とみなす。 The average pore diameter m of the coated paper for printing of the present invention is preferably 30 nm or more. The upper limit of the average pore diameter m is preferably 60 nm or less. Specifically, in the present invention, the average pore diameter is obtained from the desorption isotherm obtained by the nitrogen adsorption method. In the present application, the average pore diameter obtained by Tristar 3000 is regarded as the average pore diameter of the pigment coating layer.
以下に実施例を挙げて、本発明を具体的に説明するがこれらによって本発明は限定されない。重量部および重量％は固形分換算の値である。 Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. Parts by weight and% by weight are values in terms of solid content.
＜評価方法＞
（１）坪量
ＪＩＳ Ｐ ８１２４に準じて測定した。
（２）ＩＳＯ白色度：ＪＩＳ Ｐ８１４８に準拠し、村上色彩（株）製色差計ＣＭＳ−３５ＳＰＸにて、紫外光を含む条件にて測定した。
（３）白紙光沢度
ＪＩＳ−Ｐ８１４２に基づいて測定した。<Evaluation method>
(1) Basis weight Measured according to JIS P 8124.
(2) ISO whiteness: measured according to JIS P8148 with a color difference meter CMS-35SPX manufactured by Murakami Color Co., Ltd. under conditions including ultraviolet light.
(3) White paper glossiness It was measured based on JIS-P8142.
（４）インキ乾燥性
ローランド社製オフセット枚葉印刷機（４色）にてオフセット枚葉用インキ（東洋インキ製ＮＥＸ−Ｍ）を用い、印刷速度８０００枚／ｈｒでベタ部のインキ着肉濃度が墨２．００となるように印刷したあと、墨ベタ印刷部を印刷直後から１０分ごとに指先で触り、インキ乾燥の速さの程度を官能評価した。
Ａ：良好
Ｂ：不良(4) Ink drying property An offset sheet-fed printing machine (4 colors) manufactured by Roland Co., Ltd. is used with an offset sheet-fed ink (NEX-M manufactured by Toyo Ink) at a printing speed of 8000 sheets / hr and the ink adhesion density of a solid portion. After printing so that the ink was 2.00, the solid ink print portion was touched with a fingertip every 10 minutes immediately after printing, and the degree of ink drying speed was sensory evaluated.
A: Good B: Poor
（５）印刷光沢度（光沢度差）
ローランド社製オフセット枚葉印刷機（４色）にてオフセット枚葉用インキ（東洋インキ（株）製ＮＥＸ−Ｍ）を用い、印刷速度８０００枚／ｈｒでベタ部のインキ着肉濃度が藍１．６０、紅１．５０となる様に藍紅（ＣＭ）の順に印刷した。得られた印刷物の藍紅（ＣＭ）ベタ印刷部の光沢度を、ＪＩＳ Ｐ−８１４２に基づいて測定した。印刷光沢度から白紙光沢度を差し引いた値を光沢度差とし、光沢度差が１５ポイント以上であれば印刷部と白紙部の光沢の差異が十分に得られており、見栄えのよい印刷物といえる。
光沢度差＝印刷光沢度（％）−白紙光沢度（％）(5) Print glossiness (glossiness difference)
An offset sheet-fed printing machine (4 colors) manufactured by Roland Co., Ltd. was used with an offset sheet-fed ink (NEX-M manufactured by Toyo Ink Co., Ltd.) at a printing speed of 8000 sheets / hr and the ink inking density of the solid portion was 1 indigo. .60 and Beni 1.50 were printed in this order in the order of deep red (CM). The glossiness of the deep red (CM) solid printed portion of the obtained print was measured according to JIS P-8142. A value obtained by subtracting the blank glossiness from the printing glossiness is defined as the glossiness difference. If the glossiness difference is 15 points or more, the glossiness of the printed portion and the blank paper portion is sufficiently obtained, and it can be said that the printed matter has a good appearance. .
