JPH0557114B2 - - Google Patents
Info
- Publication number
- JPH0557114B2 JPH0557114B2 JP59166282A JP16628284A JPH0557114B2 JP H0557114 B2 JPH0557114 B2 JP H0557114B2 JP 59166282 A JP59166282 A JP 59166282A JP 16628284 A JP16628284 A JP 16628284A JP H0557114 B2 JPH0557114 B2 JP H0557114B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- paper
- recording medium
- magnesium sulfate
- inkjet recording
- 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.)
- Expired - Lifetime
Links
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 39
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 125000002091 cationic group Chemical group 0.000 claims description 19
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 19
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 18
- 239000001023 inorganic pigment Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 239000000975 dye Substances 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000011163 secondary particle Substances 0.000 claims description 8
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011164 primary particle Substances 0.000 claims description 5
- 238000001454 recorded image Methods 0.000 claims description 5
- 239000000981 basic dye Substances 0.000 claims description 4
- 239000011247 coating layer Substances 0.000 claims description 4
- 239000000982 direct dye Substances 0.000 claims description 4
- 239000000985 reactive dye Substances 0.000 claims description 4
- 239000000980 acid dye Substances 0.000 claims description 3
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 claims description 2
- 238000004040 coloring Methods 0.000 claims description 2
- 235000013305 food Nutrition 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000000976 ink Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011248 coating agent Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000000049 pigment Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- -1 alkali metal salt Chemical class 0.000 description 9
- 239000002585 base Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000005562 fading Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- AGOYDEPGAOXOCK-KCBOHYOISA-N clarithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@](C)([C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)OC)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 AGOYDEPGAOXOCK-KCBOHYOISA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 235000012745 brilliant blue FCF Nutrition 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 3
- WZISDKTXHMETKG-UHFFFAOYSA-H dimagnesium;dipotassium;trisulfate Chemical compound [Mg+2].[Mg+2].[K+].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZISDKTXHMETKG-UHFFFAOYSA-H 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000007654 immersion Methods 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
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- IHZXTIBMKNSJCJ-UHFFFAOYSA-N 3-{[(4-{[4-(dimethylamino)phenyl](4-{ethyl[(3-sulfophenyl)methyl]amino}phenyl)methylidene}cyclohexa-2,5-dien-1-ylidene)(ethyl)azaniumyl]methyl}benzene-1-sulfonate Chemical compound C=1C=C(C(=C2C=CC(C=C2)=[N+](C)C)C=2C=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S(O)(=O)=O)=C1 IHZXTIBMKNSJCJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000576 food coloring agent Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 2
- 239000013053 water resistant agent Substances 0.000 description 2
- 238000004078 waterproofing Methods 0.000 description 2
- 239000012463 white pigment Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical group C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-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
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- SGHZXLIDFTYFHQ-UHFFFAOYSA-L Brilliant Blue Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C(=CC=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 SGHZXLIDFTYFHQ-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 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
- 239000005909 Kieselgur Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 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 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 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
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- DCNGHDHEMTUKNP-UHFFFAOYSA-L diazanium;magnesium;disulfate Chemical compound [NH4+].[NH4+].[Mg+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DCNGHDHEMTUKNP-UHFFFAOYSA-L 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 235000012738 indigotine Nutrition 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZADYMNAVLSWLEQ-UHFFFAOYSA-N magnesium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[Mg+2].[Si+4] ZADYMNAVLSWLEQ-UHFFFAOYSA-N 0.000 description 1
- RDPLOLUNEKBWBR-UHFFFAOYSA-L magnesium;sodium;sulfate Chemical compound [Na+].[Mg+2].[O-]S([O-])(=O)=O RDPLOLUNEKBWBR-UHFFFAOYSA-L 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical class C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002851 polycationic polymer Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical class [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910002029 synthetic silica gel Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 210000001685 thyroid gland Anatomy 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Duplication Or Marking (AREA)
