JP2005262797A - Inkjet recording material - Google Patents
Inkjet recording material Download PDFInfo
- Publication number
- JP2005262797A JP2005262797A JP2004082071A JP2004082071A JP2005262797A JP 2005262797 A JP2005262797 A JP 2005262797A JP 2004082071 A JP2004082071 A JP 2004082071A JP 2004082071 A JP2004082071 A JP 2004082071A JP 2005262797 A JP2005262797 A JP 2005262797A
- Authority
- JP
- Japan
- Prior art keywords
- ink
- receiving layer
- recording material
- silica
- ink receiving
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 37
- 239000002184 metal Substances 0.000 claims abstract description 37
- 239000011230 binding agent Substances 0.000 claims abstract description 28
- 239000011163 secondary particle Substances 0.000 claims abstract description 28
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 19
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 18
- 239000004327 boric acid Substances 0.000 claims abstract description 16
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000005619 boric acid group Chemical group 0.000 claims abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 129
- 239000000377 silicon dioxide Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 51
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 29
- 239000012808 vapor phase Substances 0.000 claims description 19
- 239000004310 lactic acid Substances 0.000 claims description 15
- 235000014655 lactic acid Nutrition 0.000 claims description 15
- 238000004438 BET method Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 abstract description 85
- 239000011248 coating agent Substances 0.000 abstract description 82
- 239000007788 liquid Substances 0.000 abstract description 54
- 239000000049 pigment Substances 0.000 abstract description 50
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 abstract description 6
- 239000000976 ink Substances 0.000 description 173
- 239000010410 layer Substances 0.000 description 128
- 239000006185 dispersion Substances 0.000 description 30
- 239000000243 solution Substances 0.000 description 20
- 239000002245 particle Substances 0.000 description 18
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 18
- 239000011247 coating layer Substances 0.000 description 17
- -1 aluminum alkoxide Chemical class 0.000 description 16
- 235000010338 boric acid Nutrition 0.000 description 15
- 229960002645 boric acid Drugs 0.000 description 15
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000011161 development Methods 0.000 description 13
- 230000018109 developmental process Effects 0.000 description 13
- 239000011164 primary particle Substances 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- 239000004816 latex 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
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 150000001767 cationic compounds Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 5
- 239000001527 calcium lactate Substances 0.000 description 5
- 235000011086 calcium lactate Nutrition 0.000 description 5
- 229960002401 calcium lactate Drugs 0.000 description 5
- 229920006317 cationic polymer Polymers 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229940001447 lactate Drugs 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003623 enhancer Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 150000003893 lactate salts Chemical class 0.000 description 3
- OVGXLJDWSLQDRT-UHFFFAOYSA-L magnesium lactate Chemical compound [Mg+2].CC(O)C([O-])=O.CC(O)C([O-])=O OVGXLJDWSLQDRT-UHFFFAOYSA-L 0.000 description 3
- 239000000626 magnesium lactate Substances 0.000 description 3
- 235000015229 magnesium lactate Nutrition 0.000 description 3
- 229960004658 magnesium lactate Drugs 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 229910001593 boehmite Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 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 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FCTDKZOUZXYHNA-UHFFFAOYSA-N 1,4-dioxane-2,2-diol Chemical compound OC1(O)COCCO1 FCTDKZOUZXYHNA-UHFFFAOYSA-N 0.000 description 1
- ASGBOCLUVBWOPM-UHFFFAOYSA-N 1-chloropentane-2,3-dione Chemical compound CCC(=O)C(=O)CCl ASGBOCLUVBWOPM-UHFFFAOYSA-N 0.000 description 1
- BITBMHVXCILUEX-UHFFFAOYSA-N 2-chloroethylurea Chemical compound NC(=O)NCCCl BITBMHVXCILUEX-UHFFFAOYSA-N 0.000 description 1
- YNVZDODIHZTHOZ-UHFFFAOYSA-K 2-hydroxypropanoate;iron(3+) Chemical compound [Fe+3].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O YNVZDODIHZTHOZ-UHFFFAOYSA-K 0.000 description 1
- JHLGIWLLGRJIEN-UHFFFAOYSA-L 2-hydroxypropanoate;lead(2+) Chemical compound [Pb+2].CC(O)C([O-])=O.CC(O)C([O-])=O JHLGIWLLGRJIEN-UHFFFAOYSA-L 0.000 description 1
- KSNGEYQWLMRSIR-UHFFFAOYSA-L 2-hydroxypropanoate;manganese(2+) Chemical compound [Mn+2].CC(O)C([O-])=O.CC(O)C([O-])=O KSNGEYQWLMRSIR-UHFFFAOYSA-L 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 1
- 244000215068 Acacia senegal Species 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WZUKKIPWIPZMAS-UHFFFAOYSA-K Ammonium alum Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZUKKIPWIPZMAS-UHFFFAOYSA-K 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Chemical class 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- 229920000569 Gum karaya Polymers 0.000 description 1
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Chemical class 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Chemical class 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- 108010073771 Soybean Proteins Proteins 0.000 description 1
- 241000934878 Sterculia Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 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
- 235000010489 acacia gum Nutrition 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 235000011124 aluminium ammonium sulphate Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 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
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- HLKMEIITONDPGG-UHFFFAOYSA-L barium(2+);2-hydroxypropanoate Chemical compound [Ba+2].CC(O)C([O-])=O.CC(O)C([O-])=O HLKMEIITONDPGG-UHFFFAOYSA-L 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- HBWKVDXNTCJIOW-UHFFFAOYSA-L cadmium(2+);2-hydroxypropanoate Chemical compound [Cd+2].CC(O)C([O-])=O.CC(O)C([O-])=O HBWKVDXNTCJIOW-UHFFFAOYSA-L 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 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
- 238000003490 calendering Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Chemical class 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
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Abstract
Description
本発明は、インクジェット記録方式を利用したプリンターやプロッターに使用されるインクジェット記録材料、特に顔料インクに適したインクジェット記録材料に関するものである。 The present invention relates to an ink jet recording material used in a printer or plotter using an ink jet recording method, and more particularly to an ink jet recording material suitable for pigment ink.
近年、インクジェットプリンターやプロッターの目ざましい進歩により、フルカラーでしかも高精細な画像が容易に得られるようになってきた。 In recent years, due to remarkable progress of inkjet printers and plotters, full-color and high-definition images can be easily obtained.
インクジェット記録方式は、種々の作動原理によりインクの微小液滴を飛翔させて紙等の記録材料に付着させ、画像・文字等の記録を行うものである。インクジェットプリンターやプロッターはコンピューターにより作成した文字や各種図形等の画像情報のハードコピー作成装置として、種々の用途に於いて近年急速に普及している。特に多色インクジェット方式により形成されるカラー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も遜色のない記録を得ることが可能であり、更に作成部数が少ない用途に於いては、印刷技術や写真技術によるよりも安価で済むことから広く応用されつつある。 The ink jet recording system records images, characters, and the like by causing micro droplets of ink to fly and adhere to a recording material such as paper according to various operating principles. Inkjet printers and plotters have rapidly become popular in recent years in various applications as hard copy creation devices for image information such as letters and various graphics created by computers. In particular, color images formed by the multi-color ink jet method can be recorded inferior to multi-color printing by the plate making method and printing by the color photographic method, and in applications where the number of copies is small. Are being widely applied because they are less expensive than printing and photographic techniques.
さらに、用途の多様化に伴い、大判のポスターやＰＯＰアート、製図用途に使用されることが多くなってきている。これら用途ではインクジェットの高鮮鋭性を活かせ、色彩性も優れていることから、良好な画像を得ることが可能であり、宣伝効果が大きいものとなる。これらへの適用はパーソナルコンピュータレベルで、鮮鋭性や色彩性といった画像再現性や色再現性に優れた画像を簡単に得ることが可能であるためであり、インクジェット記録材料を多用する理由ともなっている。 Furthermore, with the diversification of uses, it is increasingly used for large-format posters, POP art, and drafting. In these applications, since the high sharpness of the ink jet is utilized and the color is excellent, a good image can be obtained and the advertising effect is great. Application to these is because it is possible to easily obtain an image with excellent image reproducibility and color reproducibility such as sharpness and color at the personal computer level, which is also a reason for using a lot of ink jet recording materials. .
これらインクジェット記録装置の高性能化や用途の多様化により、インクジェット記録に対するニーズは高まっており、その結果記録装置或いはインクジェット記録材料に求められる特性も要求もかなり高度になってきている。例えば、大判ポスターやＰＯＰアート、また写真画像を出力する用途の場合、その用途が屋内外の展示や個人の記録保存といったものであるため、従来以上に画像の耐候性、画像保存性が求められるようになっている。このような要望に対し、インク及びインクジェット記録材料の改良が進んでおり、従来よりはかなり良好な保存性が得られるようになってきている。しかしながら、特に耐光性に関しては未だ銀塩写真のレベルには到達しておらず、要求が満たされていないのが現状である。 Due to the high performance and diversification of applications of these ink jet recording apparatuses, the need for ink jet recording has increased, and as a result, the characteristics and requirements required for the recording apparatus or ink jet recording material have become considerably high. For example, in the case of applications such as large posters, POP art, and photographic image output, the applications are for indoor / outdoor exhibitions and personal record storage, and thus weather resistance and image storage stability are required more than before. It is like that. In response to such demands, improvements in ink and ink jet recording materials are progressing, and considerably better storability can be obtained than before. However, in particular, the light resistance has not yet reached the level of silver salt photography, and the current situation is that the requirements are not satisfied.
このような要求を満たすために、最近では顔料タイプのインクが使用されるようになってきている。顔料インクは光劣化も少なく、水によって再溶解しないため、染料タイプのインクよりも耐候性、画像保存性が向上することが知られている。しかし、インク中の色材顔料は染料と異なり溶媒に不溶であるため、インク中の色材顔料を安定に分散させる必要があり、インク中の色材顔料の比率を容易に上げられない。また、染料インクのように着色効率が高くなく、鮮明な発色を得にくい。 In order to satisfy such demands, pigment type inks have recently been used. It is known that the pigment ink has little light deterioration and does not re-dissolve with water, so that the weather resistance and the image storage stability are improved as compared with the dye type ink. However, since the color material pigment in the ink is insoluble in the solvent unlike the dye, it is necessary to stably disperse the color material pigment in the ink, and the ratio of the color material pigment in the ink cannot be easily increased. In addition, the coloring efficiency is not high like dye ink, and it is difficult to obtain a clear color.
そのため、インクジェット記録材料に対する要求も必然的に高まってきている。顔料インクの発色性、定着性を高めるために、インク受理層で使用する顔料をアルミナ水和物とすることが提案されている（例えば、特許文献１参照）。この方法で、顔料インクの発色性、定着性は向上するものの依然不十分であった。 Therefore, the demand for ink jet recording materials is inevitably increasing. In order to improve the color developability and fixability of the pigment ink, it has been proposed that the pigment used in the ink receiving layer is alumina hydrate (see, for example, Patent Document 1). Although this method improved the color developability and fixability of the pigment ink, it was still insufficient.
