JPH042113B2 - - Google Patents
Info
- Publication number
- JPH042113B2 JPH042113B2 JP60020546A JP2054685A JPH042113B2 JP H042113 B2 JPH042113 B2 JP H042113B2 JP 60020546 A JP60020546 A JP 60020546A JP 2054685 A JP2054685 A JP 2054685A JP H042113 B2 JPH042113 B2 JP H042113B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- water
- ink
- formula
- 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
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000001454 recorded image Methods 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000049 pigment Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000000975 dye Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- -1 satin white Chemical compound 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 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
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008107 starch Substances 0.000 description 4
- 235000019698 starch Nutrition 0.000 description 4
- 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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid 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
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001281 polyalkylene Polymers 0.000 description 3
- 229920000768 polyamine Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 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
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 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
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000003963 antioxidant agent 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
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910002029 synthetic silica gel Inorganic materials 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
- 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
- ZWVMLYRJXORSEP-UHFFFAOYSA-N 1,2,6-Hexanetriol Chemical compound OCCCCC(O)CO ZWVMLYRJXORSEP-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- KPTNUCBVMWICQI-UHFFFAOYSA-N 1-methyl-2h-tetrazole-5-thione;sodium Chemical compound [Na].CN1NN=NC1=S KPTNUCBVMWICQI-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
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- GVKHIGXYPDJFEO-UHFFFAOYSA-N CN1N=NN=C1.[Na] Chemical compound CN1N=NN=C1.[Na] GVKHIGXYPDJFEO-UHFFFAOYSA-N 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
- 239000004640 Melamine resin 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
- 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 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 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
- 239000000980 acid dye Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000002313 adhesive film Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 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
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 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
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 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
- 239000000835 fiber 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
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 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
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 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
- 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 1
- 150000002576 ketones Chemical class 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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- NNBBQNFHCVVQHZ-UHFFFAOYSA-N methyl carbamimidothioate;sulfuric acid Chemical compound CSC(N)=N.OS(O)(=O)=O NNBBQNFHCVVQHZ-UHFFFAOYSA-N 0.000 description 1
- 239000003094 microcapsule Substances 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
- 239000012860 organic pigment Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle 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
- 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
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002851 polycationic polymer Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol 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
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000003352 sequestering agent 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
- 239000002904 solvent Substances 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003860 storage Methods 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
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 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
- 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
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 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
- 239000013053 water resistant agent Substances 0.000 description 1
- 238000004078 waterproofing Methods 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
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 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
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
Landscapes
- 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、吸収性及び記録画像の保存性
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55−1829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、これらの耐水化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
性と耐光性を両立させることはなかなか困難であ
つた。
そこで、耐光性を向上させるために、例えば特
開昭54−68303号、同54−85804号及び同56−
18151号には、インク液中へ紫外線吸収剤を添加
した例が開示されている。しかしながらこれらの
紫外線吸収剤はインクの噴射安定性を低下させた
り、溶解度が低いために多量添加が出来ず微量添
加では効果が少ないと云う問題がある。また別の
解決策としてインクジエツト記録シートの方へベ
ンゾフエノン系、ベンゾトリアゾール系などの紫
外線吸収剤を含有させることが特開昭57−74192
号、同57−74193号及び同57−87988号で提案され
ているが、これらは水への溶解性が悪く多量に使
用することが困難であつたり、少量では効果がな
かつたり、又、乳化して用いると乳化剤の影響が
ある等の問題点がある。
(C) 発明の目的
本発明は、前述したようなインクジエツト適性
を改善し、水性インク画像の耐水性及び耐光性に
も優れた、特に水溶性黒色染料及び／又は水溶性
マゼンタ染料の耐光性、耐変褪色性を改善した記
録媒体を提供することを目的とする。
(D) 発明の構成及び作用
即ち、本発明は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、該記録媒体が下記一般式（）
で示される構造を有するヘテロ環化合物を含有す
るインクジエツト記録媒体である。
式中Ｘは基基本的にＣ，Ｎ，Ｏ、あるいはＳを
示す。更に具体的には式中Ｘは
(A) Industrial Application Field The present invention relates to a recording medium recorded using ink, and in particular, a recording medium that has high density of images and characters recorded on the medium, and has excellent absorbency and storage stability of recorded images. 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 multi-color printing, and great flexibility in recording patterns. Furthermore, it has features such as not requiring development or fixing, and is rapidly becoming popular for various uses as a recording device for various figures including Chinese characters, color images, etc. 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. That is, the recording medium should have a high density of ink dots and a bright and colorful color tone, and the ink should be absorbed quickly so that the ink will not run out or smudge even when the ink dots overlap. The horizontal diffusion of ink dots should not be larger than necessary, and the periphery should be smooth and not blurred. 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-55-1829, 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.