Description
(A) 産業上の利用分野
本発明はインクを用いて記録する記録媒体に関
するものであり、特に媒体上に記録された画像や
文字の濃度が高く、吸収性及び記録媒体の保存性
に優れたインクジエツト用記録媒体に関するもの
である。
(B) 従来技術及びその問題点
インクジエツト記録方式は、インクの微小液滴
を種々の作動原理により飛翔させて、紙などの記
録媒体に付着させ、画像、文字などの記録を行う
ものであるが、高速、低騒音、多色化が容易、記
録パターンの融通性が大きい、更に現像、定着が
不要等の特徴があり、漢字を含め各種図形及びカ
ラー画像等の記録装置として、種々の用途に於い
て急速に普及している。更に、多色インクジエツ
ト方式により形成される画像は、製版方式による
多色印刷や、カラー写真方式による印画に比較し
て遜色のない記録を得ることも可能であり、作成
部数が少なくて済む用途に於いては、写真技術に
よるよりも安価であることからフルカラー画像記
録分野にまで広く応用されつつある。
このインクジエツト記録方式で使用される記録
媒体としては、通常の印刷や筆記に使われる上質
紙やコーテツド紙を使うべく装置やインク組成の
面から努力がなされて来た。しかし、装置の高速
化、高精細化あるいはフルカラー化などインクジ
エツト記録装置の性能の向上や用途の拡大に伴な
い、記録媒体に対してもより高度な特性が要求さ
れるようになつた。すなわち、当該記録媒体とし
ては、インクドツトの濃度が高く、色調が明るく
彩やかであること、インクの吸収が早くてインク
ドツトが重なつた場合に於いてもインクが流れ出
したり滲んだりしないこと、インクドツトの横方
向への拡散が必要以上に大きくなく、かつ周辺が
滑らかでぼやけないこと。更に記録画像が紫外線
や空気中の酸素又は水に曝された場合の染料の抵
抗性を低下させず、好ましくは増強させること等
が要求される。
これらの問題を解決するために、従来からいく
つかの提案がなされて来た。例えば特開昭52−
53012号には、低サイズの原紙に表面加工用の塗
料を湿潤させてなるインクジエツト記録用紙が、
また、特開昭53−49113号には、尿素−ホルマリ
ン樹脂粉末を内添したシートに水溶性高分子を含
浸させたインクジエツト記録用紙が開示されてい
る。これらの一般紙タイプのインクジエツト記録
用紙は、インクの吸収は速やかであるが、ドツト
の周辺がぼやけ易く、ドツト濃度も低いと言う欠
点がある。
また、特開昭55−5830号には、支持体表面にイ
ンク吸収性の塗層を設けたインクジエツト記録用
紙が開示され、また、特開昭55−51583号では被
覆層中の顔料として非膠質シリカ粉末を使つた例
が、更に特開昭55−11829号ではインク吸収速度
の異なる２層構造を使つた塗抹紙の例が開示され
ている。これらのコーテツド紙タイプのインクジ
エツト記録用紙は、ドツト径やドツトの形状、ド
ツト濃度や色調の再現性と言つた点では一般紙タ
イプのインクジエツト用紙より改良されている
が、これらの記録媒体に適用されるインクは水溶
性染料を使つた水性インクが多く、記録媒体上に
形成された画像に水等がかかつた場合、染料が再
び溶解して滲み出したりして記録物の価値を著し
く減少させる問題点がある。
そこで、この欠点を改良するために、例えば特
開昭55−53591号には金属の水溶性塩を記録面に
付与する例が、また特開昭56−84992号にはポリ
カチオン高分子電解質を表面に含有する記録媒体
の例が、また、特開昭55−150396号にはインクジ
エツト記録後、該インク中の染料とレーキを形成
する耐水化剤を付与する方法が、そして更に、特
開昭56−58869号には水溶性高分子を塗布した記
録シートにインクジエツト記録後、該水溶性高分
子を不溶化することによつて、耐水化する方法
が、それぞれ開示されている。
ところが、これらの耐水方法は耐水化の効果が
弱かつたり、耐水化剤が染料と何らかの反応を起
し染料の保存性を低下させたりして、充分な耐水
性と耐火性を両立させることはなかなか困難であ
つた。
(C) 発明の目的
本発明は、インクジエツト用水性インクを記録
媒体に噴射して記録画像を形成するインクジエツ
ト記録媒体に於いて、水性インク画像の耐水性及
び耐光性を改善し、前述したような高速、高精細
で、保存性の優れた記録媒体を提供することにあ
る。
(D) 発明の構成及び作用
即ち、本発明は直接染料、酸性染料、塩基性染
料、反応性染料及び食品用色素の内少なくとも一
種の水溶性染料を含有する水性インクを用いて記
録画像を形成するインクジエツト記録媒体に於い
て、該記録媒体が一次粒子を凝集させた平均二次
粒子径が0.5〜30μmの合成シリカ或は水和アルミ
ニウム酸化物の少なくとも一種から選ばれた多孔
性無機顔料、カチオン性樹脂及び少なくとも一種
以上の硫酸マグネシウム又はその複塩を含む塗工
層を設けたことを特徴とするインクジエツト記録
媒体である。
本発明により、多孔性無機顔料は水性インクの
吸収能力を改善し、かつ色濃度及び色彩性を改善
する能力を有する。カチオン性樹脂は水性インク
中の水溶性染料を不溶化し耐水性を改善する役割
を持つ。但し、これらのカチオン性樹脂は耐光性
を減じる性質があり、本発明で使用するカチオン
性樹脂は比較的、その減少率が小さいものを選ん
ではいるがその影響はまぬがれない。
硫酸マグネシウムはカチオン性樹脂による耐光
性の低下を防止し、あるいは改善する能力がある
が、なぜそうなるのかその理由は定かではない。
本発明で云う多孔性無機顔料とは、合成シリカ
あるいは水和アルミニウム酸化物の一次粒子を凝
集させて、平均二次粒子径0.5μm〜30μmの乾燥
粉末としたもので、これらの合成シリカあるいは
水和アルミニウム酸化物は水溶性原材料から水溶
液中で合成された場合、その一次粒子は数mμか
ら数百mμの大きさを持ち、自己凝集性を有して
いる為、乾燥したから粉砕、分級するなり、乾燥
時にスプレードライヤー等を使用して目的とする
粒度に調節することによつて、多孔性無機顔料と
することが出来る。
又、合成シリカや水和アルミニウム酸化物が
1μm以下の微粉末となつている場合には水に分散
した状態から結合剤や接着剤を加えて乾燥し、粉
砕、分級したり、スプレードライヤーで噴霧乾燥
することでやはり平均二次粒子直径0.5μm〜
30μmの多孔性無機顔料とすることも可能である。
更に、コロイダルシリカ、コロイダルアルミナ
の如き微粒水分散物を0.5μm以上の粒子状に成形
するにはU.S.P−3855172号に開示されている如
く、微粒物質懸濁水中で尿素−ホルマリン樹脂等
を生成し、その生成条件を調節することにより、
目的とする二次粒子径に造粒された多孔性無機顔
料とすることも出来る。
本発明で言う合成シリカとは、四塩化ケイ素の
熱分解による乾式法シリカ、ケイ酸ナトリウムの
酸、二酸化炭素、アンモニウム塩などによる複分
解沈澱生成物等のいわゆるホワイトカーボン、ケ
イ酸ナトリウムの酸などによる熱分解やイオン交
換樹脂層を通して得られるシリカゾル又はこのシ
リカゾルを加熱熟成して得られるコロイダルシリ
カ、シリカゾルをゲル化させ、その生成条件をか
えることによつて数ミリミクロンから数十ミリミ
クロン位の一次粒子がシロキサン結合をした三次
元的な二次粒子となつたシリカゲル、更にはシリ
カゾル、ケイ酸ナトリウム、アルミン酸ナトリウ
ム等を出発物質として80℃〜120℃で加熱して生
成したいわゆる合成モレキユラーシーブ等、二酸
化ケイ素を主体とする合成ケイ素化合物を云う。
本発明で云う多孔質の水和アルミニウム酸化物
は、硫酸アルミニウム、硝酸アルミニウム、塩化
アルミニウム及びその類似物のようなアルミニウ
ム塩か、アルミン酸のナトリウムもしくはカリ塩
のようなアルミン酸アルカリ金属塩あるいはその
両者の水溶性アルミニウム化合物の水溶液から中
和あるいはイオン交換樹脂を用いてイオン交換し
て得られたゲル、これをヒドロゲルと云うが、を
通常は洗浄して塩類を除去し、次に乾燥を行つ
て、キセロゲルにすることによつて得られたもの
を云う。乾燥にスプレー乾燥等を使うことにより
塗工液に配合するに好適な粉末状にすることが出
来る。またブロツク状で乾燥した後で粉砕、分級
を行うことで粉末状にすることも可能である。こ
の様にして乾燥後得られる水和酸化物は、遊離水
分の全部とまではいかなくとも、そのほとんどが
除去されており、また結合水分も通常は幾分か除
去され、構造の大部分が不可逆的にセツトされ
て、多孔質の固体となる。この様にして得られた
多孔質の固体の細孔直径は通常50Å〜5000Åであ
り、二次粒子の水中に分散させた場合の表面電荷
はプラスチヤージ（カチオン性）となる。
本発明では上記多孔性無機顔料を下記無機ある
いは有機の顔料と併用することも出来る。この場
合、上記多孔性無機顔料は全顔料の20重量％以
上、好ましくは40重量％以上使用する。併用出来
る無機顔料としては例えば軽質炭酸カルシウム、
重質炭酸カルシウム、カオリン（白土）、タルク、
硫酸カルシウム、硫酸バリウム、酸化チタン、酸
化亜鉛、硫化亜鉛、炭酸亜鉛、サチンホワイト、
ケイ酸アルミニウム、ケイソウ土、ケイ酸カルシ
ウム、ケイ酸マグネシウム、合成無定形シリカ、
水酸化アルミニウム、アルミナ、リトポン等の白
色顔料及び有機顔料としては、スチレン系プラス
チツクピグメント、アクリル系プラスチツクピグ
メント、マイクロカプセル、尿素樹脂顔料等があ
る。
本発明で云うカチオン性樹脂は、水に溶解した
時解離してカチオン性を提するモノマー、オリゴ
マーあるいはポリマーを指すが、好ましくは４級
アンモニウム基を有し、特に好ましくは下記
（）〜（）の一般式で表わされる構造を有す
る化合物を云う。
（）
式中R1，R2，R3はアルキル基、ｍは１〜７、ｎ
は２〜10、Ｙは酸基を表わす。
（）
（）
（）
（）〜（）の式中R1，R2は−CH3、−CH2
−CH3、−CH2−CH2−OH、Ｙは酸基を表わす。
（）ポリアルキレンポリアミンジシアンジア
ミドアンモニウム塩縮合物
（）ポリアミドエピクロルヒドリン樹脂
一般式（）で表わされる化合物は、例えばナ
ルポリー607（ナルコケミカル社製）あるいはポリ
フイツクス601（昭和高分子社製）があげられる。
一般式（）〜（）で表わされる化合物はポ
リジアリルアミン誘導体で、ジアリルアミン化合
物の環化重合によつて得られ、パーコール1697
（アライドコロイド社）、Cat Floc（Calgon
Corp）、PAS（日東紡績社）、ネオフイツクス
RPD（日華化学社製）等を挙げることが出来る。
更に一般式（）で表わされる化合物は例えば
ネオフイツクスRP−70（日華化学社製）を挙げる
ことが出来る。
また一般式（）で表わされる化合物は、エピ
ノツクス1301A（デイツクハーキユレス社）、カイ
メン557H（デイツクハーキユレス社）、ポリフイ
ツクス301（昭和高分子社）等を挙げることが出来
る。これら一般式（）〜（）で表わされるカ
チオン性樹脂の含有量は通常0.1〜４ｇ／m2、好
ましくは0.2〜２ｇ／m2使用することで本発明に
よる耐水性を改善することが出来る。
本発明で云う少なくとも一種以上の硫酸マグネ
シウム又はその複塩とは、無水硫酸マグネシウ
ム、結晶水を持つ硫酸マグネシウム、更に、硫酸
マグネシウムカリウム、硫酸マグネシウムナトリ
ウム、硫酸マグネシウムアンモニウム等の各種結
晶水を持つ状態の複塩を指す。これらの硫酸マグ
ネシウム又はその複塩の少なくとも一種以上の含
有量は硫酸マグネシウム（MgSO4）分として
0.01〜４ｇ／m2、好ましくは0.2〜２ｇ／m2とす
ることで耐光性の低下を防止することが出来る。
これら多孔性無機顔料、カチオン性樹脂、少な
くとも一種以上の硫酸マグネシウム又はその複塩
を記録媒体に適用する方法としては、これらを水
に分散あるいは溶解させ、必要なら通常使用され
る接着剤や無機顔料その他の添加剤を加えて塗工
液とし、サイズプレス装置、ゲートロールコータ
ー、エアナイフコーター、ブレードコーター、ス
プレー等で塗布乾燥する。接着剤としては、例え
ば、酸化澱粉、エーテル化澱粉、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等の