Glossiness difference = Print glossiness (%)-Blank paper glossiness (%)
（６）細孔容積等
（ｉ）サンプル調製と測定
窒素吸着法により、塗工紙の細孔容積、全細孔容積、平均細孔直径を求めた。
（サンプルの調製）
縦４０ｃｍ×横１５ｃｍの紙サンプルを厚さ方向に均等になるよう２層に分割し、顔料塗工層と原紙層を含む積層体を得た。両面塗工紙の場合は当該積層体が２つ、片面塗工紙の場合は当該積層体が１つと主として原紙層からなる層が１つ得られる。顔料塗工層と原紙層を含む積層体をサンプルシートとして測定に使用した。両面塗工紙の場合はいずれか一方をサンプルシートとして測定に使用した。サンプルシートの坪量ｔ（ｇ／ｍ２）を測定した。１枚のサンプルシート中の任意の４点を選択し、短冊状に断裁した後、測定サンプルが絶乾重量１〜２ｇ程度となるように測定セルに入れた。この時の絶乾重量をｗ（ｇ）とした。真空状態、処理温度１２０℃で一晩前処理を行った。(6) Pore volume etc. (i) Sample preparation and measurement The nitrogen volume was used to determine the pore volume, total pore volume and average pore diameter of the coated paper.
(Sample preparation)
A paper sample having a length of 40 cm and a width of 15 cm was divided into two layers so as to be even in the thickness direction to obtain a laminate including a pigment coating layer and a base paper layer. In the case of double-sided coated paper, two such laminated bodies are obtained, and in the case of single-sided coated paper, one laminated body and one layer mainly composed of a base paper layer are obtained. A laminate including the pigment coating layer and the base paper layer was used as a sample sheet for measurement. In the case of double-sided coated paper, either one was used as a sample sheet for measurement. The basis weight t (g / m 2 ) of the sample sheet was measured. After selecting four arbitrary points in one sample sheet and cutting them into strips, the sample was put in a measuring cell so that the absolute dry weight was about 1 to 2 g. The absolute dry weight at this time was defined as w (g). Pretreatment was performed overnight at a treatment temperature of 120 ° C. in a vacuum.
（測定）
前記装置を用いて前記測定サンプルの顔料塗工層側から細孔容積および平均細孔直径を測定した。具体的には、脱着等温線よりＢＪＨ法を用いて前記測定サンプルの細孔容積および平均細孔直径を求め、４サンプルの平均値を取り、測定サンプルの細孔容積Ｖ’および平均細孔直径ｍ’とした。細孔容積Ｖ’については単位塗工量当たりの値に換算して本発明の顔料塗工層の細孔容積Ｖとした。得られた平均細孔直径ｍ’については、そのまま本発明の顔料塗工層の平均細孔直径ｍとした。測定サンプルの顔料塗工層重量は、顔料塗工層重量（ｇ）＝測定サンプルの絶乾重量ｗ（ｇ）×塗工量ｃ（ｇ／ｍ２）÷サンプルシートの坪量ｔ（ｇ／ｍ２）から算出した。塗工量ｃ（ｇ／ｍ２）は後述する測定方法により求めた。測定および解析には、株式会社島津製作所製トライスター３０００を使用した。(Measurement)
The pore volume and the average pore diameter were measured from the pigment coating layer side of the measurement sample using the apparatus. Specifically, the pore volume and the average pore diameter of the measurement sample are obtained from the desorption isotherm using the BJH method, and the average value of the four samples is calculated to obtain the pore volume V ′ and the average pore diameter of the measurement sample. m '. The pore volume V'was converted into a value per unit coating amount and defined as the pore volume V of the pigment coating layer of the present invention. The obtained average pore diameter m'was used as it was as the average pore diameter m of the pigment coating layer of the present invention. The pigment coating layer weight of the measurement sample is as follows: pigment coating layer weight (g) = absolute dry weight of the measurement sample w (g) x coating amount c (g / m 2 ) / basis weight t (g / of sample sheet) It was calculated from m 2 ). The coating amount c (g / m 2 ) was determined by the measuring method described later. Tristar 3000 manufactured by Shimadzu Corporation was used for measurement and analysis.