Most of the inks used for these recording media 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, causing the recording to fail. There are problems that significantly reduce the value of things. 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, with these methods, the effect of water resistance may be weak, or the water resistance agent may cause some kind of reaction with the dye, reducing the shelf life of the dye, making it difficult to achieve both sufficient water resistance and light resistance. It was quite difficult. Therefore, in order to improve the light resistance, for example, JP-A-54-68303, JP-A-54-85804 and JP-A-56-
No. 18151 discloses an example in which an ultraviolet absorber is added to an ink liquid. However, these ultraviolet absorbers have problems in that they reduce the jetting stability of the ink and have low solubility, so they cannot be added in large amounts and are less effective when added in small amounts. Another solution is to incorporate ultraviolet absorbers such as benzophenone and benzotriazole into the inkjet recording sheet according to JP-A-57-74192.
No. 57-74193 and No. 57-87988, but these have poor solubility in water and are difficult to use in large amounts, are ineffective in small amounts, and are difficult to emulsify. When used as an emulsifier, there are problems such as the influence of emulsifiers. (C) Object of the Invention The present invention improves the inkjet suitability as described above, and also provides excellent water resistance and light resistance of water-based ink images, particularly the light resistance of water-soluble black dyes and/or water-soluble magenta dyes. The purpose of the present invention is to provide a recording medium with improved resistance to change and fading. (D) Structure and operation of the invention That is, the present invention provides an inkjet recording medium that forms a recorded image using a water-based ink containing a water-soluble dye, and the recording medium has the following general formula ().
This is an inkjet recording medium containing a heterocyclic compound having the structure shown below. In the formula, X basically represents C, N, O, or S. More specifically, in the formula, X is
【式】【formula】
【式】＝Ｎ−、[Formula]=N-,
【式】−Ｏ−、又は
−Ｓ−（ここでR1，R2，R3，R4はＨあるいは−
OH、−CH3等の置換基）を示す。また式中Ｃ
＝Ｎ−で表わされる二重結合は化合物の他の構成
要素と共役していてもよい。またヘテロ環は−Ｘ
−Ｃ＝Ｎ−を含む５員環または６員環でありさら
に他の構成要素と多環を形成していてもよい。
本発明で言う一般式（）の構造を有する化合
物としては、[Formula] -O- or -S- (where R 1 , R 2 , R 3 , R 4 are H or -
substituents such as OH, -CH3 , etc.). Also, C in the formula
The double bond represented by =N- may be conjugated with other constituents of the compound. Also, the heterocycle is -X
It is a 5-membered ring or a 6-membered ring containing -C=N-, and may further form a polycyclic ring with other constituent elements. In the present invention, compounds having the structure of general formula () include:
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】等が挙げられる。またこれ
らヘテロ環化合物とヒンダードフエノール系酸化
防止剤やベンゾトリアゾール系又はベンゾフエノ
ン系紫外線吸収剤等を併用することは何ら問題な
い。更に記録媒体に適用するめに金属の塩とした
り、水溶性基を導入したり、乳化したりしてその
まま水または適当な溶媒に溶解したりして用いる
ことも可能である。記録媒体中のヘテロ環化合物
（）の含有量は0.2〜100mmol／m2、好ましくは
1.0〜50mmol／m2である。
本発明では前記ヘテロ環化合物（）を含有す
る記録媒体の作成方法としては、バルブ繊維を離
解してスラリーとし抄紙機で抄造せしめる際、途
中に設けたサイズプレス装置等でヘテロ環化合物
（）を溶解又は分散した塗工液を浸漬又は塗布
して含有させる方法、更に支持体にヘテロ環化合
物（）を含有する塗工液を通常の塗工装置を用
いて塗布してヘテロ環化合物（）を含有するイ
ンク受理層を設ける方法や、インク吸収性顔料及
び接着剤等からなるインク受理層の上に溶解又は
分散したヘテロ環化合物（）を塗布する方法等
がある。この場合一般に使われる填料や顔料、接
着剤及びその他の添加剤を併用することも可能で
ある。また、画像の耐水性を付与する必要があれ
ば、カチオン性樹脂を併用することも可能であ
り、本発明に於いては、耐水性、耐光性を同時に
向上させるためにはむしろ積極的に使用するのが
望ましい。
本発明で使用出来る填料あるいは顔料としては
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、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、リトボ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。これらの内本発明に
於いては、合成無定形シリカ及び水酸化アルミニ
ウムが好ましく用いられる。
本発明で言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
る化合物を言う。
式中R1，R2，R3はアルキル基、ｍは１〜７、
ｎは２〜20、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
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 Floe（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。
これらの一般式（）〜（）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である。
本発明で使用出来る接着剤としては、例えば、
酸澱粉、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〜120部、好ましくは５部〜70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、120部以上の
接着剤を用いると接着剤の造膜により、空隙構造
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、ポリカーボ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
ーなどで加熱及び／又は加圧下ロールニツプ間を
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。