セルロース誘導体、カゼイン、ゼラチン、大豆タ
ン白、ポリビニルアルコール及びその誘導体、無
水マレイン酸樹脂、通常のスチレン−ブタジエン
共重合体、メチルメタクリレート−ブタジエン共
重合体等の共役ジエン系重合体ラテツクス、アク
リル酸エステル及びメタクリル酸エステルの重合
体又は共重合体等のアクリル系重合体ラテツク
ス、エチレン酢酸ビニル共重合体等のビニル系重
合体ラテツクス、或はこれらの各種重合体のカル
ボキシル基等の官能基含有単量体による官能基変
性重合体ラテツクス、メラミン樹脂、尿素樹脂、
等の熱硬化合成樹脂系等の水性接着剤、及びポリ
メチルメタクリレート、ポリウレタン樹脂、不飽
和ポリエステル樹脂、塩化ビニル−酢酸ビニルコ
ポリマー、ポリビニルブチラール、アルキツド樹
脂等の合成樹脂系接着剤が、単独あるいは複合し
て用いられる。これらの接着剤は顔料100部に対
して２部〜100部、好ましくは５部〜30部が用い
られるが顔料の結着に充分な量であればその比率
は特に限定されるものではない。しかし、100部
以上の接着剤を用いると接着剤の造膜により、空
減構造を減らし、あるいは空隙を極端に小さくし
てしまうため、好ましくない。
その他の添加剤としては顔料分散剤、増粘剤、
流動性変性剤、消泡剤、抑泡剤、離型剤、発泡
剤、浸透剤、着色染料、着色顔料、螢光増白剤、
紫外線吸収剤、酸化防止剤、防腐剤、防バイ剤、
耐水化剤等を適宜配合することも出来る。
支持体としては、紙または熱可塑性樹脂フイル
ムの如きシート状物質が用いられる。紙の場合は
サイズ剤無添加あるいは適度なサイジングを施し
た紙で、填料は含まれても、また含まれなくても
よい。
また、熱可塑性フイルムの場合はポリエステ
ル、ポリスチレン、ポリ塩化ビニル、ポリメチル
メタクリレート、酢酸セルロース、ポリエチレ
ン、ポリカーポネート等の透明フイルムや、白色
顔料の充填あるいは微細な発泡による白色不透明
なフイルムが使用される。充填される白色顔料と
しては、例えば酸化チタン、硫酸カルシウム、炭
酸カルシウム、シリカ、クレー、タルク、酸化亜
鉛等の多くのものが使用される。
また、紙の表面にこれらの樹脂フイルムを貼り
合せたり溶融樹脂によつて加工したいわゆるラミ
ネート紙等も使用可能である。これらの樹脂表面
とインク受理層の接着を改善するための下引層や
コロナ放電加工等が施されていてもよい。
支持体上に塗工しただけのシートは、そのまま
でも本発明による記録用シートとして使用出来る
が、例えばスーパーカレンダー、グロスカレンダ
などの加圧又は加熱加圧下のロールニツプ間を通
して表面の平滑性を与えることも可能である。こ
の場合、スーパーカレンダー加工による過度な加
工は、せつかく形成した粒子間の空隙によるイン
ク吸収性を低下させることになるので加工程度は
制限されることがある。
本発明で云う水性インクとは、下記着色剤及び
液媒体、その他の添加剤から成る記録液体であ
る。
着色剤としては直接染料、酸性染料、塩基性染
料、反応性染料あるいは食品用色素等の水溶性染
料である。
例えば、直接染料としては
C.I.Direct Black ２，４，９，11，14，17，
19，22，27，32，36，38，41，48，49，51，
56，62，71，74，75，77，78，80，105，106，
107，108，112，113，117，132，146，154，
194
C.I.Direct Yellow １，２，４，８，11，12，
24，26，27，28，33，34，39，41，42，44，
48，50，51，58，72，85，86，87，88，98，
100，110
C.I.Direct Orange ６，８，10，26，29，39，
41，49，51，102
C.I.Direct Red １，２，４，８，９，11，13，
17，20，23，24，28，31，33，37，39，44，，
46，47，48，51，59，62，63，73，75，77，
80，81，83，84，85，，90，94，99，101，108，
110，145，189，197，220，224，225，226，
227，230
C.I.Direct Violet １，７，９，12，35，48，
51，90，94
C.I.Direct Blue １，２，６，８，15，22，25，
34，69，70，71，72，75，76，78，80，，81，82，
83，86，90，98，106，108，110，120，123，
158，163，165，192，193，194，195，196，199，
200，201，202，203，207，218，236，237，239，
246，258
C.I.Direct Green １，６，８，28，33，37，63，
64
C.I.Direct Braun 1A，２，６，25，27，44，
58，95，100，101，106，112，173，194，195，
209，210，211
酸性染料としては
C.l.Acid Black １，２，７，16，17，24，26，
28，31，41，48，52，58，60，63，94，107，
109，112，118，119，121，122，131，155，
156
C.l.Acid Yellow １，３，４，７，11，12，
13，14，17，18，19，23，25，29，34，36，
38，40，41，42，44，49，53，55，59，60，
71，72，76，78，99，111，114，116，122，
135，161，172
C.l.Acid Orange ７，８，10，33，56，64
C.l.Acid Red １，４，６，８，13，14，15，
18，19，21，26，27，30，32，34，35，37，
40，42，51，52，54，57，80，82，83，85，
87，88，89，92，94，97，106，108，110，
115，119，129，131，133，134，135，154，
155，172，176，180，184，186，187，249，
254，256，317，318
C.l.Acid Violet ７，11，15，34，35，41，43，
49，75
C.l.Acid Blue １，７，９，22，23，25，27，
29，40，41，43，45，49，51，53，55，56，
59，62，78，80，81，83，90，92，93，102，
104，111，113，117，120，124，126，145，
167，171，175，183，229，234，236
C.I.Acid Green ３，12，19，27，41，９，19，
20，25
C.I.Acid Braun ４，14
塩基性染料としては
C.I.Basic Black ２，８
C.I.Basic Yellow １，２，11，12，14，21，32，
36
C.I.Basic Orange ２，15，21，22
C.I.Basic Red １，２，９，12，13，37
C.I.Basic Violet １，３，７，10，14
C.I.Basic Blue １，３，５，７，９，24，25，
26，28，29
C.I.Basic Green １，４
C.I.Basic Braun １，12
反応性染料としては、
C.I.Reactive Black １，３，５，６，８，12，
14
C.I.Reactive Yellow １，２，３，13，14，15，
17
C.I.Reactive Orange ２，５，７，16，20，24
C.I.Reactive Red ６，７，11，12，15，17，
21，23，24，35，36，42，63，66
C.I.Reactive Violet ２，４，５，８，９
C.I.Reactive Blue ２，５，７，12，13，14，
15，17，18，19，20，21，25，27，28，37，
38，40，41
C.I.Reactive Green ５，７
C.I.Reactive Braun １，７，16
更に食品用色素としては
C.I.Food Black ２
C.I.Food Yellow ３，４，５
C.I.Food Red ２，３，７，９，14，52，87，
92，94，102，104，105，106
C.I.Food Violet ２
C.I.Food Blue １，２
C.I.Food Green ２，３
などが挙げられる。
また水性インクの液媒体としては、水及び水溶
性の各種有機溶剤、例えば、メチルアルコール、
エチルアルコール、ｎ−プロピルアルコール、イ
ソプロピルアルコール、ｎ−ブチルアルコール、
sec−ブチルアルコール、tert−ブチルアルコー
ル、イソブチルアルコール等の炭素数１〜４のア
ルキルアルコール類；ジメチルホルムアミド、ジ
メチルアセトアミド等のアミド類；アセトン、ジ
アセトンアルコール等のケトンまたはケトンアル
コール類；テトラヒドロフラン、ジオキサン等の
エテール類；ポリエチレングリコール等の、ポリ
プロピレングリコール等のポリアルキレングリコ
ール類；エチレングリコール、プロピレングリコ
ール、ブチレングリコール、トリエチレングリコ
ール、１，２，６−ヘキサントリオール、チオジ
グリコール、ヘキシレングリコール、ジエチレン
グリコール等のアルキレン基が２〜６個のアルキ
レングリコール類；グリセリン、エチレングリコ
ールメチルエーテル、ジエチレングリコールメチ
ル（又はエチル）エーテル、トリエチレングリコ
ールモノメチルエーテル等の多価アルコールの低
級アルキルエーテル類等が挙げられる。
これらの多くの水溶性有機溶剤の中でもジエチ
レングリコール等の多価アルコール、トリエチレ
ングリコールモノメチルエーテル、トリエチレン
グリコールモノエチルエーテル等の多価アルコー
ルの低級アルキルエーテルは好ましいものであ
る。
その他の添加剤としては例えばPH調節剤、金属
封鎖剤、防カビ剤、粘度調整剤、表面張力調整
剤、湿潤剤、界面活性剤、及び防錆剤等が挙げら
れる。
インクジエツト適性の測定は下記の方法によつ
た。
色濃度はシヤープ製インクジエツトカラーイメ
ージプリンター（IO−700）でシアン(C)、マゼン
タ(M)、イエロー(Y)、ブラツク（Bl）の各インク
でベタ印写して得た画像について、濃度をマクベ
ベスデンシトメーターRD514で測定した値を用
いた。
耐光性はキヤノン製インクジエツトプリンター
（Ａ−1210）を用いて、Ｃ，Ｍ，Ｙ，Blの各イン
クでベタ印写して得た画像部について、キセノン
フエードメーター（スガ試験機(株)製、FAL−25X
−HCL型）で40℃、60％、照度41w／m2で40時
間照射し、照射前後の色濃度をマクベスデンシト
メーターRD514で測定し、照射後の色濃度を照
射前の色濃度で除した値の百分率を残存率とし、
100−残存率を耐光性（退色率）として示した。
数値の小さい方が耐水性が良好なことを示す。
耐水性は同じキヤノン製インクジエツトプリン
ターを用いて、Ｃ，Ｍ，Ｙ，Blの各インクでベ
タ印写して得た画像部について30℃の流水に３分
間浸漬し、浸漬前後の濃度をマクベスデンシトメ
ーターRD514で測定し、浸漬後濃度を浸漬前濃
度で除した百分率を残存率とし、100−残存率を
耐水性（退色率）として示した。数値の小さい方
が耐水性が良好である。
インク吸収速度は、シヤープ製又はキヤノン製
インクジエツトプリンターを用いて、赤印字（マ
ゼンター＋イエロー）のベタ印字直後（約１秒
後）に紙送りして、ペーパー押えロール又は指等
に接触させ、汚れが出るか出ないかで判定した。
更に、吸収容量は、ポリエチレングリコール
（PEGNo.400）／水が１／１の溶液を用いて20℃
で10秒間一定面積のインク受理層に接触させ、余
分な液を吸収紙で取除いて、インク受理層中に吸
収された溶液の重量を測定し、平米当りのグラム
数として算出した値を用いた。値が大きい程、吸
収容量が大きく好ましいことを示す。
(E) 実施例
以下に本発明の実施例を挙げて説明するが、こ
れらの例に限定されるものではない。尚実施例に
於いて示す部及び％は重量部及び重量％を意味す
る。
実施例 １
水度370mlcsfのLBKP80部、水度410mlcsf
のNBKP20部、内填用タルク10部、内填用クレ
ー３部、ロジンサイズ剤（ニユーフオー100、デ
イツクハーキユレス社製）0.5部、バンド2.5部か