（塗工量）
特許第５８２７１８７号に記載の方法に準じて、塗工量を測定した。具体的には以下の手順により測定した。
１）測定サンプル（紙）を５ｃｍ×５ｃｍの大きさに切断し、温度２３℃、相対湿度５０％で調湿後重量ｘを測定した。
２）スチレンポリマー板上に顔料塗工層が接するように当該サンプルを置き、時計皿で挟みクリップで固定した。
３）１２０〜１５０℃の乾燥機に入れ、スチレンポリマーを溶融させ顔料塗工層と密着させ、放冷した後、温度２３℃、相対湿度５０％で約半日調湿して重量ｙを測定した。
４）前工程で得た測定サンプルを銅エチレンジアミン溶液に約３〜４時間浸漬した後、刷毛を用いて原紙層と顔料塗工層を慎重に剥離した。顔料塗工層に付着したパルプ繊維がなくなるまで、この工程を繰り返した。
５）顔料塗工層を水洗いし乾燥させ、温度２３℃、相対湿度５０％で約半日調湿後、重量ｚを測定した。
６）以下の式によって、塗工量を算出した。
塗工量ｃ（ｇ／ｍ２）＝（ｘ−Ａ）×４００
Ａ＝ｙ−ｚ(Coating amount)
The coating amount was measured according to the method described in Japanese Patent No. 5827187. Specifically, it was measured by the following procedure.
1) The measurement sample (paper) was cut into a size of 5 cm × 5 cm, and the weight x was measured after the humidity was adjusted at a temperature of 23 ° C. and a relative humidity of 50%.
2) The sample was placed on a styrene polymer plate so that the pigment coating layer was in contact, sandwiched with a watch glass and fixed with a clip.
3) It was put in a dryer at 120 to 150 ° C., the styrene polymer was melted and brought into close contact with the pigment coating layer, and after allowing to cool, the humidity y was measured at a temperature of 23 ° C. and a relative humidity of 50% for about half a day. .
4) The measurement sample obtained in the previous step was immersed in a copper ethylenediamine solution for about 3 to 4 hours, and then the base paper layer and the pigment coating layer were carefully peeled off using a brush. This process was repeated until there was no pulp fiber attached to the pigment coating layer.
5) The pigment coating layer was washed with water, dried, and conditioned at a temperature of 23 ° C. and a relative humidity of 50% for about half a day, and then the weight z was measured.
6) The coating amount was calculated by the following formula.
Coating amount c (g / m 2 ) = (x−A) × 400
A = yz
［実施例１］
化学パルプ１００重量％を用い、填料として軽質炭酸カルシウムを１３．５重量％含有する坪量７５ｇ／ｍ２の原紙を準備した。
顔料として重質炭酸カルシウム（株式会社ファイマテック製、商品名：ＦＭＴ９７、Ｄ５０＝０．８８μｍ）１００重量部を用い、これに接着剤としてスチレン・ブタジエン系共重合ラテックスを７重量部、酸化澱粉を３重量部配合して、さらに水を加えて固形分濃度６５重量％の下塗り顔料塗工液を得た。
顔料として第２の炭酸カルシウムである重質炭酸カルシウム（株式会社ファイマテック製、商品名：ＦＭＴ９７、Ｄ５０＝０．８８μｍ）５５重量部および第１の炭酸カルシウムである微粒重質炭酸カルシウム（株式会社ファイマテック製、商品名：ＦＭＴ１００、Ｄ５０＝０．６６μｍ）４５重量部を用い、これに接着剤としてスチレン・ブタジエン系共重合ラテックスを４重量部、酸化澱粉を６重量部配合して、さらに水を加えて固形分濃度６６重量％の上塗り顔料塗工液を得た。
前記原紙上に、下塗り顔料塗工液をブレードコーターで片面あたりの乾燥塗工量が６．５ｇ／ｍ２となるように両面塗工し乾燥した。さらに、その上に上塗り顔料塗工液をブレードコーターで片面あたりの乾燥塗工量が１０．５ｇ／ｍ２となるように両面塗工し、印刷用塗工紙を得た。当該印刷用塗工紙について、前述の方法にて評価した。[Example 1]
A base paper having a basis weight of 75 g / m 2 containing 100% by weight of chemical pulp and 13.5% by weight of light calcium carbonate as a filler was prepared.
As the pigment, 100 parts by weight of heavy calcium carbonate (Pharmatech Co., Ltd., trade name: FMT97, D50 = 0.88 μm) was used. To this, 7 parts by weight of styrene / butadiene copolymer latex and oxidized starch were used as an adhesive. 3 parts by weight were mixed and water was further added to obtain an undercoat pigment coating liquid having a solid content concentration of 65% by weight.