また、染料インクの画像保存性を高めたり、顔料インクの発色性、定着性を向上させる目的で、インク受理層に水溶性多価金属塩を含有させることが提案されている（例えば、特許文献２、３参照）。さらに、粒子径が数十〜数百ｎｍオーダーの微粒子顔料、親水性バインダー、ホウ酸、水溶性多価金属塩からなるインク受理層を設けた、塗層表面にひび割れがなく光沢感があり、インク吸収性の高いインクジェット記録材料も提案されている（例えば特許文献２参照）。こうした親水性バインダーと、ホウ酸のような親水性バインダーを架橋する架橋剤を併用したタイプのインクジェット記録材料は、塗層表面のひび割れがないため、顔料インクのひび割れへの落ち込みがなく、画像の発色には有利である。また、こうした多価金属の水溶性塩は、アニオン系物質を凝集させる作用があり、特にアニオン系分散剤を含有した顔料インクの発色、定着性向上に有効である。しかしながら、インク受理層塗液に水溶性多価金属塩を含有させると、塗液配合中の物質をも凝集・不安定化し、コーター等で塗工できなかったり、塗工できても塗液のポットライフに問題があった。特にホウ酸等の架橋剤を含有する塗液ではその傾向は顕著であった。
本発明の課題は、インク受理層表面にひび割れを生じさせずに、表面の光沢感が高く、顔料インクの高い吸収性と発色性を兼ね備え、安定生産可能なインクジェット記録材料を提供することにある。 SUMMARY OF THE INVENTION An object of the present invention is to provide an ink jet recording material that has high glossiness on the surface without causing cracks on the surface of the ink receiving layer, has high absorbability and color developability of pigment ink, and can be stably produced. .
上記目的を達成するために鋭意研究を重ねた結果、支持体の少なくとも一方の面に、少なくとも平均二次粒子径６００ｎｍ以下のアルミナおよび／またはアルミナ水和物、親水性バインダー、架橋剤を含有するインク受理層を有するインクジェット記録材料において、該インク受理層にさらに水溶性の乳酸金属塩を含有させたインクジェット記録材料とすることにより解決した。 As a result of extensive research to achieve the above object, at least one surface of the support contains at least an alumina and / or alumina hydrate having an average secondary particle diameter of 600 nm or less, a hydrophilic binder, and a crosslinking agent. In the ink jet recording material having an ink receiving layer, the problem has been solved by using an ink jet recording material in which the ink receiving layer further contains a water-soluble lactic acid metal salt.
親水性バインダーがポリビニルアルコールであり、架橋剤がホウ酸またはホウ酸塩であると好ましい。 It is preferable that the hydrophilic binder is polyvinyl alcohol and the crosslinking agent is boric acid or borate.
ポリビニルアルコールの平均重合度が４０００以上であると好ましい。 The average degree of polymerization of polyvinyl alcohol is preferably 4000 or more.
支持体とインク受理層との間に、少なくとも気相法シリカおよび／または平均二次粒子径が６００ｎｍ以下になるまで粉砕された湿式法シリカからなる第二のインク受理層を有すると好ましい。 It is preferable to have a second ink-receiving layer made of wet-process silica pulverized at least to vapor phase silica and / or an average secondary particle diameter of 600 nm or less between the support and the ink-receiving layer.
前記気相法シリカまたは湿式法シリカのＢＥＴ法による比表面積が、前記アルミナおよび／またはアルミナ水和物のＢＥＴ法による比表面積よりも小さいと好ましい。 The specific surface area by the BET method of the gas phase method silica or the wet method silica is preferably smaller than the specific surface area of the alumina and / or alumina hydrate by the BET method.
本発明のインクジェット記録材料は、塗液のポットライフが長いため塗工の安定性が高く、表面の光沢感に優れ、インク受理層表面にひび割れがないため、顔料インクのひび割れへの落ち込みがなく、高い吸収性と発色性を兼ね備えることが可能となる。 The inkjet recording material of the present invention has high coating stability due to the long pot life of the coating liquid, excellent surface glossiness, and no cracks on the surface of the ink receiving layer, so there is no drop in the pigment ink cracks. It is possible to have both high absorbency and color developability.
以下、本発明のインクジェット記録材料を詳細に説明する。本発明者らは、少なくとも平均二次粒子径６００ｎｍ以下の無機超微粒子、親水性バインダー、架橋剤を含有するインク受理層を有するインクジェット記録材料において、顔料インクの発色性、定着性を向上させるべく水溶性金属塩について鋭意検討した結果、本発明に至った。 Hereinafter, the ink jet recording material of the present invention will be described in detail. In order to improve the color developability and fixability of pigment inks in an inkjet recording material having an ink receiving layer containing at least inorganic ultrafine particles having an average secondary particle diameter of 600 nm or less, a hydrophilic binder, and a crosslinking agent. As a result of intensive studies on water-soluble metal salts, the present invention has been achieved.
顔料インクの発色性、定着性を向上させる目的で、インク受理層に水溶性多価金属塩を含有させることが知られている。こうした多価金属の水溶性塩は、アニオン系物質を凝集させる作用があり、特にアニオン系分散剤を含有した顔料インクの発色、定着性向上に有効である。しかしながら、インク受理層塗液に水溶性多価金属塩を含有させると、塗液配合中の物質をも凝集・不安定化し、コーター等で塗工できなかったり、塗工できても塗液のポットライフに問題があった。特に、インク受理層塗液が少なくとも平均二次粒子径６００ｎｍ以下のアルミナおよび／あるいはアルミナ水和物、親水性バインダー、架橋剤を含有する場合には、液性の悪化は顕著であった。本発明のように、水溶性金属塩として乳酸金属塩を用いると、顔料インクの発色向上、定着性向上の効果を維持しつつ、塗液の液性が良化し、ポットライフを長くすることができ、安定にインクジェット記録材料を製造することが可能となる。 It is known that a water-soluble polyvalent metal salt is contained in the ink receiving layer for the purpose of improving the color developability and fixability of the pigment ink. Such a water-soluble salt of a polyvalent metal has an action of aggregating an anionic substance, and is particularly effective for improving the coloring and fixing properties of a pigment ink containing an anionic dispersant. However, if a water-soluble polyvalent metal salt is contained in the ink-receiving layer coating liquid, the substances in the coating liquid are also agglomerated and unstable, and cannot be applied with a coater or the like. There was a problem with the pot life. In particular, when the ink-receiving layer coating solution contains at least alumina having an average secondary particle diameter of 600 nm or less and / or alumina hydrate, a hydrophilic binder, and a crosslinking agent, the deterioration of the liquid property is remarkable. When a lactic acid metal salt is used as the water-soluble metal salt as in the present invention, the liquidity of the coating liquid is improved and the pot life is prolonged while maintaining the effect of improving the color development and fixing property of the pigment ink. This makes it possible to produce an inkjet recording material stably.
本発明でいう顔料インクとは、色材顔料、分散溶媒、その他の添加剤等からなる記録液体であり、特に限定されない。また、分散溶媒は、水および各種有機溶剤のいずれを用いたものでも良い。 The pigment ink as used in the present invention is a recording liquid comprising a colorant pigment, a dispersion solvent, other additives, and the like, and is not particularly limited. Further, the dispersion solvent may be any of water and various organic solvents.
本発明において、水溶性の乳酸金属塩とは、水に１質量％以上溶解する乳酸金属塩を指す。例えば、乳酸リチウム、乳酸カリウム、乳酸ナトリウム等の乳酸の一価金属塩、乳酸亜鉛、乳酸カルシウム、乳酸マグネシウム、乳酸マンガン、乳酸カドミウム、乳酸鉄、乳酸銀、乳酸銅、乳酸鉛、乳酸バリウム、乳酸ビスマス、乳酸ストロンチウム、乳酸アルミニウム等の乳酸の多価金属塩、および下記一般式１で表される多価金属の塩基性乳酸塩等が挙げられる。多価金属の塩基性乳酸塩は、ヒドロキシアクオ金属イオンが重合した多核錯体となった化合物も含む。これらのうち、顔料インクの発色性・定着性の点で、乳酸の多価金属塩および多価金属の塩基性乳酸塩が好ましく使用される。特に、乳酸カルシウム、乳酸マグネシウム、乳酸アルミニウムおよびこれら金属の塩基性乳酸塩が、顔料インクの発色性・定着性および塗液液性の点で好ましく使用される。 In the present invention, the water-soluble lactic acid metal salt refers to a lactic acid metal salt that is dissolved in water by 1% by mass or more. For example, monovalent metal salts of lactic acid such as lithium lactate, potassium lactate and sodium lactate, zinc lactate, calcium lactate, magnesium lactate, manganese lactate, cadmium lactate, iron lactate, silver lactate, copper lactate, lead lactate, barium lactate, lactic acid Examples thereof include polyvalent metal salts of lactic acid such as bismuth, strontium lactate, and aluminum lactate, and basic lactates of polyvalent metals represented by the following general formula 1. The basic lactate of a polyvalent metal includes a compound that is a polynuclear complex obtained by polymerizing hydroxyaquo metal ions. Of these, polyvalent metal salts of lactic acid and basic lactates of polyvalent metals are preferably used from the viewpoint of color development and fixing properties of the pigment ink. In particular, calcium lactate, magnesium lactate, aluminum lactate, and basic lactates of these metals are preferably used in terms of color development / fixing properties and coating liquid properties of the pigment ink.
Ｍ（ＯＨ）p-x（ＣＨ3ＣＨＯＨＣＯＯ）x・ｎＨ2Ｏ 一般式１
（Ｍは金属元素、ｎは０以上の整数、ｐは金属原子の原子価、ｘは１以上ｐ−１以下の自然数）
M (OH) px (CH 3 CHOHCOO) x · nH 2 O General formula 1
(M is a metal element, n is an integer of 0 or more, p is a valence of a metal atom, x is a natural number of 1 or more and p-1 or less)
本発明において、インク受理層は平均二次粒子径６００ｎｍ以下のアルミナおよび／またはアルミナ水和物を含有する。無機超微粒子としてアルミナおよび／またはアルミナ水和物を使用すると、顔料インクの発色性、定着性および表面の光沢感が向上するため好ましい。しかしながら、アルミナおよび／またはアルミナ水和物を水等の溶剤に分散させた分散液は、チキソ性が高く、攪拌等の剪断力がかかっていると液性は良好であるが、静置すると塗液の粘度が上昇していき、流動性が低下する性質を有している。このため、アルミナおよび／またはアルミナ水和物、親水性バインダー、架橋剤を含有するインク受理層塗液は、塗液の安定性に劣り、これにさらに顔料インクの発色性、定着性向上のため、水溶性金属塩を配合すると、塗液の安定性はいっそう悪化する問題を生じていた。本発明のように、金属塩として水溶性の乳酸金属塩を配合すると、無機超微粒子としてアルミナおよび／またはアルミナ水和物を使用した場合、塗液の安定性は大きく向上するため好ましい。本発明において、水溶性の乳酸金属塩のインク受理層中の含有量は、顔料インクの発色性、定着性、インク受理層塗液の安定性の点から、乾燥固形分比率で０．０１質量％以上４質量％以下であることが好ましく、より好ましくは０．０５％以上２％以下である。 In the present invention, the ink receiving layer contains alumina and / or alumina hydrate having an average secondary particle diameter of 600 nm or less. Use of alumina and / or alumina hydrate as the ultrafine inorganic particles is preferable because the color development property, fixing property and surface glossiness of the pigment ink are improved. However, a dispersion in which alumina and / or alumina hydrate is dispersed in a solvent such as water has high thixotropy, and the liquidity is good when a shearing force such as stirring is applied. The viscosity of the liquid increases and the fluidity decreases. For this reason, the ink-receiving layer coating liquid containing alumina and / or alumina hydrate, hydrophilic binder, and cross-linking agent is inferior in the stability of the coating liquid, and in addition to improving the color development and fixing properties of the pigment ink. When a water-soluble metal salt is blended, the stability of the coating solution is further deteriorated. When a water-soluble lactic acid metal salt is added as a metal salt as in the present invention, it is preferable to use alumina and / or alumina hydrate as the inorganic ultrafine particles because the stability of the coating liquid is greatly improved. In the present invention, the content of the water-soluble lactic acid metal salt in the ink receiving layer is 0.01 mass in terms of dry solid content from the viewpoint of the color development property of the pigment ink, the fixing property, and the stability of the ink receiving layer coating liquid. % Or more and 4% by mass or less, more preferably 0.05% or more and 2% or less.