らなるスラリーから、長網抄紙機にて坪量68ｇ／
m2の原紙を抄造し、抄造時にサイズプレス装置で
酸化澱粉を1.5ｇ／m2付着させて酸性コート原紙
を製造した。この原紙のステキヒトサイズ度は33
秒であつた。
塗工液として、多孔性無機顔料の合成シリカ
（サイロイド620、富士デヴイソン社製）100部、
水溶性樹脂のポリビニルアルコール（PVA117、
クラレ社製90部、カチオン性樹脂のポリフイツク
ス601（昭和高分子社製）10部、結晶硫酸マグネシ
ウム（MgSO4・7H2O）10部、その他消泡剤、螢
光剤少量から成る濃度16％の水性塗工液を作り、
エアーナイフコーターで前記酸性原紙に固型分９
ｇ／m2になるように塗抹、乾燥した。次いで軽く
スーパーカレンダーを通して、実施例１の記録用
紙とした。この記録用紙のベツク平滑度は105秒
であつた。本記録用紙についてインクジエツト適
正を評価した結果を表１に示す。
比較例 １
実施例１の塗工液から結晶硫酸マグネシウムを
抜いた他は実施例１と全く同様にして、比較例１
の記録用紙を得た。この記録用紙のベツク平滑度
は102秒であつた。この記録用紙についてインク
ジエツト適正を評価した結果を表１に示す。
比較例 ２
実施例１の塗工液からカチオン性樹脂を抜いた
他は実施例１と全く同様にして、比較例２の記録
用紙を得た。この記録用紙のベツク平滑度は95秒
であつた。この記録用紙についてインクジエツト
適正を評価した結果を表１に示す。
比較例 ３
実施例１の塗工液中の多孔性無機顔料（サイロ
イド620）を塗工用カオリン（ウルトラホワイト
90エンゲルハード社製）100部と置換えた他は実
施例１と全く同様にして比較例３の記録用紙を得
た。
この記録用紙のベツク平滑度は260秒であつた。
この記録用紙についてインクジエツト適正を評価
した結果を表１に示す。
比較例 ４
実施例１の塗工液中の硫酸マグネシウムに代え
て塩化カルシウムを使つた他は実施例１と全く同
様にして比較例４の記録用紙を得た。この記録用
紙のベツク平滑度は110秒であつた。この記録用
紙についてインクジエツト適性を評価した結果を
表１に示す。
実施例 ２〜７
水度370mlcsfのLBKP80部、水度400mlcsf
のNBKP20部、重質炭酸カルシウム13部、カチ
オン澱粉１部、アルキルケテンダイマーサイズ剤
（ハーコンＷ デイツクハーキユレス社製）0.12
部及びポリアルキレンポリアミンエピクロルヒド
リン樹脂0.4部から成るスラリーから、長網抄紙
機にて坪量68ｇ／m2の原紙を抄造し、抄造時にサ
イズプレス装置で酸化澱粉を固型分で1.5ｇ／m2
付着させて中性コート原紙を製造した。この原紙
のステキヒトサイズ度は35秒であつた。
第１塗工液として、合成シリカ（ニツプルシー
ルLP、日本シリカ工業社製）100部を水400部に
分散したスラリーをビスコミルを通して、凝集粒
子を粉砕し、ポリビニルアルコール15部を加えて
濃度18％の水性第１塗工液を作り、エアナイフコ
ーターで前記中性コート原紙に固型分13ｇ／m2に
なるように塗抹、乾燥し下塗り紙を作製した。次
いで第２塗工液として合成シリカ（サイロイド
74、富士デヴイソン社製）100部、水溶性樹脂の
ポリビニルアルコール（PVA117、クラレ社製）
40部、カチオン性樹脂としてネオフイツクス
RPD（日華化学社製）７部、無水硫酸マグネシウ
ム（MgSO4）を各々１部、５部、10部、20部、
40部、60部、その他、消泡剤少量から成る濃度13
％の第２塗工液を作り、エアナイフコーターで前
記第１塗工液下塗り紙の上に、固型分５ｇ／m2に
なるように塗抹、乾燥した。次いでスーパーカレ
ンダーを通して各々実施例２、３、４、５、６、
７、の記録用紙とした。この記録用紙についてイ
ンクジエツト適性を評価した結果を表２に示す。
比較例 ５
実施例２〜７で使用した第２塗工液中の無水硫
酸マグネシウムを無添加とした他は実施例２〜７
と全く同様にして比較例５の記録用紙とした。こ
の記録用紙についてインクジエツト適正を評価し
た結果を表２に示す。
実施例 ８
実施例４で使用した無水硫酸マグネシウムに代
えて硫酸マグネシウムカリウム（K2Mg2（SO2）3）
10部を使用した他は実施例２〜７と全く同様にし
て実施例８の記録用紙を得た。この記録用紙につ
いてインクジエツト適性を評価した結果を表２に
示す。
比較例 ６〜10
実施例８で使用した硫酸マグネシウムカリウム
に代えて各々、KCl、NaCl、Na2SO4、CaCl2・
2H2O、ZnCl2を使用した他は実施例８と全く同
様にして各々比較例６、７、８、９、10の記録用
紙を得た。これらの記録用紙についてインクジエ
ツト適性を評価した結果を表２に示す。
実施例 ９
実施例１の塗工液中の多孔性無機顔料の合成シ
リカ（サイロイド620）を平均二次粒子径が
7.2μmで平均細孔直径が140オングストロームの
多孔質の水和アルミニウム酸化物100部と置換え
た以外は実施例１と全く同様にして実施例９の記
録用紙を得た。この記録用紙のベツク平滑度は
110秒であつた。この記録用紙についてインクジ
エツト適性を評価した結果を表１に示す。
〔表１の結果〕
実施例１は合成シリカ、カチオン性樹脂及び硫
酸マグネシウムの３者が必須で、インク吸収能
力、色濃度、耐水性、吸収容量、及び吸収速度が
バランス良い。
比較例１は実施例１において、硫酸マグネシウ
ムを除いたものであるが、Ｍ（マゼンタ）とB1
（ブラツク）での耐光性退色率が大きく悪い結果
である。
同様に、比較例２は、実施例１において、カチ
オン性樹脂を除いたもので、耐光性の退色率も大
きく、ＭとB1の耐光性の退色率も大きい。
更に、比較例３は、実施例１において合成シリ
カを塗工用カオリンに置換えた場合を示し、各色
の記録濃度が大幅に低下し、吸収容量も小さく記
録画像はインクが溢れて解像度が低下し、画像品
位が悪いことを示す。又、吸収速度も遅く、記録
後ペーパー押さえロール又は指等で接触した場
合、汚れが出て、実用上不可である。
又、比較例４は、比較例１において硫酸マグネ
シウムを塩化カルシウムに置換えたものでB1の
耐光性の退色率が大きくやはり実用上問題があ
る。
実施例９は、実施例１において合成シリカから
水和アルミニウム酸化物に置換えたもので、実施
例１と同様な効果があり、バランスが良く実用上
優れたインクジエツト記録用紙を提供できる。
〔表２の結果〕
実施例は色濃度、耐水性、耐光性、吸収容量、
吸収速度のバランスが良く、実用上問題がない
が、比較例はＭとB1の耐光性の退色率が大きく、
実用上非常に問題であることを示す。
(A) Industrial Application Field The present invention relates to a recording medium that is recorded using ink, and in particular, a medium that has high density of images and characters recorded on the medium, and has excellent absorbency and storage stability of the recording medium. This invention relates to an inkjet recording medium. (B) Prior art and its problems The inkjet recording method uses various operating principles to fly minute droplets of ink and make them adhere to a recording medium such as paper, thereby recording images, characters, etc. , high speed, low noise, easy multicolor printing, great flexibility in recording patterns, and no need for development or fixing, making it suitable for a variety of uses as a recording device for various shapes and color images, including kanji. It is rapidly spreading in the world. Furthermore, images formed using the multicolor inkjet method can produce records that are comparable to multicolor printing using the plate making method or printing using the color photographic method, making it ideal for applications that require fewer copies to be produced. Since it is cheaper than photographic technology, it is being widely applied to the field of full-color image recording. Efforts have been made in terms of equipment and ink composition to use high-quality paper or coated paper used for ordinary printing and writing as the recording medium used in this inkjet recording method. However, as the performance of inkjet recording devices has improved and their applications have expanded, such as higher speeds, higher definitions, and full-color inkjet recording devices, more sophisticated characteristics have come to be required of recording media. In other words, the recording medium must have high ink dot density, bright and colorful tones, ink absorption is fast and the ink will not run out or smudge even when ink dots overlap, and the ink dots must be The horizontal diffusion of the image should not be larger than necessary, and the surrounding area should be smooth and not blurry. Furthermore, it is required that the resistance of the dye when the recorded image is exposed to ultraviolet rays, oxygen in the air, or water be not reduced, but preferably increased. Several proposals have been made to solve these problems. For example, JP-A-52-
No. 53012 describes inkjet recording paper, which is made by moistening a low-size base paper with a coating for surface treatment.