As the pigment, 55 parts by weight of the second calcium carbonate, heavy calcium carbonate (Pharmatech Co., Ltd., trade name: FMT97, D50 = 0.88 μm), and the first calcium carbonate, fine heavy calcium carbonate (K.K. 45 parts by weight of FMT100, product name: FMT100, D50 = 0.66 μm), 4 parts by weight of a styrene-butadiene copolymer latex and 6 parts by weight of oxidized starch as an adhesive are added to the mixture, and water is further added. Was added to obtain a topcoat pigment coating liquid having a solid content concentration of 66% by weight.
Both surfaces of the base paper were coated with the undercoat pigment coating liquid by a blade coater so that the dry coating amount per surface was 6.5 g / m 2 and dried. Further, a top coat pigment coating solution was coated on the both sides with a blade coater so that the dry coating amount per one side would be 10.5 g / m 2 to obtain a coated paper for printing. The coated paper for printing was evaluated by the method described above.
［実施例２］
顔料として自製苛性化軽質炭酸カルシウム（Ｄ５０＝１．３８μｍ）９７重量部および自製苛性化軽質炭酸カルシウム（Ｄ５０＝１．０２μｍ）３重量部を用い、これに接着剤としてスチレン・ブタジエン系共重合ラテックスを２．５重量部、酸化澱粉を２１重量部配合して、さらに水を加えて固形分濃度５０重量％の下塗り顔料塗工液を得た。
顔料として第１の炭酸カルシウムである自製微粒苛性化軽質炭酸カルシウム（Ｄ５０＝０．６４μｍ）４４．５重量部および第２の炭酸カルシウムである自製苛性化軽質炭酸カルシウム（Ｄ５０＝１．０２μｍ）５５重量部を用い、これに接着剤としてスチレン・ブタジエン系共重合ラテックスを４重量部および酸化澱粉を６重量部、蒸煮をしていない澱粉粒（日本コーンスターチ社製、商品名：Ｙ−３Ｐ）を０．５重量部配合して、さらに水を加えて固形分濃度６６重量％の上塗り顔料塗工液を得た。
前記原紙上に、下塗り顔料塗工液をゲートロールコーターで片面あたりの乾燥塗工量が４．５ｇ／ｍ２となるように両面塗工し乾燥した。さらに、その上に上塗り顔料塗工液をブレードコーターで片面あたりの乾燥塗工量が１０．５ｇ／ｍ２となるように両面塗工し、印刷用塗工紙を得た。当該印刷用塗工紙について、前述の方法にて評価した。[Example 2]
97 parts by weight of self-made causticized light calcium carbonate (D50 = 1.38 μm) and 3 parts by weight of self-made causticized light calcium carbonate (D50 = 1.02 μm) were used as pigments, and a styrene-butadiene copolymer latex was used as an adhesive. Was mixed with 2.5 parts by weight of oxidized starch and 21 parts by weight of oxidized starch, and water was further added to obtain an undercoat pigment coating liquid having a solid content concentration of 50% by weight.
44.5 parts by weight of self-made fine-grained causticized light calcium carbonate (D50 = 0.64 μm) which is the first calcium carbonate as a pigment, and self-made causticized light calcium carbonate (D50 = 1.02 μm) 55 which is the second calcium carbonate 55 4 parts by weight of styrene / butadiene copolymer latex and 6 parts by weight of oxidized starch as an adhesive, and starch granules not cooked (product name: Y-3P manufactured by Japan Corn Starch Co., Ltd.) 0.5 parts by weight was added, and water was further added to obtain a top-coating pigment coating liquid having a solid content concentration of 66% by weight.
Both surfaces of the base paper were coated with the undercoat pigment coating liquid by a gate roll coater so that the dry coating amount per surface was 4.5 g / m 2 and dried. Further, a top coat pigment coating solution was coated on the both sides with a blade coater so that the dry coating amount per one side was 10.5 g / m 2 , to obtain a coated paper for printing. The coated paper for printing was evaluated by the method described above.