本発明に用いられるアルミナとしては、酸化アルミニウムのγ型結晶であるγ−アルミナが好ましく、中でもδグループ結晶が好ましい。 As the alumina used in the present invention, γ-alumina which is a γ-type crystal of aluminum oxide is preferable, and among them, a δ group crystal is preferable.
本発明に用いられるアルミナ水和物は、下記の一般式により表すことができる。Ａｌ2Ｏ3・ｎＨ3Ｏアルミナ水和物は組成や結晶形態の違いにより、ジプサイト、バイアライト、ノルストランダイト、ベーマイト、ベーマイトゲル（擬ベーマイト）、ジアスポア、無定形非晶質等に分類される。中でも、上記の式中、ｎの値が１である場合はベーマイト構造のアルミナ水和物を表し、ｎが１を越え３未満である場合は擬ベーマイト構造のアルミナ水和物を表し、ｎが３以上では非晶質構造のアルミナ水和物を表す。特に、本発明に好ましいアルミナ水和物は、少なくともｎが１を越え３未満の擬ベーマイト構造のアルミナ水和物である。 The alumina hydrate used in the present invention can be represented by the following general formula. Al 2 O 3 · nH 3 O alumina hydrate is classified into gypsite, vialite, norstrandite, boehmite, boehmite gel (pseudoboehmite), diaspore, amorphous amorphous, etc., depending on the composition and crystal form. The In particular, in the above formula, when the value of n is 1, it represents an alumina hydrate having a boehmite structure, and when n is more than 1 and less than 3, it represents an alumina hydrate having a pseudo boehmite structure, where n is 3 or more represents an amorphous alumina hydrate. In particular, the preferred alumina hydrate for the present invention is an alumina hydrate having a pseudo boehmite structure in which at least n is more than 1 and less than 3.
また、アルミナ水和物の分散液を安定化させるために、通常は種々の酸類が分散液に添加される。このような酸類としては、硝酸、塩酸、乳酸、臭化水素酸、酢酸、蟻酸、塩化第二鉄、塩化アルミニウム等を挙げることができるが、本発明はこれらに限定されるものではない。 In order to stabilize the dispersion of alumina hydrate, various acids are usually added to the dispersion. Examples of such acids include nitric acid, hydrochloric acid, lactic acid, hydrobromic acid, acetic acid, formic acid, ferric chloride, aluminum chloride and the like, but the present invention is not limited to these.
本発明に用いられるアルミナ水和物の形状は、平板状、繊維状、針状、球状、棒状等のいずれでもよく、インク吸収性の観点から好ましい形状は平板状である。平板状のアルミナ水和物は、平均アスペクト比３〜８であり、好ましくは平均アスペクト比が３〜６である。アスペクト比は、粒子の「厚さ」に対する「直径」の比で表される。ここで粒子の直径とは、アルミナ水和物を電子顕微鏡で観察したときの粒子の投影面積に等しい円の直径を表す。 The shape of the alumina hydrate used in the present invention may be any of a flat plate shape, a fiber shape, a needle shape, a spherical shape, a rod shape, and the like, and a preferable shape is a flat shape from the viewpoint of ink absorbability. The plate-like alumina hydrate has an average aspect ratio of 3 to 8, and preferably an average aspect ratio of 3 to 6. The aspect ratio is expressed as the ratio of the “diameter” to the “thickness” of the particles. Here, the diameter of the particle represents the diameter of a circle equal to the projected area of the particle when the alumina hydrate is observed with an electron microscope.
本発明に用いられるアルミナ水和物は、アルミニウムイソプロポキシド等のアルミニウムアルコキシドの加水分解、アルミニウム塩のアルカリによる中和、アルミン酸塩の加水分解等公知の方法によって製造することができる。また、アルミナ水和物の粒子径、細孔径、細孔容積、比表面積等の物性は、析出温度、熟成温度、熟成時間、液のｐＨ、液の濃度、共存化合物等の条件によって制御することができる。 The alumina hydrate used in the present invention can be produced by a known method such as hydrolysis of aluminum alkoxide such as aluminum isopropoxide, neutralization of aluminum salt with alkali, hydrolysis of aluminate. The physical properties of alumina hydrate, such as particle size, pore size, pore volume, and specific surface area, should be controlled by conditions such as precipitation temperature, aging temperature, aging time, solution pH, solution concentration, and coexisting compounds. Can do.
アルコキシドからアルミナ水和物を得る方法としては、特開昭５７−８８０７４号公報、同６２−５６３２１号公報、特開平４−２７５９１７号公報、同６−６４９１８号公報、同７−１０５３５号公報、同７−２６７６３３号公報、米国特許第２，６５６，３２１号明細書等にアルミニウムアルコキシドを加水分解する方法として開示されている。これらのアルミニウムアルコキシドとしてはイソプロポキシド、２−ブトキシド等が挙げられる。 As methods for obtaining alumina hydrates from alkoxides, JP-A-57-88074, JP-A-62-256321, JP-A-4-275717, JP-A-6-64918, JP-A-7-10535, JP-A-7-267633, US Pat. No. 2,656,321 and the like disclose a method for hydrolyzing aluminum alkoxide. These aluminum alkoxides include isopropoxide, 2-butoxide and the like.
本発明で使用するアルミナ水和物において平均一次粒子径が３ｎｍ〜２５ｎｍのアルミナ水和物が好ましい。特に好ましい平均一次粒子径は５ｎｍ〜２０ｎｍのものである。またこれらが凝集した二次粒子径としては、５０ｎｍ〜２００ｎｍにするのが好ましい。 The alumina hydrate used in the present invention is preferably an alumina hydrate having an average primary particle size of 3 nm to 25 nm. A particularly preferable average primary particle diameter is 5 nm to 20 nm. Further, the secondary particle diameter in which these are aggregated is preferably 50 nm to 200 nm.
本発明のインク受理層には、皮膜としての特性を維持し、透明性が高くインクの浸透性が高い親水性バインダーが用いられる。親水性バインダーとしては、例えば、酸化澱粉、エーテル化澱粉、リン酸エステル化澱粉などの澱粉誘導体；メチルセルロース、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などのセルロース誘導体；ポリビニルアルコール、またはシラノール変性ポリビニルアルコールなどのポリビニルアルコール誘導体；カゼイン、ゼラチンおよびそれらの変性物、大豆蛋白、プルラン、アラビアゴム、カラヤゴム、アルブミン等の天然高分子樹脂またはこれらの誘導体、ポリアクリルアミド、ポリビニルピロリドン等のビニルポリマー、アルギン酸、ポリエチレンイミン、ポリプロピレングリコール、ポリエチレングリコール、無水マレイン酸またはその共重合体等が挙げられ、単独あるいは併用して用いることができるが、本発明はこれらに限定されるものではない。接着力、成膜性等の点から、ポリビニルアルコール、またはシラノール変性ポリビニルアルコールなどのポリビニルアルコール誘導体が好ましい。塗液粘度の調整、および成膜性等の点で、ポリビニルアルコールの中でも特に好ましいのは、ケン化度が８０％以上のポリビニルアルコールであり、さらに好ましくはケン化度が８８％以上９６％未満のポリビニルアルコールである。また、塗層のひび割れ抑制の観点から、ポリビニルアルコールの平均重合度は大きい方が好ましく、平均重合度４０００以上が好ましい。また、塗液の取り扱い性から、上限は６０００以下であることが好ましい。 In the ink receiving layer of the present invention, a hydrophilic binder that maintains the characteristics as a film and has high transparency and high ink permeability is used. Examples of the hydrophilic binder include starch derivatives such as oxidized starch, etherified starch, and phosphate esterified starch; cellulose derivatives such as methylcellulose, carboxymethylcellulose, and hydroxyethylcellulose; polyvinyl alcohol derivatives such as polyvinyl alcohol and silanol-modified polyvinyl alcohol Casein, gelatin and modified products thereof, soy protein, pullulan, gum arabic, Karaya gum, albumin and other natural polymer resins or derivatives thereof, vinyl polymers such as polyacrylamide and polyvinylpyrrolidone, alginic acid, polyethyleneimine, polypropylene glycol, Examples thereof include polyethylene glycol, maleic anhydride or a copolymer thereof, and these can be used alone or in combination. The present invention is not limited to, et al. Polyvinyl alcohol derivatives such as polyvinyl alcohol or silanol-modified polyvinyl alcohol are preferred from the viewpoints of adhesive strength, film formability, and the like. Among the polyvinyl alcohols, polyvinyl alcohol having a saponification degree of 80% or more, more preferably 88% or more and less than 96%, is particularly preferable among polyvinyl alcohols in terms of adjustment of the coating liquid viscosity and film formability. Of polyvinyl alcohol. Further, from the viewpoint of suppressing cracks in the coating layer, the average degree of polymerization of polyvinyl alcohol is preferably large, and the average degree of polymerization is preferably 4000 or more. Moreover, it is preferable that an upper limit is 6000 or less from the handleability of a coating liquid.
本発明のインク受理層は、親水性バインダーの効果を損ねない範囲で、親水性バインダー以外のバインダーを配合してもよい。例えば、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などの共役ジエン系共重合体ラテックス、アクリル酸エステルおよびメタクリル酸エステルの重合体または共重合体などのアクリル系共重合体ラテックス、エチレン−酢酸ビニル共重合体、塩化ビニル−酢酸ビニル共重合体などのビニル系共重合体ラテックス、ポリウレタン樹脂ラテックス、アルキッド樹脂ラテックス、不飽和ポリエステル樹脂ラテックス、あるいはこれらの各種共重合体のカルボキシ基などの官能基含有単量体による官能基変性共重合体ラテックス等のラテックス系バインダー、メラミン樹脂、尿素樹脂などの熱硬化合成樹脂などの水性接着剤等が挙げられる。 The ink receiving layer of the present invention may contain a binder other than the hydrophilic binder as long as the effect of the hydrophilic binder is not impaired. For example, conjugated diene copolymer latex such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, acrylic copolymer latex such as polymer or copolymer of acrylic acid ester and methacrylic acid ester, ethylene -Vinyl-based copolymer latex such as vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyurethane resin latex, alkyd resin latex, unsaturated polyester resin latex, carboxy group of these various copolymers, etc. Examples thereof include latex binders such as functional group-modified copolymer latex with functional group-containing monomers, and aqueous adhesives such as thermosetting synthetic resins such as melamine resins and urea resins.