Further, JP-A-53-49113 discloses an inkjet recording paper in which a sheet containing urea-formalin resin powder is impregnated with a water-soluble polymer. Although these general paper type inkjet recording papers absorb ink quickly, they have the disadvantage that the periphery of dots tends to become blurred and the dot density is low. Further, JP-A No. 55-5830 discloses an inkjet recording paper having an ink-absorbing coating layer on the surface of the support, and JP-A No. 55-51583 discloses a non-colloidal pigment as a pigment in the coating layer. An example using silica powder is disclosed in JP-A-55-11829, and an example of smear paper using a two-layer structure with different ink absorption speeds is disclosed. These coated paper-type inkjet recording papers are improved over general paper-type inkjet recording papers in terms of dot diameter, dot shape, dot density, and color tone reproducibility, but there are Many inks are water-based inks that use water-soluble dyes, and if the image formed on the recording medium is exposed to water, the dye may dissolve again and ooze out, significantly reducing the value of the recorded material. There is a problem. Therefore, in order to improve this drawback, for example, JP-A-55-53591 discloses an example in which a water-soluble metal salt is applied to the recording surface, and JP-A-56-84992 discloses a method in which a polycationic polymer electrolyte is applied. An example of a recording medium containing on the surface is disclosed in JP-A-55-150396, and a method of applying a water-resistant agent that forms a lake with the dye in the ink after inkjet recording, and JP-A-55-150396 describes No. 56-58869 discloses a method for making a recording sheet coated with a water-soluble polymer waterproof by insolubilizing the water-soluble polymer after inkjet recording. However, these waterproofing methods have a weak effect on water resistance, or the waterproofing agent causes some kind of reaction with the dye, reducing the shelf life of the dye, making it impossible to achieve both sufficient water resistance and fire resistance. It was quite difficult. (C) Purpose of the Invention The present invention improves the water resistance and light resistance of an aqueous ink image in an inkjet recording medium in which a recorded image is formed by jetting an inkjet aqueous ink onto the recording medium. Our goal is to provide high-speed, high-definition recording media with excellent storage stability. (D) Structure and operation of the invention That is, the present invention forms a recorded image using an aqueous ink containing at least one type of water-soluble dye among direct dyes, acid dyes, basic dyes, reactive dyes, and food colorings. In the inkjet recording medium, the recording medium is composed of a porous inorganic pigment selected from at least one of synthetic silica or hydrated aluminum oxide having an average secondary particle diameter of 0.5 to 30 μm, which is agglomerated primary particles, and a cationic inkjet recording medium. The present invention is an inkjet recording medium characterized by being provided with a coating layer containing a synthetic resin and at least one kind of magnesium sulfate or its double salt. According to the present invention, porous inorganic pigments have the ability to improve the absorption capacity of aqueous inks and improve color density and chromaticity. The cationic resin has the role of insolubilizing the water-soluble dye in the water-based ink and improving water resistance. However, these cationic resins have the property of reducing light resistance, and although the cationic resin used in the present invention is selected to have a relatively small reduction rate, this influence cannot be avoided. Magnesium sulfate has the ability to prevent or improve the reduction in light resistance caused by cationic resins, but the reason for this is not clear. The porous inorganic pigment referred to in the present invention is a dry powder obtained by aggregating primary particles of synthetic silica or hydrated aluminum oxide to form a dry powder with an average secondary particle size of 0.5 μm to 30 μm. When aluminum oxide is synthesized in an aqueous solution from water-soluble raw materials, its primary particles have a size of several microns to several hundred microns and have self-agglomerating properties, so they must be dried, then crushed, and classified. By adjusting the particle size to the desired size using a spray dryer or the like during drying, a porous inorganic pigment can be obtained. In addition, synthetic silica and hydrated aluminum oxide
If it is a fine powder of 1 μm or less, it can be dispersed in water, added with a binder or adhesive, dried, crushed, classified, or spray-dried with a spray dryer to reduce the average secondary particle diameter to 0.5. μm~
Porous inorganic pigments of 30 μm are also possible. Furthermore, in order to form fine aqueous dispersions such as colloidal silica and colloidal alumina into particles of 0.5 μm or more, urea-formalin resin etc. are generated in a suspension of fine particles as disclosed in USP-3855172. , by adjusting its generation conditions,
It can also be a porous inorganic pigment granulated to a desired secondary particle size. The synthetic silica referred to in the present invention refers to dry process silica produced by thermal decomposition of silicon tetrachloride, so-called white carbon such as double decomposition precipitation products produced by sodium silicate acid, carbon dioxide, ammonium salt, etc., and produced by sodium silicate acid. Silica sol obtained through thermal decomposition or an ion-exchange resin layer, or colloidal silica obtained by heating and aging this silica sol, and by gelling the silica sol and changing the formation conditions, primary particles ranging from several millimicrons to several tens of millimicrons can be produced. Silica gel particles are three-dimensional secondary particles with siloxane bonds, and also so-called synthetic molecules produced by heating silica sol, sodium silicate, sodium aluminate, etc. as starting materials at 80°C to 120°C. Refers to synthetic silicon compounds mainly composed of silicon dioxide, such as sieves. The porous hydrated aluminum oxide referred to in the present invention is an aluminum salt such as aluminum sulfate, aluminum nitrate, aluminum chloride and the like, or an alkali metal salt of aluminate such as sodium or potassium aluminate salt or its like. A gel obtained by neutralizing or ion-exchanging an aqueous solution of both water-soluble aluminum compounds using an ion-exchange resin, which is called a hydrogel, is usually washed to remove salts and then dried. It refers to the product obtained by making it into xerogel. By using spray drying or the like for drying, it can be made into a powder suitable for blending into a coating solution. It is also possible to make a powder by drying it in block form and then crushing and classifying it. The hydrated oxide thus obtained after drying has most, if not all, of its free water removed, and usually some of its bound water as well, with most of its structure being removed. It irreversibly sets into a porous solid. The pore diameter of the porous solid thus obtained is usually 50 Å to 5,000 Å, and the surface charge of the secondary particles when dispersed in water is plascharge (cationic). In the present invention, the above porous inorganic pigment can also be used in combination with the following inorganic or organic pigments. In this case, the porous inorganic pigment is used in an amount of 20% by weight or more, preferably 40% by weight or more of the total pigment. Examples of inorganic pigments that can be used in combination include light calcium carbonate,
Heavy calcium carbonate, kaolin (white clay), talc,
Calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, zinc carbonate, satin white,
Aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica,
Examples of white pigments and organic pigments such as aluminum hydroxide, alumina, and lithopone include styrene plastic pigments, acrylic plastic pigments, microcapsules, and urea resin pigments. The cationic resin referred to in the present invention refers to a monomer, oligomer, or polymer that dissociates and exhibits cationic properties when dissolved in water, preferably having a quaternary ammonium group, and particularly preferably the following () to (). A compound having a structure represented by the general formula. () In the formula, R 1 , R 2 , R 3 are alkyl groups, m is 1 to 7, n
is 2 to 10, and Y represents an acid group. () () () In the formulas () to (), R 1 and R 2 are −CH 3 and −CH 2
-CH3 , -CH2 - CH2 -OH and Y represent acid groups. () Polyalkylene polyamine dicyandiamide ammonium salt condensate () Polyamide epichlorohydrin resin Examples of the compound represented by the general formula () include Nalpoly 607 (manufactured by Nalco Chemical Co., Ltd.) and Polyfix 601 (manufactured by Showa Kobunshi Co., Ltd.). The compounds represented by general formulas () to () are polydiallylamine derivatives, obtained by cyclopolymerization of diallylamine compounds, and Percoll 1697
(Allied Colloids), Cat Floc (Calgon
Corp), PAS (Nitto Boseki), Neo Fixtures
Examples include RPD (manufactured by NICCA Chemical Co., Ltd.). Furthermore, examples of the compound represented by the general formula () include Neofix RP-70 (manufactured by NICCA Chemical Co., Ltd.). Further, examples of the compound represented by the general formula () include Epinox 1301A (Dietzk Hercules Co., Ltd.), Kymen 557H (Dietzk Hercules Co., Ltd.), Polyfix 301 (Showa Kobunshi Co., Ltd.), and the like. The water resistance according to the present invention can be improved by using the cationic resins represented by the general formulas () to () in a content of usually 0.1 to 4 g/m 2 , preferably 0.2 to 2 g/m 2 . In the present invention, at least one kind of magnesium sulfate or its double salt refers to anhydrous magnesium sulfate, magnesium sulfate with water of crystallization, and various types of magnesium sulfate with water of crystallization, such as potassium magnesium sulfate, sodium magnesium sulfate, and ammonium magnesium sulfate. Refers to double salt. The content of at least one of these magnesium sulfates or double salts thereof is expressed as magnesium sulfate (MgSO 4 ).