［実施例３］
実施例１において調製した上塗り顔料塗工液の、第１の炭酸カルシウム、スチレン・ブタジエン系共重合ラテックス、および酸化澱粉の配合量を表１に示す量に変更し、かつ蒸煮をしていない澱粉粒（日本コーンスターチ社製、商品名：Ｙ−３Ｐ）を０．５重量部配合した上塗り顔料塗工液を調製した。当該塗工液を用いた以外は実施例１と同様にして印刷用塗工紙を製造し、評価した。[Example 3]
The amount of the first calcium carbonate, the styrene-butadiene copolymer latex, and the oxidized starch in the topcoat pigment coating liquid prepared in Example 1 was changed to the amounts shown in Table 1, and the starch was not cooked. A top-coating pigment coating liquid containing 0.5 parts by weight of particles (manufactured by Japan Corn Starch Co., Ltd., trade name: Y-3P) was prepared. A coated paper for printing was produced and evaluated in the same manner as in Example 1 except that the coating liquid was used.
［実施例４］
顔料として重質炭酸カルシウム（株式会社ファイマテック製、商品名：ＦＭＴ９０、Ｄ５０＝１．１５μｍ）１００重量部を用い、これに接着剤としてスチレン・ブタジエン系共重合ラテックスを７重量部、酸化澱粉を３重量部配合して、さらに水を加えて固形分濃度７０重量％の下塗り顔料塗工液を得た。
顔料として第２の炭酸カルシウムである重質炭酸カルシウム（イメリス製、商品名：Ｃ９０、Ｄ５０＝１．１８μｍ）５５重量部および第１の炭酸カルシウムである微粒重質炭酸カルシウム（イメリス製、カービラックス、Ｄ５０＝０．６４μｍ）４４．５重量部を用い、これに接着剤としてスチレン・ブタジエン系共重合ラテックスを４重量部および酸化澱粉を６重量部、蒸煮をしていない澱粉粒（日本コーンスターチ社製、商品名：Ｙ−３Ｐ）を０．５重量部配合して、さらに水を加えて固形分濃度６６重量％の上塗り顔料塗工液を得た。これらの塗工液を用いて実施例１と同様にして印刷用塗工紙を製造し、評価した。[Example 4]
As the pigment, 100 parts by weight of heavy calcium carbonate (Pharmatech Co., Ltd., trade name: FMT90, D50 = 1.15 μm) was used, and 7 parts by weight of styrene / butadiene copolymer latex and starch oxide were used as an adhesive. 3 parts by weight were mixed, and water was further added to obtain an undercoat pigment coating liquid having a solid content concentration of 70% by weight.
55 parts by weight of a second calcium carbonate, a heavy calcium carbonate (made by Imerys, trade name: C90, D50 = 1.18 μm) as a pigment, and fine calcium carbonate, which is the first calcium carbonate (made by Imerys, Carvilax , D50 = 0.64 μm) 44.5 parts by weight, to which is added 4 parts by weight of styrene-butadiene copolymer latex and 6 parts by weight of oxidized starch, starch grains that have not been cooked (Japan Corn Starch Co., Ltd. (Manufactured, trade name: Y-3P) was mixed with 0.5 part by weight, and water was further added to obtain a topcoat pigment coating liquid having a solid content concentration of 66% by weight. Using these coating solutions, coated paper for printing was manufactured and evaluated in the same manner as in Example 1.
［比較例１］
顔料として重質炭酸カルシウム（株式会社ファイマテック製、商品名：ＦＭＴ７５、Ｄ５０＝１．６５μｍ）を８５重量部、カオリン（イメリス社製、商品名：ＫＣＳ、Ｄ５０＝４．０５μｍ）１５重量部、接着剤としてスチレン・ブタジエン系共重合ラテックスを４．３重量部、酸化澱粉を６．５重量部配合して、さらに水を加えて固形分濃度６６重量％の顔料塗工液を得た。当該塗工液を用いて実施例１と同様にして１層の顔料塗工層を有する印刷用塗工紙を製造し、評価した。[Comparative Example 1]
85 parts by weight of heavy calcium carbonate (Pharmatech Co., Ltd., trade name: FMT75, D50 = 1.65 μm) as a pigment, 15 parts by weight of kaolin (Imeris Co., Ltd., trade name: KCS, D50 = 4.05 μm), As an adhesive, 4.3 parts by weight of styrene / butadiene copolymer latex and 6.5 parts by weight of oxidized starch were mixed, and water was further added to obtain a pigment coating liquid having a solid content concentration of 66% by weight. Using the coating liquid, a printing coated paper having one pigment coating layer was produced and evaluated in the same manner as in Example 1.