本発明におけるインク受理層は、前記親水性バインダーとともに架橋剤を含有する。架橋剤を含有すると、インク受理層のひび割れがよりいっそう発生しにくくなるため好ましい。架橋剤としては、例えば、ホルムアルデヒド、グルタルアルデヒドの如きアルデヒド系化合物、ジアセチル、クロルペンタンジオンの如きケトン化合物、ビス（２−クロロエチル尿素）、２−ヒドロキシ−４，６−ジクロロ−１，３，５−トリアジン、米国特許第３，２８８，７７５号記載の如き反応性のハロゲンを有する化合物、ジビニルスルホン、米国特許第３，６３５，７１８号記載の如き反応性のオレフィンを持つ化合物、米国特許第２，７３２，３１６号記載の如きＮ−メチロール化合物、米国特許第３，１０３，４３７号記載の如きイソシアナート類、米国特許第３，０１７，２８０号、同２，９８３，６１１号記載の如きアジリジン化合物類、米国特許第３，１００，７０４号記載の如きカルボジイミド系化合物類、米国特許第３，０９１，５３７号記載の如きエポキシ化合物、ムコクロル酸の如きハロゲンカルボキシアルデヒド類、ジヒドロキシジオキサンの如きジオキサン誘導体、クロム明ばん、硫酸ジルコニウム、ホウ酸およびホウ酸塩の如き無機架橋剤等があり、これらを１種または２種以上組み合わせて用いることができる。これらの中でも、特にホウ酸またはホウ酸塩が好ましい。本発明において用いられるホウ酸としては、オルトホウ酸だけでなくメタホウ酸、次ホウ酸等が使用できる。ホウ酸塩はこれらの可溶性塩が好ましく、具体的には、Ｎａ4Ｂ4Ｏ7・１０Ｈ2Ｏ、ＮａＢＯ2・４Ｈ2０、Ｋ2Ｂ4Ｏ7・５Ｈ2Ｏ、ＮＨ4ＨＢ4Ｏ7・３Ｈ2Ｏ、ＮＨ4ＢＯ2等が挙げられるが、これらに限定されるものではない。 The ink receiving layer in the invention contains a crosslinking agent together with the hydrophilic binder. The inclusion of a cross-linking agent is preferred because cracks in the ink receiving layer are more unlikely to occur. Examples of the crosslinking agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and chloropentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5. Triazine, a compound having a reactive halogen as described in US Pat. No. 3,288,775, divinyl sulfone, a compound having a reactive olefin as described in US Pat. No. 3,635,718, US Pat. N-methylol compounds as described in U.S. Pat. No. 3,732,316, isocyanates as described in U.S. Pat. No. 3,103,437, aziridines as described in U.S. Pat. Nos. 3,017,280 and 2,983,611. Compounds, carbodiimide compounds as described in US Pat. No. 3,100,704, US patents There are epoxy compounds as described in US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane, chromium alum, zirconium sulfate, boric acid and inorganic cross-linking agents such as borate, etc. These can be used alone or in combination of two or more. Among these, boric acid or borate is particularly preferable. As boric acid used in the present invention, not only orthoboric acid but also metaboric acid and hypoboric acid can be used. The borate is preferably a soluble salt such as Na 4 B 4 O 7 .10H 2 O, NaBO 2 .4H 2 0, K 2 B 4 O 7 .5H 2 O, NH 4 HB 4 O. 7 · 3H 2 O, NH 4 BO 2 and the like, but not limited thereto.
架橋剤の添加量は、塗液粘度の調整、塗層のひび割れ等の点で、親水性バインダーの乾燥固形分に対して１〜４０質量％であることが好ましく、より好ましくは２〜２０質量％である。 The addition amount of the crosslinking agent is preferably 1 to 40% by mass, more preferably 2 to 20% by mass with respect to the dry solid content of the hydrophilic binder in terms of adjustment of the coating liquid viscosity, cracking of the coating layer, and the like. %.
本発明におけるインク受理層は、顔料インクおよび染料インクの定着性、耐水性を高める目的で、水溶性の乳酸金属塩以外に、水溶性の乳酸金属塩の効果を損なわない範囲でさらにカチオン性化合物を含有することもできる。カチオン性化合物としては、カチオン性ポリマーまたは水溶性金属化合物を使用できる。カチオン性ポリマーとしては、ポリエチレンイミン、ポリジアリルアミン、ポリアリルアミン、アルキルアミン重合物、特開昭５９−２０６９６号、同昭５９−３３１７６号、同昭５９−３３１７７号、同昭５９−１５５０８８号、同昭６０−１１３８９号、同昭６０−４９９９０号、同昭６０−８３８８２号、同昭６０−１０９８９４号、同昭６２−１９８４９３号、同昭６３−４９４７８号、同昭６３−１１５７８０号、同昭６３−２８０６８１号、同平１−４０３７１号、同平６−２３４２６８号、同平７−１２５４１１号、同平１０−１９３７７６号公報等に記載された１〜３級アミノ基、４級アンモニウム塩基を有するポリマー等が挙げられる。水溶性金属化合物としては、例えば水溶性の多価金属塩が挙げられ、中でもアルミニウムもしくは周期律表４Ａ族金属（例えばジルコニウム、チタン）からなる化合物が好ましく使用される。 The ink receiving layer in the present invention is a cationic compound in addition to the water-soluble lactic acid metal salt, in order not to impair the effect of the water-soluble lactic acid metal salt, for the purpose of improving the fixability and water resistance of the pigment ink and dye ink. Can also be contained. As the cationic compound, a cationic polymer or a water-soluble metal compound can be used. As the cationic polymer, polyethyleneimine, polydiallylamine, polyallylamine, alkylamine polymer, JP-A-59-20696, JP-A-59-33176, JP-A-59-33177, JP-A-59-155088, Sho 60-11389, Sho 60-49990, Sho 60-83882, Sho 60-109894, Sho 62-198493, Sho 63-49478, Sho 63-115780, Shosho 63-280681, No. 1-40371, No. 6-234268, No. 7-125411, No. 10-193976, etc. The polymer which has is mentioned. Examples of the water-soluble metal compound include water-soluble polyvalent metal salts, and among them, a compound made of aluminum or a group 4A metal (for example, zirconium or titanium) of the periodic table is preferably used.
本発明において、支持体と前記インク受理層（以下、本発明のアルミナおよび／またはアルミナ水和物、親水性バインダー、架橋剤、水溶性の乳酸金属塩を含有するインク受理層を第一のインク受理層として説明する。）との間に、少なくとも気相法シリカおよび／または平均二次粒子径が６００ｎｍ以下になるまで粉砕された湿式法シリカからなる第二のインク受理層を有すると好ましい。第二のインク受理層は主にインク吸収性を付与するための層である。該構成とすることで、インク受理層表面のひび割れが発生しにくくなり、顔料インクのひび割れへの落ち込みがなくなるため発色が向上し、表面光沢が高くインク吸収性を兼ね備えたインクジェット記録材料とすることが可能となる。 In the present invention, a support and the ink receiving layer (hereinafter referred to as an ink receiving layer containing the alumina and / or alumina hydrate of the present invention, a hydrophilic binder, a cross-linking agent, and a water-soluble lactic acid metal salt) are used as the first ink. And a second ink receiving layer made of wet method silica pulverized until the average secondary particle diameter becomes 600 nm or less. The second ink receiving layer is a layer mainly for imparting ink absorbability. By adopting such a configuration, it is difficult to generate cracks on the surface of the ink receiving layer, and since there is no drop into the cracks of the pigment ink, the color development is improved, and the inkjet recording material has high surface gloss and high ink absorption. Is possible.
本発明に係わる第二のインク受理層は、気相法シリカおよび／または平均二次粒子径が６００ｎｍ以下になるまで粉砕された湿式法シリカを含有する。特に気相法シリカが好ましく使用できる。気相法シリカは乾式法シリカとも呼ばれ、一般的には火炎加水分解法によって作られる。具体的には四塩化ケイ素を水素及び酸素と共に燃焼して作る方法が一般的に知られているが、四塩化ケイ素の代わりにメチルトリクロロシランやトリクロロシラン等のシラン類も、単独または四塩化ケイ素と混合した状態で使用することができる。気相法シリカは日本アエロジル（株）からアエロジル、（株）トクヤマからＱＳタイプとして市販されている。 The second ink-receiving layer according to the present invention contains gas phase method silica and / or wet method silica pulverized until the average secondary particle size is 600 nm or less. In particular, gas phase method silica can be preferably used. Vapor phase silica is also called dry silica and is generally made by flame hydrolysis. Specifically, a method of making silicon tetrachloride by burning with hydrogen and oxygen is generally known, but silanes such as methyltrichlorosilane and trichlorosilane can be used alone or silicon tetrachloride instead of silicon tetrachloride. Can be used in a mixed state. Vapor phase silica is commercially available as Aerosil from Nippon Aerosil Co., Ltd. and QS type from Tokuyama Co., Ltd.
本発明に用いられる気相法シリカの平均一次粒子径は、第一のインク受理層の塗層のひび割れ、表面光沢、顔料インクの発色の点から５ｎｍ以上５０ｎｍ以下が好ましく、より好ましくは、１０ｎｍ以上４０ｎｍ以下、特に好ましくは１５ｎｍ以上３０ｎｍ以下である。また、ＢＥＴ法による比表面積は、第二のインク受理層の塗層のひび割れ、インク吸収性の点から３０ｍ2／ｇ以上３００ｍ2／ｇ以下が好ましく、特に好ましくは４０ｍ2／ｇ以上１５０ｍ2／ｇ以下が好ましい。尚、本発明でいう平均一次粒子径とは、微粒子の電子顕微鏡観察により一定面積内に存在する１００個の一次粒子各々の投影面積に等しい円の直径を粒子の粒子径として平均粒子径を求めたものであり、本発明で云うＢＥＴ法とは、気相吸着法による粉体の表面積測定法の一つであり、吸着等温線から１ｇの試料の持つ総表面積、即ち比表面積を求める方法である。通常吸着気体としては、窒素ガスが多く用いられ、吸着量を被吸着気体の圧、または容積の変化から測定する方法が最も多く用いられている。多分子吸着の等温線を表すのに最も著名なものは、Brunauer、Emmett、Tellerの式であってＢＥＴ式と呼ばれ表面積決定に広く用いられている。ＢＥＴ式に基づいて吸着量を求め、吸着分子１個が表面で占める面積を掛けて、表面積が得られる。 The average primary particle diameter of the vapor phase silica used in the present invention is preferably 5 nm or more and 50 nm or less, more preferably 10 nm, from the viewpoint of cracking of the coating layer of the first ink receiving layer, surface gloss, and color development of the pigment ink. It is not less than 40 nm and particularly preferably not less than 15 nm and not more than 30 nm. Further, the BET specific surface area, coating layer cracking of the second ink-receiving layer is preferably 30 m 2 / g or more 300 meters 2 / g or less from the viewpoint of ink absorbency, particularly preferably 40 m 2 / g or more 150 meters 2 / G or less is preferable. The average primary particle diameter as used in the present invention is an average particle diameter obtained by observing the diameter of a circle equal to the projected area of each of 100 primary particles existing within a certain area by observation of fine particles with an electron microscope. The BET method referred to in the present invention is one of the powder surface area measurement methods by the vapor phase adsorption method, and is a method for obtaining the total surface area, that is, the specific surface area of a 1 g sample from the adsorption isotherm. is there. Usually, nitrogen gas is often used as the adsorbed gas, and the most frequently used method is to measure the amount of adsorption from the change in pressure or volume of the gas to be adsorbed. The most prominent expression for expressing the isotherm of multimolecular adsorption is the Brunauer, Emmett, and Teller formula, called the BET formula, which is widely used for determining the surface area. The adsorption amount is obtained based on the BET equation, and the surface area is obtained by multiplying the area occupied by one adsorbed molecule on the surface.