本発明で言う水性インクとは、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
料が好ましく用いられる。
例えば、直接染料としてはExamples include [Formula]. Further, there is no problem in using these heterocyclic compounds together with hindered phenol antioxidants, benzotriazole-based or benzophenone-based ultraviolet absorbers, and the like. Furthermore, in order to apply it to a recording medium, it is also possible to use it as a metal salt, introduce a water-soluble group, or emulsify it and dissolve it in water or a suitable solvent as it is. The content of the heterocyclic compound ( ) in the recording medium is 0.2 to 100 mmol/m 2 , preferably
It is 1.0-50 mmol/ m2 . In the present invention, the method for producing a recording medium containing the heterocyclic compound () is as follows: When valve fibers are disintegrated into a slurry and made into paper using a paper machine, the heterocyclic compound () is prepared using a size press device installed midway. A method of incorporating a dissolved or dispersed coating liquid by dipping or coating, and a method of applying a coating liquid containing a heterocyclic compound () to a support using a normal coating device to coat the heterocyclic compound (). There are a method of providing an ink-receiving layer containing the ink-absorbing pigment, a method of applying a dissolved or dispersed heterocyclic compound () on the ink-receiving layer made of an ink-absorbing pigment, an adhesive, and the like. In this case, it is also possible to use commonly used fillers, pigments, adhesives and other additives. In addition, if it is necessary to impart water resistance to the image, it is possible to use a cationic resin in combination, and in the present invention, it is rather actively used in order to simultaneously improve water resistance and light resistance. It is desirable to do so. Examples of fillers or pigments that can be used in the present invention include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, and diatom. White pigments such as earth, calcium silicate, magnesium silicate, synthetic amorphous silica, aluminum hydroxide, alumina, lithobon, etc. and organic pigments include styrene plastic pigments, acrylic plastic pigments, microcapsules, urea resin pigments, etc. be. Among these, synthetic amorphous silica and aluminum hydroxide are preferably used in the present invention. 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 () Refers 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 represents 2 to 20, 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 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 Floe (Calgon)
Corp), PAS (Nitto Boseki Co., Ltd.), 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.). The content of the cationic resin represented by these general formulas () to () is usually 0.1 to 4 g/m 2 , preferably 0.2 to 2 g/m 2 . Examples of adhesives that can be used in the present invention include:
Acid starch, etherified starch, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, casein, gelatin, soy protein,
Polyvinyl alcohol and its derivatives, maleic anhydride resins, conjugated diene polymer latexes such as ordinary styrene-butadiene copolymers, methyl methacrylate-butadiene copolymers, and polymers or copolymers of acrylic esters and methacrylic esters. Acrylic polymer latex such as ethylene vinyl acetate copolymer, vinyl polymer latex such as ethylene-vinyl acetate copolymer, functional group-modified polymer latex with monomers containing functional groups such as carboxyl groups of these various polymers, melamine resin. , urea resin, etc., and synthetic resin adhesives such as polymethyl methacrylate, polyurethane resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, and alkyd resin. , used alone or in combination. These adhesives contain 2 parts per 100 parts of pigment.
Parts to 120 parts, preferably 5 parts to 70 parts, are used, but the ratio is not particularly limited as long as it is sufficient to bind the pigment. However, if 120 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 waterproofing agent and the like may 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 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 formed by fine foaming are used. 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 or corona discharge processing 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 also be heated and/or passed between roll nips under pressure using a super calender, gloss calender, etc. to impart surface smoothness. It is possible.