Deterioration of light resistance can be prevented by setting the amount to 0.01 to 4 g/m 2 , preferably 0.2 to 2 g/m 2 . The method of applying these porous inorganic pigments, cationic resins, and at least one kind of magnesium sulfate or its double salt to a recording medium is to disperse or dissolve them in water and, if necessary, use commonly used adhesives or inorganic pigments. Other additives are added to form a coating solution, which is coated and dried using a size press device, gate roll coater, air knife coater, blade coater, spray, etc. Examples of adhesives include oxidized starch, etherified starch, cellulose derivatives such as carboxymethylcellulose and hydroxyethylcellulose, casein, gelatin, soybean protein, polyvinyl alcohol and its derivatives, maleic anhydride resin, and ordinary styrene-butadiene copolymers. Conjugated diene polymer latex such as methyl methacrylate-butadiene copolymer, acrylic polymer latex such as polymer or copolymer of acrylic acid ester and methacrylic acid ester, vinyl polymer latex such as ethylene vinyl acetate copolymer Polymer latexes, functional group-modified polymer latexes with monomers containing functional groups such as carboxyl groups of these various polymers, melamine resins, urea resins,
water-based adhesives such as thermosetting synthetic resins, etc., and synthetic resin adhesives such as polymethyl methacrylate, polyurethane resins, unsaturated polyester resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral, alkyd resins, etc. alone or in combination. It is used as These adhesives are used in an amount of 2 parts to 100 parts, preferably 5 parts to 30 parts, per 100 parts of the pigment, but the ratio is not particularly limited as long as the amount is sufficient to bind the pigment. However, if 100 parts or more of adhesive is used, the adhesive film formation reduces the void structure or makes the voids extremely small, which is not preferable. Other additives include pigment dispersants, thickeners,
Fluidity modifier, antifoaming agent, foam suppressor, mold release agent, foaming agent, penetrating agent, colored dye, colored pigment, fluorescent whitening agent,
UV absorbers, antioxidants, preservatives, anti-bacterial agents,
A water resistant agent and the like can also be added as appropriate. As the support, a sheet material such as paper or thermoplastic resin film is used. In the case of paper, it is paper with no sizing agent added or with appropriate sizing, and may or may not contain filler. In addition, in the case of thermoplastic films, transparent films such as polyester, polystyrene, polyvinyl chloride, polymethyl methacrylate, cellulose acetate, polyethylene, polycarbonate, etc., and white opaque films filled with white pigment or made by fine foaming are used. Ru. As the white pigment to be filled, many pigments are used, such as titanium oxide, calcium sulfate, calcium carbonate, silica, clay, talc, and zinc oxide. It is also possible to use so-called laminated paper, which is obtained by pasting these resin films on the surface of paper or by processing it with molten resin. A subbing layer, corona discharge processing, etc. may be applied to improve the adhesion between the resin surface and the ink receiving layer. A sheet simply coated on a support can be used as it is as a recording sheet according to the present invention, but it may be necessary to impart surface smoothness by passing it between roll nips under pressure or heat and pressure using, for example, a super calender or gloss calender. is also possible. In this case, the degree of processing may be limited because excessive processing by supercalender processing will reduce ink absorbency due to the gaps between particles that have been formed. The aqueous ink referred to in the present invention is a recording liquid comprising the following colorant, liquid medium, and other additives. The coloring agent may be a direct dye, an acid dye, a basic dye, a reactive dye, or a water-soluble dye such as food coloring. For example, direct dyes include CIDirect Black 2, 4, 9, 11, 14, 17,
19, 22, 27, 32, 36, 38, 41, 48, 49, 51,
56, 62, 71, 74, 75, 77, 78, 80, 105, 106,
107, 108, 112, 113, 117, 132, 146, 154,
194 CIDirect Yellow 1, 2, 4, 8, 11, 12,
24, 26, 27, 28, 33, 34, 39, 41, 42, 44,
48, 50, 51, 58, 72, 85, 86, 87, 88, 98,
100, 110 CIDirect Orange 6, 8, 10, 26, 29, 39,
41, 49, 51, 102 CIDirect Red 1, 2, 4, 8, 9, 11, 13,
17, 20, 23, 24, 28, 31, 33, 37, 39, 44,,
46, 47, 48, 51, 59, 62, 63, 73, 75, 77,
80, 81, 83, 84, 85, 90, 94, 99, 101, 108,
110, 145, 189, 197, 220, 224, 225, 226,
227, 230 CIDirect Violet 1, 7, 9, 12, 35, 48,
51, 90, 94 CIDirect Blue 1, 2, 6, 8, 15, 22, 25,
34, 69, 70, 71, 72, 75, 76, 78, 80,, 81, 82,
83, 86, 90, 98, 106, 108, 110, 120, 123,
158, 163, 165, 192, 193, 194, 195, 196, 199,
200, 201, 202, 203, 207, 218, 236, 237, 239,
246, 258 CIDirect Green 1, 6, 8, 28, 33, 37, 63,
64 CIDirect Braun 1A, 2, 6, 25, 27, 44,
58, 95, 100, 101, 106, 112, 173, 194, 195,
209, 210, 211 As acidic dyes, ClAcid Black 1, 2, 7, 16, 17, 24, 26,
28, 31, 41, 48, 52, 58, 60, 63, 94, 107,
109, 112, 118, 119, 121, 122, 131, 155,
156 ClAcid Yellow 1, 3, 4, 7, 11, 12,
13, 14, 17, 18, 19, 23, 25, 29, 34, 36,
38, 40, 41, 42, 44, 49, 53, 55, 59, 60,
71, 72, 76, 78, 99, 111, 114, 116, 122,
135, 161, 172 ClAcid Orange 7, 8, 10, 33, 56, 64 ClAcid Red 1, 4, 6, 8, 13, 14, 15,
18, 19, 21, 26, 27, 30, 32, 34, 35, 37,
40, 42, 51, 52, 54, 57, 80, 82, 83, 85,
87, 88, 89, 92, 94, 97, 106, 108, 110,
115, 119, 129, 131, 133, 134, 135, 154,
155, 172, 176, 180, 184, 186, 187, 249,
254, 256, 317, 318 ClAcid Violet 7, 11, 15, 34, 35, 41, 43,
49, 75 ClAcid Blue 1, 7, 9, 22, 23, 25, 27,
29, 40, 41, 43, 45, 49, 51, 53, 55, 56,
59, 62, 78, 80, 81, 83, 90, 92, 93, 102,
104, 111, 113, 117, 120, 124, 126, 145,
167, 171, 175, 183, 229, 234, 236 CIAcid Green 3, 12, 19, 27, 41, 9, 19,
20, 25 CIAcid Braun 4, 14 Basic dyes include CIBasic Black 2, 8 CIBasic Yellow 1, 2, 11, 12, 14, 21, 32,
36 CIBasic Orange 2, 15, 21, 22 CIBasic Red 1, 2, 9, 12, 13, 37 CIBasic Violet 1, 3, 7, 10, 14 CIBasic Blue 1, 3, 5, 7, 9, 24, 25,
26,28,29 CIBasic Green 1,4 CIBasic Braun 1,12 Reactive dyes include CIReactive Black 1,3,5,6,8,12,
14 CIReactive Yellow 1, 2, 3, 13, 14, 15,
17 CIReactive Orange 2, 5, 7, 16, 20, 24 CIReactive Red 6, 7, 11, 12, 15, 17,
21, 23, 24, 35, 36, 42, 63, 66 CIReactive Violet 2, 4, 5, 8, 9 CIReactive Blue 2, 5, 7, 12, 13, 14,
15, 17, 18, 19, 20, 21, 25, 27, 28, 37,
38, 40, 41 CIReactive Green 5, 7 CIReactive Braun 1, 7, 16 Furthermore, as food colorants, CIFood Black 2 CIFood Yellow 3, 4, 5 CIFood Red 2, 3, 7, 9, 14, 52, 87,
92, 94, 102, 104, 105, 106 CI Food Violet 2 CI Food Blue 1, 2 CI Food Green 2, 3, etc. In addition, the liquid medium for the aqueous ink includes water and various water-soluble organic solvents, such as methyl alcohol,
Ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol,
Alkyl alcohols having 1 to 4 carbon atoms such as sec-butyl alcohol, tert-butyl alcohol and isobutyl alcohol; Amides such as dimethylformamide and dimethylacetamide; Ketones or ketone alcohols such as acetone and diacetone alcohol; tetrahydrofuran and dioxane Ethers such as polyethylene glycol, polyalkylene glycols such as polypropylene glycol; ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol Examples include alkylene glycols having 2 to 6 alkylene groups; lower alkyl ethers of polyhydric alcohols such as glycerin, ethylene glycol methyl ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl ether. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether are preferred. Examples of other additives include PH regulators, sequestrants, antifungal agents, viscosity regulators, surface tension regulators, wetting agents, surfactants, and rust preventives. Ink jet suitability was measured by the following method. Color density is the density of images obtained by solid printing with cyan (C), magenta (M), yellow (Y), and black (Bl) inks using a Sharp inkjet color image printer (IO-700). Values measured with a Macbebes densitometer RD514 were used. Light resistance was determined using a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for the image area obtained by solid printing with C, M, Y, and Bl inks using a Canon inkjet printer (A-1210). , FAL−25X
- HCL type) at 40℃, 60%, illumination intensity 41w/ m2 for 40 hours, the color density before and after irradiation was measured with Macbeth densitometer RD514, and the color density after irradiation was divided by the color density before irradiation. The percentage of the value obtained is the survival rate,
100-residual rate was shown as light resistance (fading rate).