本発明の第二のインク受容層には、気相法シリカをカチオン性化合物の存在下で、該気相法シリカの平均二次粒子径が６００ｎｍ以下、好ましくは５０〜４００ｎｍ、更に好ましくは１００〜３００ｎｍに分散したものが使用できる。分散方法としては、通常のプロペラ撹拌、タービン型撹拌、ホモミキサー型撹拌等で気相法シリカとカチオン性化合物及び分散媒を予備混合し、次にボールミル、ビーズミル、サンドグラインダー等のメディアミル、高圧ホモジナイザー、超高圧ホモジナイザー等の圧力式分散機、超音波分散機、及び薄膜旋回型分散機等を使用して分散を行うことが好ましい。尚、ここでいう気相法シリカの平均二次粒子径とは、希薄分散液をレーザー回折／散乱式粒度分布測定装置で測定して得られる。 In the second ink-receiving layer of the present invention, vapor phase silica is present in the presence of a cationic compound, and the average secondary particle size of the vapor phase silica is 600 nm or less, preferably 50 to 400 nm, more preferably 100. Those dispersed in ˜300 nm can be used. As a dispersion method, premixed gas phase silica, a cationic compound, and a dispersion medium by ordinary propeller stirring, turbine type stirring, homomixer type stirring, etc., then a media mill such as a ball mill, a bead mill, a sand grinder, a high pressure It is preferable to perform dispersion using a pressure disperser such as a homogenizer or an ultrahigh pressure homogenizer, an ultrasonic disperser, a thin film swirl disperser, or the like. The average secondary particle diameter of the vapor phase silica referred to here is obtained by measuring a dilute dispersion with a laser diffraction / scattering type particle size distribution analyzer.
本発明において第二のインク受理層で使用される湿式法シリカは、製造方法によって沈降法シリカ、ゲル法シリカに分類される。沈降法シリカは珪酸ソーダと硫酸をアルカリ条件で反応させて製造され、粒子成長したシリカ粒子が凝集・沈降し、その後濾過、水洗、乾燥、粉砕・分級の行程を経て製品化される。沈降法シリカとしては、例えば日本シリカ（株）からニップシールとして、（株）トクヤマからトクシールとして市販されている。ゲル法シリカは珪酸ソーダと硫酸を酸性条件下で反応させて製造する。熟成中に微小粒子は溶解し、他の一次粒子どうしを結合するように再析出するため、明確な一次粒子は消失し、内部空隙構造を有する比較的硬い凝集粒子を形成する。例えば、日本シリカ（株）からニップゲルとして、グレースジャパン（株）からサイロイド、サイロジェットとして市販さている。 In the present invention, the wet method silica used in the second ink receiving layer is classified into a precipitation method silica and a gel method silica depending on the production method. Precipitated silica is produced by reacting sodium silicate and sulfuric acid under alkaline conditions, and the silica particles that have grown are agglomerated and settled, and are then commercialized through the steps of filtration, washing, drying, pulverization and classification. Precipitated silica is commercially available, for example, from Nippon Silica Co., Ltd. as a nip seal, and from Tokuyama Co., Ltd. as Toku Seal. Gel silica is produced by reacting sodium silicate and sulfuric acid under acidic conditions. During aging, the microparticles dissolve and reprecipitate so as to bind the other primary particles, so that the distinct primary particles disappear and form relatively hard aggregated particles having an internal void structure. For example, it is commercially available from Nippon Silica as nip gel and from Grace Japan as syloid and silo jet.
本発明では、平均二次粒子径６００ｎｍ以下に粉砕した湿式法シリカが使用される。本発明に用いられる湿式法シリカ粒子としては、平均一次粒子径５０ｎｍ以下、好ましくは３〜４０ｎｍであり、且つ平均凝集粒子径が５〜５０μｍである湿式法シリカ粒子が好ましく、これをカチオン性化合物の存在下で平均二次粒子径６００ｎｍ以下、好ましくは５０〜４００ｎｍ程度まで微粉砕した湿式法シリカ微粒子を使用する。ここでいう粉砕された湿式法シリカの平均二次粒子径とは、希薄分散液をレーザー回折／散乱式粒度分布測定装置で測定して得られる。 In the present invention, wet process silica pulverized to an average secondary particle diameter of 600 nm or less is used. The wet process silica particles used in the present invention are preferably wet process silica particles having an average primary particle diameter of 50 nm or less, preferably 3 to 40 nm, and an average aggregate particle diameter of 5 to 50 μm. Wet silica fine particles finely pulverized to an average secondary particle size of 600 nm or less, preferably about 50 to 400 nm in the presence of The average secondary particle size of the pulverized wet process silica mentioned here is obtained by measuring a dilute dispersion with a laser diffraction / scattering type particle size distribution analyzer.
通常の方法で製造された湿式法シリカは、１μｍ以上の平均凝集粒子径を有するため、これを微粉砕して使用する。粉砕方法としては、水性媒体中に分散したシリカを機械的に粉砕する湿式分散法が好ましく使用できる。この際、分散液の初期粘度上昇が抑制され、高濃度分散が可能となり、粉砕・分散効率が上昇してより微粒子に粉砕することができることから、吸油量が２１０ｍｌ／１００ｇ以下、平均凝集粒子径５μｍ以上の沈降法シリカを使用することが好ましい。高濃度分散液を使用することによって、記録用紙の生産性も向上する。吸油量は、ＪＩＳ Ｋ−５１０１の記載に基づき測定される。 Since the wet process silica produced by a normal method has an average aggregate particle diameter of 1 μm or more, it is used after being finely pulverized. As a pulverization method, a wet dispersion method in which silica dispersed in an aqueous medium is mechanically pulverized can be preferably used. At this time, the increase in the initial viscosity of the dispersion is suppressed, high concentration dispersion is possible, and the pulverization / dispersion efficiency is increased so that the particles can be further pulverized. Therefore, the oil absorption is 210 ml / 100 g or less, the average aggregated particle diameter It is preferable to use precipitated silica of 5 μm or more. By using a high-concentration dispersion, the productivity of recording paper is also improved. The oil absorption is measured based on the description of JIS K-5101.
本発明の平均二次粒子径が６００ｎｍ以下の湿式法シリカ微粒子を得る具体的な方法としては、まず水中でシリカ粒子とカチオン性化合物を混合（添加はどちらが先であっても、また同時でも良い）しても良く、又それぞれの分散液あるいは水溶液を混合しても良く、のこぎり歯状ブレード型分散機、プロペラ羽根型分散機、またはローターステーター型分散機等の分散装置の少なくとも１つを用いて予備分散液を得る。必要であれば更に適度の低沸点溶剤等を添加してもよい。シリカ予備分散物の固形分濃度は高いほうが好ましいが、あまり高濃度になると分散不可能となるため、好ましい範囲としては１５〜４０質量％、より好ましくは２０〜３５質量％である。次に、より強い機械的手段を与えることによって、平均二次粒子径が６００ｎｍ以下の湿式法シリカ微粒子分散液が得られる。機械的手段としては公知の方法が採用でき、例えばボールミル、ビーズミル、サンドグラインダー等のメディアミル、高圧ホモジナイザー、超高圧ホモジナイザー等の圧力式分散機、超音波分散機、及び薄膜旋回型分散機等を使用することができる。 As a specific method for obtaining wet method silica fine particles having an average secondary particle diameter of 600 nm or less of the present invention, first, silica particles and a cationic compound are mixed in water (whichever comes first or at the same time). And each dispersion or aqueous solution may be mixed, and at least one dispersion device such as a sawtooth blade type dispersion device, a propeller blade type dispersion device, or a rotor stator type dispersion device is used. To obtain a preliminary dispersion. If necessary, an appropriate low boiling point solvent may be added. The higher the solid content concentration of the silica pre-dispersion, the higher the concentration. However, since the dispersion becomes impossible when the concentration is too high, the preferred range is 15 to 40% by mass, and more preferably 20 to 35% by mass. Next, by applying a stronger mechanical means, a wet process silica fine particle dispersion having an average secondary particle diameter of 600 nm or less is obtained. As a mechanical means, a known method can be adopted, for example, a media mill such as a ball mill, a bead mill, a sand grinder, a high pressure homogenizer, a pressure disperser such as an ultra high pressure homogenizer, an ultrasonic disperser, a thin film swirl disperser, etc. Can be used.
上記気相法シリカ及び湿式法シリカの分散に使用するカチオン性化合物としては、前記第一のインク受理層で使用するカチオン性化合物として例示した化合物が使用可能である。中でも、カチオン性ポリマーとしてはジアリルアミン誘導体が好ましく用いられる。分散性および分散液粘度の面で、これらのカチオンポリマーの分子量は、２，０００〜１０万程度が好ましく、特に２，０００〜３万程度が好ましい。また、水溶性金属化合物としては、水溶性アルミニウム化合物が好ましく用いられる。水溶性アルミニウム化合物としては、例えば無機塩としては塩化アルミニウムまたはその水和物、硫酸アルミニウムまたはその水和物、アンモニウムミョウバン等が知られている。さらに、無機系の含アルミニウムカチオンポリマーである塩基性ポリ水酸化アルミニウム化合物が知られており、好ましく用いられる。 As the cationic compound used for dispersion of the gas phase method silica and the wet method silica, the compounds exemplified as the cationic compound used in the first ink receiving layer can be used. Of these, diallylamine derivatives are preferably used as the cationic polymer. In terms of dispersibility and dispersion viscosity, the molecular weight of these cationic polymers is preferably about 2,000 to 100,000, and particularly preferably about 2,000 to 30,000. As the water-soluble metal compound, a water-soluble aluminum compound is preferably used. As a water-soluble aluminum compound, for example, as an inorganic salt, aluminum chloride or a hydrate thereof, aluminum sulfate or a hydrate thereof, ammonium alum and the like are known. Furthermore, a basic polyaluminum hydroxide compound which is an inorganic aluminum-containing cationic polymer is known and preferably used.