［比較例２］
顔料として重質炭酸カルシウム（イメリス社製、商品名：Ｃ９７、Ｄ５０＝０．９１μｍ）を１００重量部、接着剤としてスチレン・ブタジエン系共重合ラテックスを７．６重量部、酸化澱粉を６重量部配合して、さらに水を加えて固形分濃度６６重量％の顔料塗工液を得た。当該塗工液を用いて実施例１と同様にして１層の顔料塗工層を有する印刷用塗工紙を製造し、評価した。[Comparative Example 2]
100 parts by weight of heavy calcium carbonate (manufactured by Imerys Co., Ltd., trade name: C50, 0.91 μm) as a pigment, 7.6 parts by weight of styrene-butadiene copolymer latex as an adhesive, and 6 parts by weight of oxidized starch. After mixing, water was added to obtain a pigment coating liquid having a solid content concentration of 66% by weight. Using the coating liquid, a printing coated paper having one pigment coating layer was produced and evaluated in the same manner as in Example 1.
［比較例３］
顔料として重質炭酸カルシウム（株式会社ファイマテック製、商品名：ＦＭＴ９７、Ｄ５０＝０．８８μｍ）を５５重量部、カオリン（イメリス社製、商品名：ＫＣＳ、Ｄ５０＝４．０５μｍ）４５重量部、接着剤としてスチレン・ブタジエン系共重合ラテックスを４重量部、酸化澱粉を６重量部配合して、さらに水を加えて固形分濃度６６重量％の顔料塗工液を得た。当該塗工液を用いて実施例１と同様にして１層の顔料塗工層を有する印刷用塗工紙を製造し、評価した。[Comparative Example 3]
55 parts by weight of heavy calcium carbonate (Pharmatech Co., Ltd., trade name: FMT97, D50 = 0.88 μm) as a pigment, 45 parts by weight of kaolin (Imeris Co., Ltd., trade name: KCS, D50 = 4.05 μm), 4 parts by weight of styrene-butadiene copolymer latex and 6 parts by weight of oxidized starch were mixed as an adhesive, and water was further added to obtain a pigment coating solution having a solid content concentration of 66% by weight. Using the coating liquid, a printing coated paper having one pigment coating layer was produced and evaluated in the same manner as in Example 1.
［比較例４］
顔料として重質炭酸カルシウム（株式会社ファイマテック製、商品名：ＦＭＴ９７、Ｄ５０＝０．８８μｍ）を５５重量部および微粒重質炭酸カルシウム（株式会社ファイマテック製、商品名：ＦＭＴ１００ＹＦ、Ｄ５０＝０．６０μｍ）４５重量部、接着剤としてスチレン・ブタジエン系共重合ラテックスを４重量部、酸化澱粉を６重量部配合して、さらに水を加えて固形分濃度６６重量％の顔料塗工液を得た。当該塗工液を用いて実施例１と同様にして１層の顔料塗工層を有する印刷用塗工紙を製造し、評価した。[Comparative Example 4]
As a pigment, 55 parts by weight of heavy calcium carbonate (manufactured by Phimatec Co., Ltd., trade name: FMT97, D50 = 0.88 μm) and fine-grained heavy calcium carbonate (manufactured by Phimatec Co., Ltd., trade name: FMT100YF, D50 = 0. 60 μm) 45 parts by weight, 4 parts by weight of styrene / butadiene copolymer latex as an adhesive and 6 parts by weight of oxidized starch, and water was further added to obtain a pigment coating solution having a solid content concentration of 66% by weight. . Using the coating liquid, a printing coated paper having one pigment coating layer was produced and evaluated in the same manner as in Example 1.
本発明の印刷用塗工紙は、インキ乾燥性と印刷光沢度のバランスに優れることが明らかである。 It is clear that the coated printing paper of the present invention has an excellent balance between ink drying property and printing glossiness.
Claims (6)
最外顔料塗層が０．８０μｍ以下の平均粒子径（Ｄ５０）を有する炭酸カルシウムを含む、印刷用塗工紙。At least one side of the base paper has two or more pigment coating layers,
A coated paper for printing, wherein the outermost pigment coating layer contains calcium carbonate having an average particle diameter (D50) of 0.80 μm or less.
The coated paper for printing according to any one of claims 1 to 5, wherein the coating amount of the outermost pigment coating layer is larger than the coating amount of the innermost pigment coating layer.
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