The smaller the number, the better the water resistance. Water resistance was determined by using the same Canon inkjet printer to print solid images using C, M, Y, and Bl inks, immersing them in running water at 30°C for 3 minutes, and measuring the density before and after immersion using Macbeth density. The residual rate was determined by dividing the concentration after immersion by the concentration before immersion, and 100-residual rate was expressed as water resistance (fading rate). The smaller the number, the better the water resistance. To measure the ink absorption speed, use a Sharp or Canon inkjet printer, feed the paper immediately after solid red printing (magenta + yellow) (about 1 second later), and contact it with a paper presser roll or your finger. Judgment was made based on whether dirt appeared or not. Furthermore, the absorption capacity was measured at 20°C using a 1/1 solution of polyethylene glycol (PEG No. 400)/water.
Contact with a fixed area of the ink receiving layer for 10 seconds, remove excess liquid with absorbent paper, measure the weight of the solution absorbed into the ink receiving layer, and use the value calculated as grams per square meter. there was. The larger the value, the larger the absorption capacity, which is preferable. (E) Examples The present invention will be described below with reference to Examples, but the invention is not limited to these examples. Note that parts and percentages shown in the examples mean parts by weight and percentages by weight. Example 1 80 parts of LBKP with water level 370mlcsf, water level 410mlcsf
From a slurry consisting of 20 parts of NBKP, 10 parts of talc for internal filling, 3 parts of clay for internal filling, 0.5 parts of rosin sizing agent (Newfor 100, manufactured by Deitsku Hercules), and 2.5 parts of band, on a Fourdrinier paper machine. Basis weight 68g/
An acid coated base paper was produced by making a base paper of 1.5 g/m 2 by using a size press during paper making. The Steckigt size degree of this base paper is 33
It was hot in seconds. As a coating liquid, 100 parts of porous inorganic pigment synthetic silica (Syroid 620, manufactured by Fuji Davison),
Water-soluble resin polyvinyl alcohol (PVA117,
Contains 90 parts manufactured by Kuraray Co., Ltd., 10 parts of cationic resin Polyfix 601 (manufactured by Showa Kobunshi Co., Ltd.), 10 parts of crystalline magnesium sulfate (MgSO 4 7H 2 O), and a small amount of other antifoaming agents and fluorescent agents at a concentration of 16%. Make a water-based coating solution of
The solid content of 9 is applied to the acidic base paper using an air knife coater.
It was smeared at a concentration of g/m 2 and dried. The paper was then lightly passed through a super calender to obtain the recording paper of Example 1. The Beck smoothness of this recording paper was 105 seconds. Table 1 shows the results of evaluating the suitability of inkjet for this recording paper. Comparative Example 1 Comparative Example 1 was prepared in the same manner as in Example 1 except that crystalline magnesium sulfate was removed from the coating solution of Example 1.
Record sheets were obtained. The Beck smoothness of this recording paper was 102 seconds. Table 1 shows the results of evaluating the inkjet suitability of this recording paper. Comparative Example 2 A recording paper of Comparative Example 2 was obtained in exactly the same manner as in Example 1 except that the cationic resin was removed from the coating solution of Example 1. The Beck smoothness of this recording paper was 95 seconds. Table 1 shows the results of evaluating the inkjet suitability of this recording paper. Comparative Example 3 The porous inorganic pigment (Syroid 620) in the coating solution of Example 1 was mixed with kaolin for coating (Ultra White).
A recording paper of Comparative Example 3 was obtained in exactly the same manner as in Example 1 except that 100 copies of 90 (manufactured by Engelhard) were used. The Beck smoothness of this recording paper was 260 seconds.
Table 1 shows the results of evaluating the inkjet suitability of this recording paper. Comparative Example 4 A recording paper of Comparative Example 4 was obtained in exactly the same manner as in Example 1 except that calcium chloride was used in place of magnesium sulfate in the coating solution of Example 1. The Beck smoothness of this recording paper was 110 seconds. Table 1 shows the results of evaluating the inkjet suitability of this recording paper. Examples 2 to 7 80 parts of LBKP with a water content of 370 mlcsf, a water content of 400 mlcsf
20 parts of NBKP, 13 parts of heavy calcium carbonate, 1 part of cationic starch, 0.12 parts of alkyl ketene dimer sizing agent (Haakon W manufactured by Deitzk Hercules)
A base paper with a basis weight of 68 g/m 2 is made from a slurry consisting of 1 part and 0.4 parts of polyalkylene polyamine epichlorohydrin resin using a Fourdrinier paper machine, and during paper making, oxidized starch is added in solid content to 1.5 g/m 2 using a size press machine.
A neutral coated base paper was produced. The Steckigt size degree of this base paper was 35 seconds. As the first coating liquid, a slurry of 100 parts of synthetic silica (Nippur Seal LP, manufactured by Nippon Silica Kogyo Co., Ltd.) dispersed in 400 parts of water was passed through a Viscomill to crush aggregated particles, and 15 parts of polyvinyl alcohol was added to give a concentration of 18%. An aqueous first coating solution was prepared and applied to the neutral coated base paper using an air knife coater so that the solid content was 13 g/m 2 , and dried to prepare an undercoated paper. Next, synthetic silica (thyroid) was used as the second coating liquid.
74, manufactured by Fuji Davison Co., Ltd.) 100 parts, water-soluble resin polyvinyl alcohol (PVA117, manufactured by Kuraray Co., Ltd.)
40 parts, neofix as cationic resin
7 parts of RPD (manufactured by Nicca Chemical Co., Ltd.), 1 part, 5 parts, 10 parts, 20 parts of anhydrous magnesium sulfate (MgSO 4 ),
Concentration 13 consisting of 40 parts, 60 parts, and a small amount of antifoaming agent.
% of the second coating solution was prepared, and it was spread on the undercoated paper of the first coating solution using an air knife coater so that the solid content was 5 g/m 2 and dried. Examples 2, 3, 4, 5, 6, respectively, were then passed through a supercalender.
7, was used as the recording paper. Table 2 shows the results of evaluating the inkjet suitability of this recording paper. Comparative Example 5 Examples 2 to 7 except that anhydrous magnesium sulfate in the second coating liquid used in Examples 2 to 7 was not added.
A recording sheet of Comparative Example 5 was prepared in exactly the same manner as described above. Table 2 shows the results of evaluating the suitability of inkjet for this recording paper. Example 8 Potassium magnesium sulfate (K 2 Mg 2 (SO 2 ) 3 ) was used in place of the anhydrous magnesium sulfate used in Example 4.