本発明において、第二のインク受理層で使用される気相法シリカまたは湿式法シリカのＢＥＴ法による比表面積は、第一のインク受理層で使用されるアルミナおよび／またはアルミナ水和物のＢＥＴ法による比表面積よりも小さいことが好ましい。こうした構成とすることで、第二のインク受理層の塗層の上に第一のインク受理層を設けた際に、塗層のひび割れの発生がよりいっそう抑制され、良好な顔料インクの発色が得やすくなる。おそらく、第二のインク受理層で使用される気相法シリカあるいは湿式シリカのＢＥＴ法による比表面積が、第一のインク受理層で使用されるアルミナ水和物のＢＥＴ法による比表面積よりも小さいため、第一のインク受理層への第二のインク受理層中のバインダー成分等の落ち込みが少なくなり、インク吸収性への悪影響がほとんどなく、該インク受理層の塗層のひび割れが発生しにくくなるものと推定される。 In the present invention, the specific surface area of the vapor phase silica or wet method silica used in the second ink receiving layer by the BET method is the BET of alumina and / or alumina hydrate used in the first ink receiving layer. It is preferably smaller than the specific surface area obtained by the method. With this configuration, when the first ink-receiving layer is provided on the coating layer of the second ink-receiving layer, the occurrence of cracks in the coating layer is further suppressed, and good pigment ink color development is achieved. It becomes easy to obtain. Perhaps the specific surface area of the vapor phase silica or wet silica used in the second ink receiving layer by the BET method is smaller than the specific surface area of the alumina hydrate used in the first ink receiving layer by the BET method. Therefore, there is less drop of the binder component in the second ink receiving layer to the first ink receiving layer, there is almost no adverse effect on the ink absorbability, and the coating layer of the ink receiving layer is hardly cracked. It is estimated that
本発明において、第一のインク受理層は、アルミナおよびアルミナ水和物をそれぞれ単独で用いてもよいし併用してもよいが、前記アルミナまたはアルミナ水和物の第一のインク受理層中の含有比率（併用した場合は合計の含有比率）は、第一のインク受理層中の全固形分に対して５０質量％以上が好ましく、７０質量％以上がより好ましく、特に８０質量％以上が好ましい。また、第二のインク受理層は、気相法シリカおよび平均二次粒子径が６００ｎｍ以下になるまで粉砕された湿式法シリカを、それぞれ単独で用いてもよいし併用してもよいが、前記気相法シリカまたは粉砕された湿式法シリカの第二のインク受理層における含有比率（併用した場合は合計の含有比率）は、第二のインク受理層中の全固形分に対して５０質量％以上が好ましく、７０質量％以上がより好ましく、特に８０質量％以上が好ましい。また、本発明において、第一および第二のインク受理層は、本発明の効果を損ねない範囲で、上記した微粒子以外の無機または有機の白色顔料を含有することができる。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、二酸化チタン、酸化亜鉛、硫化亜鉛、炭酸亜鉛、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、珪酸マグネシウム、合成非晶質シリカ、水酸化アルミニウム、リトポン、ゼオライト、加水ハロイサイト、炭酸マグネシウム、水酸化マグネシウムなどの白色無機顔料、スチレン系プラスチックピグメント、アクリル系プラスチックピグメント、ポリエチレン、尿素樹脂、メラミン樹脂等の有機顔料、また、平均二次粒子径が６００ｎｍ以下の無機超微粒子、例えば、特開平８−７２３８７公報などに記載されている気相法アルミナ、特開昭６０−２１９０８３号公報、同６１−１９３８９号公報、同６１−１８８１８３号公報、同６３−１７８０７４号公報、特開平５−５１４７０号公報などに記載されているようなコロイダルシリカ、特公平４−１９０３７号公報、特開昭６２−２８６７８７号公報に記載されているようなシリカ／アルミナハイブリッドゾル、その他にも、ヘクタイト、モンモリロナイトなどのスメクタイト粘土（特開平７−８１２１０号公報）、ジルコニアゾル、クロミアゾル、イットリアゾル、セリアゾル、酸化鉄ゾル、ジルコンゾル、酸化アルミニウムゾル、酸化アンチモンゾルなどを代表的なものとして挙げることができる。 In the present invention, for the first ink receiving layer, alumina and alumina hydrate may be used alone or in combination, respectively, but the alumina or alumina hydrate in the first ink receiving layer in the first ink receiving layer may be used. The content ratio (total content ratio when used in combination) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more based on the total solid content in the first ink receiving layer. . The second ink-receiving layer may be a vapor-phase silica and a wet-method silica pulverized until the average secondary particle size is 600 nm or less, and may be used alone or in combination. The content ratio of the vapor-phase process silica or the pulverized wet process silica in the second ink-receiving layer (the total content ratio when used together) is 50% by mass with respect to the total solid content in the second ink-receiving layer. The above is preferable, 70 mass% or more is more preferable, and 80 mass% or more is particularly preferable. In the present invention, the first and second ink receiving layers can contain an inorganic or organic white pigment other than the fine particles described above within a range not impairing the effects of the present invention. For example, light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate, magnesium silicate, synthetic non White inorganic pigments such as crystalline silica, aluminum hydroxide, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide, organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, urea resin, melamine resin, etc. Inorganic ultrafine particles having an average secondary particle size of 600 nm or less, for example, vapor-phase method alumina described in JP-A-8-72387, JP-A-60-219083, JP-A-61-19389, 61-1881 No. 3, No. 63-178074, JP-A-5-51470, etc., colloidal silica, JP-B-4-19037, JP-A 62-286787. In addition to such silica / alumina hybrid sol, smectite clay such as hectite and montmorillonite (JP-A-7-81210), zirconia sol, chromia sol, yttria sol, ceria sol, iron oxide sol, zircon sol, aluminum oxide sol, oxidation A typical example is antimony sol.
本発明の第二のインク受理層は、前記第一のインク受理層で例示したバインダーを使用することができる。中でも、皮膜としての特性を維持し、透明性が高くインクの浸透性が高い親水性バインダーが好ましく用いられる。また、塗層のひび割れ抑制等を目的に、第一のインク受理層で例示した架橋剤を使用することができる。 For the second ink receiving layer of the present invention, the binder exemplified in the first ink receiving layer can be used. Among them, a hydrophilic binder that maintains the characteristics as a film and has high transparency and high ink permeability is preferably used. Moreover, the crosslinking agent illustrated by the 1st ink receiving layer can be used for the purpose of the crack suppression of a coating layer, etc.
これらの親水性バインダーの配合量は、塗層のひび割れ、インク吸収性の点で、第一のインク受理層では、全乾燥固形分比率で、３〜１５質量％であることが好ましく、４〜１０質量％であることが特に好ましい。第二のインク受理層では、全乾燥固形分比率で、８〜２５質量％であることが好ましく、１０〜２０質量％であることが特に好ましい。 The blending amount of these hydrophilic binders is preferably 3 to 15% by mass in terms of the total dry solid content in the first ink receiving layer in terms of cracking of the coating layer and ink absorbability. 10% by mass is particularly preferable. In the second ink receiving layer, the total dry solid content ratio is preferably 8 to 25% by mass, and particularly preferably 10 to 20% by mass.
更に、本発明の第一および第二のインク受理層には、その他の添加剤として、顔料分散剤、増粘剤、流動性改良剤、粘度安定剤、ｐＨ調整剤、界面活性剤、消泡剤、抑泡剤、離型剤、発泡剤、浸透剤、着色染料、着色顔料、蛍光増白剤、紫外線吸収剤、酸化防止剤、レベリング剤、防腐剤、防バイ剤、耐水化剤、湿潤紙力増強剤、乾燥紙力増強剤などを適宜添加することもできる。 Further, in the first and second ink receiving layers of the present invention, as other additives, a pigment dispersant, a thickener, a fluidity improver, a viscosity stabilizer, a pH adjuster, a surfactant, an antifoaming agent Agent, foam suppressor, mold release agent, foaming agent, penetrating agent, coloring dye, coloring pigment, fluorescent brightening agent, ultraviolet absorber, antioxidant, leveling agent, antiseptic, antibacterial agent, waterproofing agent, wetting A paper strength enhancer, a dry paper strength enhancer, etc. can also be added suitably.
本発明に用いる支持体は透明、半透明および不透明のいずれであっても良く、紙、各種不織布、織布、合成樹脂フィルム、合成樹脂ラミネート紙、合成紙、金属箔、セラミック紙、ガラス板など、あるいはこれらを組み合わせた複合シートを目的に応じて任意に用いることが出来るが、これらに限定されるものではない。紙のごとき透気性のある支持体を用いる場合、本発明のインク受理層を設けた場合でも、インク受理層塗液が支持体に浸透し、塗層のひび割れを生じることがある。このため、透気性のある支持体を使用する場合は、浸透性を制御する目的で、顔料を主成分とする層を支持体上に塗工する等して、浸透性を制御した支持体を使用することが好ましい。 The support used in the present invention may be transparent, translucent or opaque, such as paper, various nonwoven fabrics, woven fabric, synthetic resin film, synthetic resin laminated paper, synthetic paper, metal foil, ceramic paper, glass plate, etc. Alternatively, a composite sheet combining these can be arbitrarily used depending on the purpose, but is not limited thereto. When an air-permeable support such as paper is used, even when the ink-receiving layer of the present invention is provided, the ink-receiving layer coating liquid may penetrate into the support and cause cracks in the coating layer. For this reason, when using a permeable support, for the purpose of controlling the permeability, a layer having a pigment as a main component is coated on the support, etc. It is preferable to use it.
支持体として用いる紙としては、ＬＢＫＰ、ＮＢＫＰ等の化学パルプ、ＧＰ、ＰＧＷ、ＲＭＰ、ＴＭＰ、ＣＴＭＰ、ＣＭＰ、ＣＧＰ等の機械パルプ、ＤＩＰ等の古紙パルプ等の木材パルプと従来公知の顔料を主成分として、バインダー及びサイズ剤や定着剤、歩留まり向上剤、カチオン化剤、紙力増強剤等の各種添加剤を１種以上用いて混合し、長網抄紙機、円網抄紙機、ツインワイヤー抄紙機等の各種装置で製造された原紙、更に原紙に、澱粉、ポリビニルアルコール等でのサイズプレスやアンカーコート層を設けた原紙や、それらの上にコート層を設けたアート紙、コート紙、キャストコート紙等の塗工紙も含まれる。この様な原紙及び塗工紙に、そのまま本発明における塗層を設けても良いし、平坦化をコントロールする目的で、マシンカレンダー、ＴＧカレンダー、ソフトカレンダー等のカレンダー装置を使用しても良い。 As the paper used as the support, chemical pulp such as LBKP and NBKP, wood pulp such as GP, PGW, RMP, mechanical pulp such as TMP, CTMP, CMP, and CGP, waste paper pulp such as DIP, and conventionally known pigments are mainly used. As a component, a binder, a sizing agent, a fixing agent, a yield improver, a cationizing agent, a paper strength enhancer and the like are mixed using one or more kinds of additives, a long net paper machine, a circular net paper machine, a twin wire paper machine. Base paper manufactured by various devices such as a machine, base paper provided with size press or anchor coat layer with starch, polyvinyl alcohol, etc., or art paper, coated paper, cast with a coat layer on them Coated paper such as coated paper is also included. Such a base paper and coated paper may be provided with the coating layer in the present invention as they are, or a calendar device such as a machine calendar, a TG calendar, and a soft calendar may be used for the purpose of controlling flattening.