In this case, the degree of processing may be limited because excessive processing by supercalendering will reduce the ink absorbency due to the carefully formed voids between particles. The aqueous ink referred to in the present invention is a recording liquid comprising the following colorant, liquid medium, and other additives. As the coloring agent, water-soluble dyes such as direct dyes, acid dyes, basic dyes, reactive dyes, and food colorings are preferably used. For example, as a direct dye,
【表】【table】
【表】【table】
【表】
などが挙げられる。
また水性インク液媒体としては、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
エーテル類；ポリエチレングリコール、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調整剤、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。
本発明により、一般式（）の構造を有するヘ
テロ環化合物を含有させた記録媒体に、水性染料
を含有する水性インクを用いて記録すると画像の
耐光性が向上する。
その理由は定かではないが染料の褪色や変色は
紫外線等によつて光酸化を受けるためと考えら
れ、一般式（）の構造を有するヘテロ環化合物
はこの光酸化反応を抑制するのではないと考えら
れる。
インクジエツト適性の測定は下記の方法によつ
た。
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，Bk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)社製、FAL−
25X−HCL型）で40℃、60％、照度41w／m2で16
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耐光性（残
存率）として示した。
また照射射前後の反射率を分光反射濃度計（日
立カラーアナライザー607型）を用いて10nmごと
に反射率を測定後JIS−Ｚ−8722記載のＣ光源の
系数を用いてＸ，Ｙ，Ｚを計算後JIS−Ｚ−8730
に従つてＬ，ａ，ｂを求め照射前後の色度差△Ｅ
を得た。この値を変褪色量として示した。
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，Bk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耐水性の値とした。数値が高
い程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＋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、汚れが出ないかで判定した。
(E) 実施例
以下に本発明の実施例を挙げて説明するが、こ
られ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 １〜３
水度370mlCSFのLBKP80部、水度400ml
CSF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）
0.08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２ｇ／
m2付着させて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21秒であつた。
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、ポリビニルアルコール
（PVA110、クラレ社製）65部、カチオン性樹脂
（ポリフイクス601、昭和高分子社製）５部、及び
消泡剤少量から成る固型分18％の液を作成し固型
分10ｇ／m2となるように塗布乾燥して、インク受
理層を持つベース紙を作製した。
別に塗布液として２−メルカプトベンゾチアゾ
ール、２−メルカプトベンズイミダゾール、２−
メルカプトベンズオキサゾール各１部をエタノー
ル99部に溶解した液を前記ベース紙の表面に固型
分で0.5ｇ／m2となるように塗布乾燥し、次いで
軽くスーパーカレンダーを掛けて仕上げそれぞれ
実施例１〜３の記録紙とした。この記録紙につい
てインクジエツト適性を測定した結果を表−１に
示す。
比較例 １
実施例１で用いた塗布液から２−メルカプトベ
ンゾチアゾールを除いた他は実施例１と全く同様
にして比較例１の記録紙とした。この記録紙につ
いてインクジエツト適性を測定した結果を表１に
示す。
実施例 ４〜６
水度370mlCSFのLBKP80部、水度400ml
CSFのNBKP20部からなるパルプスラリーにタ
ルク20部、カチオン澱粉（Cato Ｆ、王子ナシヨ
ナル社製）0.5部を添加して坪量65ｇ／m2の長網
抄紙機で抄造し、抄造時にサイズプレス装置でポ
リビニルアルコール（PVA117、クラレ社製）２
％、ホワイトカーボン（ニツプシルLP、日本シ
リカ社製）６％、５−メルカプト−１−メチルテ
トラゾール−ナトリウム塩を各々0.2，2.0，4.0％
よりなるサイズピレス液60ｇ／m2付着させ、乾燥
後マシンカレンダーを通して仕上げ実施例４〜６
の記録紙とした。この記録紙についてインクジエ
ツト適性を測定した結果を表１に示す。
比較例 ２
実施例４のサイズプレス液で５−メルカプト−
１−メチルテトラゾール−ナトリウム塩を2.0％
硫酸メチルイソチオ尿素におきかえた以外は実施
例４と全く同様にして比較例２の記録紙とした。
この記録紙についてインクジエツト適性を測定し
た結果を表１に示す。[Table] etc. In addition, water-based ink liquid media include 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, polypropylene glycol, etc.; polyalkylene glycols such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol, etc. Alkylene glycols having 2 to 6 alkylene groups; examples include 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. Other additives include, for example, PH regulators, metal sequestrants, antifungal agents, viscosity regulators, surface tension regulators, wetting agents, surfactants, and rust preventives. According to the present invention, when recording is performed using an aqueous ink containing an aqueous dye on a recording medium containing a heterocyclic compound having the structure of general formula (2), the light fastness of an image is improved. The reason for this is not clear, but it is thought that the fading or discoloration of dyes is due to photooxidation caused by ultraviolet rays, etc., and that the heterocyclic compound having the structure of general formula () suppresses this photooxidation reaction. Conceivable. Ink jet suitability was measured by the following method. Light resistance was measured using a xenon fade meter (Suga Test Instruments Co., Ltd.) for the image area obtained by solid printing with C, M, Y, and Bk inks using a Canon inkjet printer (A-1210). Manufactured by FAL-