A recording sheet of Example 8 was obtained in exactly the same manner as Examples 2 to 7 except that 10 copies were used. Table 2 shows the results of evaluating the inkjet suitability of this recording paper. Comparative Examples 6 to 10 In place of the magnesium potassium sulfate used in Example 8, KCl, NaCl, Na 2 SO 4 , CaCl 2 .
Recording sheets of Comparative Examples 6, 7, 8, 9, and 10 were obtained in exactly the same manner as in Example 8 except that 2H 2 O and ZnCl 2 were used. Table 2 shows the results of evaluating the inkjet suitability of these recording papers. Example 9 Synthetic silica (Syroid 620), the porous inorganic pigment in the coating solution of Example 1, was mixed with an average secondary particle size of
A recording sheet of Example 9 was obtained in exactly the same manner as in Example 1 except that 100 parts of porous hydrated aluminum oxide having a diameter of 7.2 μm and an average pore diameter of 140 angstroms was used. The smoothness of this recording paper is
It was hot in 110 seconds. Table 1 shows the results of evaluating the inkjet suitability of this recording paper. [Results in Table 1] In Example 1, synthetic silica, cationic resin, and magnesium sulfate are essential, and the ink absorption ability, color density, water resistance, absorption capacity, and absorption rate are well balanced. Comparative Example 1 is the same as Example 1 except that magnesium sulfate is removed, but M (magenta) and B1
(Black) The light resistance fading rate was very poor. Similarly, in Comparative Example 2, the cationic resin was removed from Example 1, and the fading rate of light resistance was high, and the fading rate of light resistance of M and B1 was also high. Furthermore, Comparative Example 3 shows a case in which the synthetic silica in Example 1 was replaced with kaolin for coating, and the recording density of each color was significantly lowered, and the absorption capacity was also small, resulting in a recorded image overflowing with ink and a decrease in resolution. , indicates poor image quality. In addition, the absorption speed is slow, and if the paper is touched with a paper pressure roll or a finger after recording, it will stain, making it impractical for practical use. Moreover, Comparative Example 4 is obtained by replacing magnesium sulfate with calcium chloride in Comparative Example 1, and the fading rate of the light resistance of B1 is large, which also poses a practical problem. Example 9, in which synthetic silica in Example 1 was replaced with hydrated aluminum oxide, had the same effects as Example 1 and could provide a well-balanced and practically excellent inkjet recording paper. [Results in Table 2] Examples include color density, water resistance, light resistance, absorption capacity,
The absorption speed is well balanced and there is no practical problem, but the comparative example has a large fading rate of light resistance of M and B1.
This shows that this is a serious problem in practice.
【表】【table】
【表】【table】
【表】【table】
【表】
○は吸収速度が速く、印字後ペーパー押えロー
ル又は指等に接触したときに汚れが出ずに良
好なことを示す。
(F) 発明の効果
本発明による多孔性無機顔料、カチオン性樹脂
及び硫酸マグネシウムを含有する実施例１〜９に
於いては、インク吸収能力、色濃度及び保存性
（耐光性及び耐水性）の全てに於いて極めて優れ、
特に硫酸マグネシウムを使用していない比較例に
比べ耐光性（Bl及びマゼンタ）が極めて改良さ
れていて、インクジエツト用紙として優れたもの
であることが明らかである。[Table] ○ indicates that the absorption speed is fast and there is no stain when it comes into contact with the paper presser roll or fingers after printing.
(F) Effects of the Invention In Examples 1 to 9 containing the porous inorganic pigment, cationic resin, and magnesium sulfate according to the present invention, ink absorption ability, color density, and storage stability (light resistance and water resistance) were improved. Excellent in everything,
In particular, the light resistance (Bl and magenta) was significantly improved compared to the comparative example in which magnesium sulfate was not used, and it is clear that the paper is excellent as an inkjet paper.
Claims (1)
料及び食品用色素の内の少なくとも一種の水溶性
染料を含有する水性インクを用いて記録画像を形
成するインクジエツト記録媒体に於いて、該記録
媒体が一次粒子を凝集させた平均二次粒子径が
0.5〜30μmの合成シリカ或は水和アルミニウム酸
化物の少なくとも一種から選ばれた多孔性無機顔
料、カチオン性樹脂及び少なくとも一種以上の硫
酸マグネシウム又はその複塩を含む塗工層を設け
たことを特徴とするインクジエツト記録媒体。 ２ カチオン性樹脂が４級アンモニウム基を含む
水溶性樹脂である特許請求の範囲第１項記載のイ
ンクジエツト記録媒体。 ３ 少なくとも一種以上の硫酸マグネシウム又は
その複塩の含有量が硫酸マグネシウム分として
0.01〜４ｇ／m2の範囲である特許請求の範囲第１
項又は第２項記載のインクジエツト記録媒体。[Scope of Claims] 1. An inkjet recording medium for forming recorded images using an aqueous ink containing at least one water-soluble dye selected from direct dyes, acid dyes, basic dyes, reactive dyes, and food colorings. In the recording medium, the average secondary particle diameter of aggregated primary particles is
A coating layer containing a porous inorganic pigment selected from at least one type of synthetic silica or hydrated aluminum oxide with a diameter of 0.5 to 30 μm, a cationic resin, and at least one type of magnesium sulfate or its double salt is provided. An inkjet recording medium. 2. The inkjet recording medium according to claim 1, wherein the cationic resin is a water-soluble resin containing a quaternary ammonium group. 3 The content of at least one kind of magnesium sulfate or its double salt is as magnesium sulfate.
Claim 1 in the range of 0.01 to 4 g/m 2
The inkjet recording medium according to item 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59166282A JPS6143593A (en) | 1984-08-07 | 1984-08-07 | Ink jet recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59166282A JPS6143593A (en) | 1984-08-07 | 1984-08-07 | Ink jet recording medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6143593A JPS6143593A (en) | 1986-03-03 |
| JPH0557114B2 true JPH0557114B2 (en) | 1993-08-23 |
Family
ID=15828475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59166282A Granted JPS6143593A (en) | 1984-08-07 | 1984-08-07 | Ink jet recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6143593A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013605A3 (en) * | 1998-12-24 | 2000-07-05 | Tokuyama Corporation | Cationic polymer-modified silica dispersion and production process for the same |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3943159B2 (en) * | 1995-05-31 | 2007-07-11 | 三菱製紙株式会社 | Inkjet recording sheet |
| GB2346157A (en) * | 1999-01-28 | 2000-08-02 | Rexam Coated Products Limited | Surface-treated paper for use as recording medium |
| JP3328602B2 (en) * | 1999-03-31 | 2002-09-30 | 日本製紙株式会社 | Inkjet recording paper |
| AU2002213734A1 (en) * | 2000-11-17 | 2002-05-27 | Sihl | Ink jet printing material |
| WO2003076201A1 (en) * | 2002-03-08 | 2003-09-18 | Nippon Paper Industries Co., Ltd. | Inkjet recording paper |
| DE60315695T2 (en) * | 2002-10-24 | 2008-06-05 | Nippon Paper Industries Co. Ltd. | HEAT-SENSITIVE RECORDING MEDIUM |
| KR101063209B1 (en) | 2002-11-21 | 2011-09-07 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Recording sheet with ink receiving layer and coating liquid for forming ink receiving layer |
| JP4639069B2 (en) * | 2004-11-05 | 2011-02-23 | セーレン株式会社 | Pigment printing method |
| CN101910326A (en) | 2007-12-28 | 2010-12-08 | 佳能株式会社 | Surface-modified inorganic pigment, colored surface-modified inorganic pigment, recording medium and production processes thereof, and image forming method and recorded image |
| US20100129553A1 (en) * | 2008-11-27 | 2010-05-27 | International Paper Company | Optical Brightening Compositions For High Quality Inkjet Printing |
| CA2772385C (en) * | 2009-08-31 | 2017-03-14 | Newpage Corporation | Paper substrate with inkjet-receptive coating comprising cationic porous silica |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5920696A (en) * | 1982-07-28 | 1984-02-02 | Jujo Paper Co Ltd | Ink jet recording paper |
| JPS5978885A (en) * | 1982-10-27 | 1984-05-07 | Ricoh Co Ltd | Ink jet recording sheet |
-
1984
- 1984-08-07 JP JP59166282A patent/JPS6143593A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5920696A (en) * | 1982-07-28 | 1984-02-02 | Jujo Paper Co Ltd | Ink jet recording paper |
| JPS5978885A (en) * | 1982-10-27 | 1984-05-07 | Ricoh Co Ltd | Ink jet recording sheet |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1013605A3 (en) * | 1998-12-24 | 2000-07-05 | Tokuyama Corporation | Cationic polymer-modified silica dispersion and production process for the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6143593A (en) | 1986-03-03 |
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