本発明において、各インク受理層の乾燥塗工量は特に限定されるものではないが、インク吸収性、塗層のひび割れの点で、各インク受理層の乾燥塗工量の範囲は３〜１６ｇ／ｍ2、より好ましくは５〜１２ｇ／ｍ2である。 In the present invention, the dry coating amount of each ink receiving layer is not particularly limited, but the range of the dry coating amount of each ink receiving layer is 3 to 16 g in terms of ink absorbency and cracking of the coating layer. / M 2 , more preferably 5 to 12 g / m 2 .
本発明においてインク受理層を設ける際に、塗工する方法は、特に限定されず、公知の塗工方法を用いることができる。例えば、エアーナイフコーター、カーテンコーター、スライドリップコーター、ダイコーター、ブレードコーター、ゲートロールコーター、バーコーター、ロッドコーター、ロールコーター、ビルブレードコーター、ショートドエルブレードコーター、サイズプレスなどの各種装置により塗工することができる。 In the present invention, when the ink receiving layer is provided, a coating method is not particularly limited, and a known coating method can be used. For example, coating with various devices such as air knife coater, curtain coater, slide lip coater, die coater, blade coater, gate roll coater, bar coater, rod coater, roll coater, bill blade coater, short dwell blade coater, size press, etc. can do.
本発明において、塗液塗工後に乾燥する方法は、特に限定されず、公知の乾燥方法を用いることができる。 In the present invention, the method of drying after coating the coating liquid is not particularly limited, and a known drying method can be used.
本発明において、各インク受理層を塗工、乾燥後、平坦化をコントロールしたり表面光沢をさらに高めたりする目的で、カレンダー処理により、平滑化しても良い。その際のカレンダー処理装置としては、グロスカレンダー、スーパーカレンダー、ソフトカレンダーなどが挙げられる。また、公知のキャストコート法を用いて光沢面を形成することができる。 In the present invention, each ink receiving layer may be smoothed by calendaring for the purpose of controlling flattening or further increasing the surface gloss after coating and drying. Examples of the calendar processing device at that time include a gloss calendar, a super calendar, and a soft calendar. Moreover, a glossy surface can be formed using a known cast coating method.
以下に本発明を実施例を挙げて説明するが、本発明はこれらの例に限定されるものではない。また、実施例に於いて示す「部」および「％」は特に明示しない限り質量部および質量％を示す。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” indicate parts by mass and mass% unless otherwise specified.
＜第一のインク受理層塗液１＞
水４００部に、６０％硝酸２部、擬ベーマイト構造を有するアルミナ水和物（平均一次粒子径１５ｎｍ、ＢＥＴ法による比表面積１６０ｍ2／ｇ）１００部を添加し、のこぎり歯状ブレード型分散機を使用して、２０．２％のアルミナ水和物分散液を作製した。こうして得たアルミナ水和物分散液５００部、４％ホウ酸水溶液１０部、４％乳酸カルシウム水溶液２０部、８％ポリビニルアルコール（ケン化度８８％、平均重合度４５００）１００部、界面活性剤０．３部、水２０部を混合し、固形分濃度１７．０％の第一のインク受理層塗液１を調製した。なお、レーザー回折／散乱式粒度分布測定装置で測定して得られたアルミナ水和物微粒子の平均二次粒子径は１５０ｎｍであった。
<First Ink Receiving Layer Coating Liquid 1>
To 400 parts of water, 2 parts of 60% nitric acid and 100 parts of alumina hydrate having a pseudo boehmite structure (average primary particle diameter 15 nm, specific surface area 160 m 2 / g by BET method) are added, and a sawtooth blade type disperser Was used to make a 20.2% alumina hydrate dispersion. 500 parts of the alumina hydrate dispersion thus obtained, 10 parts of 4% boric acid aqueous solution, 20 parts of 4% aqueous calcium lactate solution, 100 parts of 8% polyvinyl alcohol (saponification degree 88%, average polymerization degree 4500), surfactant 0.3 parts and 20 parts of water were mixed to prepare a first ink-receiving layer coating liquid 1 having a solid concentration of 17.0%. The average secondary particle diameter of the alumina hydrate fine particles obtained by measurement with a laser diffraction / scattering particle size distribution analyzer was 150 nm.
＜第一のインク受理層塗液２〜８＞
第一のインク受理層塗液１で使用した乳酸カルシウム水溶液を表１のように変更した以外は同様にして、第一のインク受理層塗液２〜８を調製した。
<First ink receiving layer coating liquids 2 to 8>
First ink receiving layer coating solutions 2 to 8 were prepared in the same manner except that the calcium lactate aqueous solution used in the first ink receiving layer coating solution 1 was changed as shown in Table 1.
＜第一のインク受理層塗液９＞
第一のインク受理層塗液１でホウ酸を使用しなかった以外は同様にして、第一のインク受理層塗液９を調製した。
<First Ink Receiving Layer Coating Liquid 9>
A first ink-receiving layer coating solution 9 was prepared in the same manner except that boric acid was not used in the first ink-receiving layer coating solution 1.
＜塗液の安定性＞
上記のようにして調製した第一のインク受理層塗液１〜９の調液直後、および２０℃６５％環境下で１時間静置後の、ブルックフィールド粘度計で粘度を測定した。結果を表１に示す。
<Stability of coating liquid>
The viscosity was measured with a Brookfield viscometer immediately after preparation of the first ink-receiving layer coating solutions 1 to 9 prepared as described above and after standing for 1 hour in an environment of 20 ° C. and 65%. The results are shown in Table 1.
表１に示すように、平均二次粒子径６００ｎｍ以下のアルミナ水和物、親水性バインダー、ホウ酸、および水溶性の乳酸塩を含有する第一のインク受理層塗液１〜４は、水溶性の乳酸塩を添加していない第一のインク受理層塗液８に比べ、塗液の経時安定性に優れ、ポットライフを長くすることが可能となり、安定にインクジェット記録材料を製造することが可能となる。乳酸塩以外の金属塩を用いた第一のインク受理層塗液５〜７は、金属塩を添加していない第一のインク受理層塗液８よりも、塗液の経時安定性は悪化し、塗工不能となった。 As shown in Table 1, the first ink-receiving layer coating liquids 1 to 4 containing an alumina hydrate having an average secondary particle diameter of 600 nm or less, a hydrophilic binder, boric acid, and a water-soluble lactate are water-soluble. Compared with the first ink-receiving layer coating liquid 8 to which no soluble lactate is added, the coating liquid is excellent in stability over time, the pot life can be prolonged, and an inkjet recording material can be produced stably. It becomes possible. The first ink-receiving layer coating solutions 5 to 7 using a metal salt other than lactate are less stable over time than the first ink-receiving layer coating solution 8 to which no metal salt is added. , Coating became impossible.
＜支持体１＞
濾水度４５０ｍｌＣＳＦのＬＢＫＰ７０部、濾水度４５０ｍｌＣＳＦのＮＢＫＰ３０部から成る木材パルプ１００部に、軽質炭酸カルシウム／重質炭酸カルシウム／タルクの比率が３０／３５／３５の顔料５部、市販アルキルケテンダイマー０．１部、市販カチオン系アクリルアミド０．０３部、市販カチオン化澱粉１．０部、硫酸バンド０．５部を調製後、長網抄紙機を用いて坪量１０５ｇ／ｍ2で抄造した。こうして得た紙の上に、下記顔料層塗液１を乾燥塗工量が７ｇ／ｍ2となるように、エアーナイフコーターで塗工、乾燥して支持体１を作製した。
<Support 1>
100 parts of wood pulp comprising 70 parts of LBKP with a freeness of 450 ml CSF and 30 parts of NBKP with a freeness of 450 ml CSF, 5 parts of a pigment having a light calcium carbonate / heavy calcium carbonate / talc ratio of 30/35/35, and a commercially available alkyl ketene dimer After preparing 0.1 part, 0.03 part of commercially available cationic acrylamide, 1.0 part of commercially available cationized starch, and 0.5 part of sulfuric acid band, the paper was made with a basis weight of 105 g / m 2 using a long net paper machine. On the paper thus obtained, the following pigment layer coating solution 1 was coated with an air knife coater and dried so that the dry coating amount was 7 g / m 2 , thereby preparing support 1.
＜顔料層塗液１＞
合成非晶質シリカ（平均二次粒子径２．３μｍ）１００部をホモジナイザーを用いて水４００部に分散し、これに１０％ポリビニルアルコール（完全鹸化、重合度１７００）水溶液２５０部、５０％エチレン−酢酸ビニル共重合体ラテックス３０部、界面活性剤０．３部、水を混合し、固形分濃度１８．０％の顔料層塗液１を調製した。
<Pigment layer coating solution 1>
100 parts of synthetic amorphous silica (average secondary particle size 2.3 μm) is dispersed in 400 parts of water using a homogenizer, and 250 parts of an aqueous solution of 10% polyvinyl alcohol (fully saponified, degree of polymerization 1700), 50% ethylene. -30 parts of vinyl acetate copolymer latex, 0.3 part of surfactant and water were mixed to prepare a pigment layer coating solution 1 having a solid content concentration of 18.0%.
＜第二のインク受理層塗液１＞
水４００部に、５０％ジメチルジアリルアンモニウムクロライドホモポリマー（分子量９，０００）８部、気相法シリカ（平均一次粒子径１６ｎｍ、ＢＥＴ法による比表面積１３０ｍ2／ｇ）１００部を添加し、のこぎり歯状ブレード型分散機を使用して予備分散液を作製した。得られた予備分散液を高圧ホモジナイザーで処理して、２０．５％のシリカ分散液を得た。こうして得たシリカ分散液５００部、４％ホウ酸水溶液２０部、８％ポリビニルアルコール（ケン化度８８％、平均重合度３５００）２５０部、界面活性剤０．３部、水５４部を混合し、固形分濃度１５．０％の第二のインク受理層塗液１を調製した。なお、レーザー回折／散乱式粒度分布測定装置で測定して得られた気相法シリカ微粒子の平均二次粒子径は４００ｎｍであった。
<Second ink receiving layer coating liquid 1>
To 400 parts of water, 8 parts of 50% dimethyldiallylammonium chloride homopolymer (molecular weight 9,000) and 100 parts of vapor phase silica (average primary particle diameter 16 nm, specific surface area 130 m 2 / g by BET method) are added and sawed A preliminary dispersion was prepared using a toothed blade type disperser. The obtained preliminary dispersion was treated with a high-pressure homogenizer to obtain a 20.5% silica dispersion. 500 parts of the silica dispersion thus obtained, 20 parts of 4% boric acid aqueous solution, 250 parts of 8% polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500), surfactant 0.3 parts and water 54 parts were mixed. A second ink-receiving layer coating solution 1 having a solid content concentration of 15.0% was prepared. In addition, the average secondary particle diameter of the vapor phase method silica fine particles obtained by measurement with a laser diffraction / scattering particle size distribution measuring apparatus was 400 nm.