25X-HCL type) at 40℃, 60%, illuminance 41w/ m2 16
The color density before and after irradiation was measured using a Macbeth densitometer RD514, and the percentage of the color density after irradiation divided by the color density before irradiation was expressed as light resistance (residual rate). In addition, after measuring the reflectance before and after irradiation every 10 nm using a spectral reflection densitometer (Hitachi Color Analyzer Model 607), X, Y, and Z were measured using the C light source system described in JIS-Z-8722. After calculation JIS-Z-8730
Accordingly, calculate L, a, b and find the chromaticity difference △E before and after irradiation.
I got it. This value was shown as the amount of discoloration. Water resistance was determined by using the same Canon inkjet printer to print solid images using C, M, Y, and Bk inks, immersing them in running water at 30°C for 3 minutes, and measuring the density before and after immersion using Macbeth density. The water resistance value was determined by dividing the concentration after immersion by the concentration before immersion. The higher the value, the better the water resistance. The ink absorption speed is measured immediately after solid red printing (magenta + yellow) (about 1 second) using a Sharp or Canon inkjet printer.
The paper was fed to the paper, and the paper was brought into contact with a paper presser roll or a finger, and judgment was made based on whether dirt appeared. (E) Examples The present invention will be described below with reference to examples, but the invention is not limited to these examples. In addition, parts and percentages shown in the examples mean parts by weight and percentages by weight. Examples 1 to 3 80 parts of LBKP in 370 ml CSF, 400 ml water
20 parts of NBKP of CSF, 13 parts of ground calcium carbonate,
1 part cationic starch, alkyl ketene dimer sizing agent (Harcon W, manufactured by Deitsku Hercules)
From a slurry consisting of 0.08 parts of polyalkylene polyamine epichlorohydrin resin and 0.4 parts of polyalkylene polyamine epichlorohydrin resin, base paper with a basis weight of 68 g/m 2 is made using a Fourdrinier paper machine, and during paper making, 2 g/m2 of oxidized starch is added in solids using a size press machine.
m2 was deposited to produce coated base paper. The Steckigt size degree of this base paper was 21 seconds. As a coating liquid, 100 parts of synthetic silica (Thyroid 74, manufactured by Fuji Davison Co., Ltd.), 65 parts of polyvinyl alcohol (PVA110, manufactured by Kuraray Co., Ltd.), 5 parts of a cationic resin (Polyfix 601, manufactured by Showa Kobunshi Co., Ltd.), and an antifoaming agent. A small amount of liquid with a solid content of 18% was prepared, coated to a solid content of 10 g/m 2 and dried to produce a base paper with an ink-receiving layer. Separately, as a coating liquid, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-
Example 1 A solution prepared by dissolving 1 part each of mercaptobenzoxazole in 99 parts of ethanol was applied onto the surface of the base paper to a solid content of 0.5 g/m 2 , dried, and then lightly supercalendered to finish. -3 recording paper. Table 1 shows the results of measuring the inkjet suitability of this recording paper. Comparative Example 1 A recording paper of Comparative Example 1 was prepared in exactly the same manner as in Example 1, except that 2-mercaptobenzothiazole was removed from the coating solution used in Example 1. Table 1 shows the results of measuring the inkjet suitability of this recording paper. Examples 4 to 6 80 parts of LBKP in 370ml CSF, 400ml water level
20 parts of talc and 0.5 parts of cationic starch (Cato F, manufactured by Oji National Co., Ltd.) were added to a pulp slurry consisting of 20 parts of NBKP of CSF, and paper was made using a Fourdrinier paper machine with a basis weight of 65 g/ m2 , and a size press was used during paper making. Polyvinyl alcohol (PVA117, manufactured by Kuraray) 2
%, white carbon (Nipsil LP, Nippon Silica Co., Ltd.) 6%, 5-mercapto-1-methyltetrazole-sodium salt 0.2, 2.0, 4.0%, respectively.
Apply Pires liquid 60g/ m2 and finish after drying through a machine calender Examples 4 to 6
It was used as a recording paper. Table 1 shows the results of measuring the inkjet suitability of this recording paper. Comparative Example 2 5-mercapto- with the size press liquid of Example 4
2.0% 1-methyltetrazole-sodium salt
A recording paper of Comparative Example 2 was prepared in exactly the same manner as in Example 4 except that methylisothiourea sulfate was used.
Table 1 shows the results of measuring the inkjet suitability of this recording paper.
【表】【table】
【表】
(F) 発明の効果
表１から明らかなように本発明によるヘテロ環
化合物を記録媒体中に含有する実施例１〜６に於
いては、比較例に較べ黒インク画像及びマジエン
タインク画像の耐光性、光変褪色が著しく改善さ
れる。[Table] (F) Effect of the invention As is clear from Table 1, in Examples 1 to 6 containing the heterocyclic compound according to the present invention in the recording medium, black ink images and magenta ink were The light fastness and photofading of images are significantly improved.
Claims (1)
録画像を形成するインクジエツト記録媒体に於い
て、該記録媒体が下記一般式（）で示される構
造を有するヘテロ環化合物を含有することを特徴
とするインクジエツト記録媒体。 （） （式中Ｘは基本的にＣ，Ｎ，Ｏ、あるいはＳを
示す。また式中Ｃ＝Ｎ−で表わした二重結合は
化合物の他の構成要素と共役していてもよい。）[Scope of Claims] 1. An inkjet recording medium in which a recorded image is formed using an aqueous ink containing a water-soluble dye, wherein the recording medium contains a heterocyclic compound having a structure represented by the following general formula (). An inkjet recording medium characterized by: () (In the formula, X basically represents C, N, O, or S. Also, the double bond represented by C=N- in the formula may be conjugated with other constituent elements of the compound.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60020546A JPS61177279A (en) | 1985-02-04 | 1985-02-04 | Ink jet recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60020546A JPS61177279A (en) | 1985-02-04 | 1985-02-04 | Ink jet recording medium |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61177279A JPS61177279A (en) | 1986-08-08 |
| JPH042113B2 true JPH042113B2 (en) | 1992-01-16 |
Family
ID=12030150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60020546A Granted JPS61177279A (en) | 1985-02-04 | 1985-02-04 | Ink jet recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61177279A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6846525B2 (en) | 1993-03-19 | 2005-01-25 | Xerox Corporation | Recording sheets containing purine, pyrimidine, benzimidazole, imidazolidine, urazole, pyrazole, triazole, benzotriazole, tetrazole, and pyrazine compounds |
| US6180238B1 (en) * | 1993-03-19 | 2001-01-30 | Xerox Corporation | Recording sheets containing oxazole, isooxazole, oxazolidinone, oxazoline salt, morpholine, thiazole, thiazolidine, thiadiazole, and phenothiazine compounds |
| US5441795A (en) * | 1993-03-19 | 1995-08-15 | Xerox Corporation | Recording sheets containing pyridinium compounds |
| JP2003211824A (en) | 2002-01-17 | 2003-07-30 | Konica Corp | Void-type inkjet image receiving layer, inkjet recording material and method for manufacturing it |
| US7090903B2 (en) | 2002-10-07 | 2006-08-15 | Konica Corporation | Ink-jet recording sheet |
| JP2006130431A (en) | 2004-11-08 | 2006-05-25 | Konica Minolta Photo Imaging Inc | Method of manufacturing inkjet recording medium |
| US20090311494A1 (en) | 2008-06-17 | 2009-12-17 | Fujifilm Corporation | Relief printing plate precursor for laser engraving, relief printing plate, and process for producing relief printing plate |
-
1985
- 1985-02-04 JP JP60020546A patent/JPS61177279A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61177279A (en) | 1986-08-08 |
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| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term |