＜第二のインク受理層塗液２＞
第二のインク受理層塗液１の気相法シリカを、平均一次粒子径１２ｎｍ、ＢＥＴ法による比表面積２００ｍ2／ｇの気相法シリカに変更した以外は同様にして、第二のインク受理層塗液２を調製した。なお、レーザー回折／散乱式粒度分布測定装置で測定して得られた気相法シリカ微粒子の平均二次粒子径は３５０ｎｍであった。
<Second ink receiving layer coating liquid 2>
Similarly, the second ink-receiving layer coating liquid 1 was changed to gas-phase method silica having an average primary particle diameter of 12 nm and a specific surface area of 200 m 2 / g by the BET method. Layer coating solution 2 was prepared. The average secondary particle diameter of the vapor phase silica particles obtained by measurement with a laser diffraction / scattering particle size distribution analyzer was 350 nm.
＜第二のインク受理層塗液３＞
水２４０部に、５０％ジメチルジアリルアンモニウムクロライドホモポリマー（分子量９，０００）８部、沈降法シリカ（ＢＥＴ法による比表面積１３０ｍ2／ｇ、平均一次粒子径１６ｎｍ、平均凝集粒子径６μｍ）１００部を添加し、のこぎり歯状ブレード型分散機を使用して予備分散液を作製した。得られた予備分散液をビーズミルで処理して、固形分濃度２９．９％のシリカ分散液を得た。こうして得たシリカ分散液３３５部、４％ホウ酸水溶液２０部、８％ポリビニルアルコール（ケン化度８８％、平均重合度３５００）３００部、界面活性剤０．３部、水１８０部を混合し、固形分濃度１５．０％の第二のインク受理層塗液３を調製した。なお、レーザー回折／散乱式粒度分布測定装置で測定して得られたシリカ微粒子の平均二次粒子径は４００ｎｍであった。
<Second ink receiving layer coating solution 3>
240 parts of water, 8 parts of 50% dimethyldiallylammonium chloride homopolymer (molecular weight 9,000), precipitated silica (specific surface area 130 m 2 / g by BET method, average primary particle diameter 16 nm, average aggregated particle diameter 6 μm) 100 parts And a preliminary dispersion was prepared using a sawtooth blade type disperser. The obtained preliminary dispersion was treated with a bead mill to obtain a silica dispersion having a solid concentration of 29.9%. 335 parts of the silica dispersion thus obtained, 20 parts of 4% boric acid aqueous solution, 300 parts of 8% polyvinyl alcohol (saponification degree 88%, average polymerization degree 3500), surfactant 0.3 parts, water 180 parts were mixed. A second ink-receiving layer coating solution 3 having a solid content concentration of 15.0% was prepared. The average secondary particle diameter of the silica fine particles obtained by measurement with a laser diffraction / scattering type particle size distribution analyzer was 400 nm.
（サンプル１）
支持体１の顔料層上に、第一のインク受理層塗液１を乾燥塗工量が７．５ｇ／ｍ2になるようにエアーナイフコーターで塗工、乾燥した。こうして得たインク受理層の上に、さらに、第一のインク受理層塗液１を乾燥塗工量が７．５ｇ／ｍ2になるようにエアーナイフコーターで塗工、乾燥して、本発明のインクジェット記録材料を作製した。
(Sample 1)
On the pigment layer of the support 1, the first ink-receiving layer coating liquid 1 was applied and dried with an air knife coater so that the dry coating amount was 7.5 g / m 2 . On the ink receiving layer thus obtained, the first ink receiving layer coating liquid 1 is further applied and dried with an air knife coater so that the dry coating amount becomes 7.5 g / m 2. Inkjet recording material was prepared.
（サンプル２）
支持体１の顔料層上に、第二のインク受理層塗液１を乾燥塗工量が７ｇ／ｍ2になるようにエアーナイフコーターで塗工、乾燥した。次いで第二のインク受理層の上に、第一のインク受理層塗液１を乾燥塗工量が８ｇ／ｍ2になるようにエアーナイフコーターで塗工、乾燥して、本発明のインクジェット記録材料を作製した。
(Sample 2)
On the pigment layer of the support 1, the second ink-receiving layer coating liquid 1 was applied and dried with an air knife coater so that the dry coating amount was 7 g / m 2 . Next, the first ink-receiving layer coating liquid 1 is applied onto the second ink-receiving layer with an air knife coater so that the dry coating amount is 8 g / m 2 and dried, and then the ink jet recording of the present invention. The material was made.
（サンプル３）
第一のインク受理層塗液１の代わりに、第一のインク受理層塗液２を用いた以外は、サンプル２と同様にして本発明のインクジェット記録材料を作製した。
(Sample 3)
An ink jet recording material of the present invention was produced in the same manner as Sample 2, except that the first ink receiving layer coating liquid 2 was used instead of the first ink receiving layer coating liquid 1.
（サンプル４）
第一のインク受理層塗液１の代わりに、第一のインク受理層塗液３を用いた以外は、サンプル２と同様にして本発明のインクジェット記録材料を作製した。
(Sample 4)
An ink jet recording material of the present invention was produced in the same manner as Sample 2, except that the first ink receiving layer coating liquid 3 was used instead of the first ink receiving layer coating liquid 1.
（サンプル５）
第一のインク受理層塗液１の代わりに、第一のインク受理層塗液４を用いた以外は、サンプル２と同様にして本発明のインクジェット記録材料を作製した。
(Sample 5)
An ink jet recording material of the present invention was prepared in the same manner as Sample 2, except that the first ink receiving layer coating liquid 4 was used instead of the first ink receiving layer coating liquid 1.
（サンプル６）
第二のインク受理層塗液１の代わりに、第二のインク受理層塗液２を用いた以外は、サンプル２と同様にして本発明のインクジェット記録材料を作製した。
(Sample 6)
An ink jet recording material of the present invention was produced in the same manner as Sample 2, except that the second ink receiving layer coating liquid 2 was used instead of the second ink receiving layer coating liquid 1.
（サンプル７）
第二のインク受理層塗液１の代わりに、第二のインク受理層塗液３を用いた以外は、サンプル２と同様にして本発明のインクジェット記録材料を作製した。
(Sample 7)
An ink jet recording material of the present invention was prepared in the same manner as Sample 2, except that the second ink receiving layer coating liquid 3 was used instead of the second ink receiving layer coating liquid 1.
（比較サンプル１）
第一のインク受理層塗液９を用いた以外は、サンプル１と同様にしてインクジェット記録材料を作製した。
(Comparative sample 1)
An ink jet recording material was prepared in the same manner as Sample 1 except that the first ink receiving layer coating solution 9 was used.
（比較サンプル２）
第一のインク受理層塗液１の代わりに、第一のインク受理層塗液９を用いた以外は、サンプル２と同様にしてインクジェット記録材料を作製した。
(Comparative sample 2)
An ink jet recording material was prepared in the same manner as in Sample 2, except that the first ink-receiving layer coating liquid 9 was used instead of the first ink-receiving layer coating liquid 1.
（比較サンプル３）
第一のインク受理層塗液１の代わりに、第一のインク受理層塗液８を用いた以外は、サンプル２と同様にしてインクジェット記録材料を作製した。
(Comparative sample 3)
An ink jet recording material was prepared in the same manner as in Sample 2, except that the first ink receiving layer coating liquid 8 was used instead of the first ink receiving layer coating liquid 1.
（比較サンプル４）
第一のインク受理層塗液１の代わりに、第一のインク受理層塗液８を用い、第二のインク受理層塗液１の代わりに、第二のインク受理層塗液３を用いた以外は、サンプル２と同様にしてインクジェット記録材料を作製した。
(Comparative sample 4)
Instead of the first ink receiving layer coating liquid 1, the first ink receiving layer coating liquid 8 was used, and instead of the second ink receiving layer coating liquid 1, the second ink receiving layer coating liquid 3 was used. Except for the above, an ink jet recording material was prepared in the same manner as Sample 2.
＜インクジェット記録材料の光沢＞
上記のようにして作製したインクジェット記録材料について、インク受理層面のＪＩＳ Ｐ８１４２で規定される７５度鏡面光沢度を測定した。結果を表２に示した。
<Glossiness of inkjet recording material>
About the inkjet recording material produced as mentioned above, 75 degree specular glossiness prescribed | regulated by JISP8142 of an ink receiving layer surface was measured. The results are shown in Table 2.
＜塗層表面のひび割れ＞
上記のようにして作製したインクジェット記録材料について、塗層表面のひび割れを観察した。各シートのインク受理層塗工面に、セイコーエプソン株式会社製ＭＣ−１００００（顔料インク使用、プリンタ設定：ＭＣ光沢用紙、きれい）を用いて、黒のベタ印字を行った。塗層表面のひび割れは、印字部を光学顕微鏡で観察し、下記の基準により１〜５の数値で評価した。３以上であれば実用上問題ないレベルである。結果を表２に示した。
５：全くひび割れが認められない。
４：小さいひび割れが少し認められる。
３：やや大きめのひび割れがあるものの、肉眼では認識できない。
２：大きいひびがあり、よく見ると肉眼で認識できる。
１：肉眼ではっきり認識できる。
<Coating surface crack>
About the inkjet recording material produced as mentioned above, the crack of the coating layer surface was observed. Black solid printing was performed on the ink-receiving layer coated surface of each sheet using MC-10000 (using pigment ink, printer setting: MC glossy paper, clean) manufactured by Seiko Epson Corporation. Cracks on the surface of the coating layer were evaluated with numerical values of 1 to 5 by observing the printed portion with an optical microscope and using the following criteria. If it is 3 or more, it is a level which is satisfactory practically. The results are shown in Table 2.
5: No cracks are observed.
4: Some small cracks are observed.
3: Although there is a slightly large crack, it cannot be recognized with the naked eye.
2: There are large cracks that can be recognized with the naked eye if you look closely.
1: Visible to the naked eye.
＜印字特性＞
上記のようにして作製したインクジェット記録材料に、セイコーエプソン株式会社製ＭＣ−１００００（顔料インク使用、プリンタ設定：ＭＣ光沢用紙、きれい）を用いて、黒、シアン、マゼンタ、イエロー各色のベタ印字を行い、画像濃度、インク吸収性の評価を行った。黒の画像濃度について、濃度計（マクベスＲＤ９１８）を用いて測定した。また、印字部のインク吸収性は目視により評価した。インク吸収性は、下記基準により１〜５の数値で評価した。３以上であれば実用上問題ないレベルである。結果を表２に示した。
５：各色の境界部のにじみが全くなく、各インクで均一な発色が得られている。
４：境界部がやや不明瞭となっているが、各インクで均一な発色が得られている。
３：境界部のにじみが見られるものの、各インクで均一な発色が得られている。
２：境界部のにじみが明確に見られ、一部のインクで発色が不均一になっている。
１：インクが溢れ、吸収性に劣る。
<Printing characteristics>
Solid ink printing of black, cyan, magenta, and yellow is performed on the ink-jet recording material produced as described above using MC-10000 (using pigment ink, printer setting: MC glossy paper, clean) manufactured by Seiko Epson Corporation. And image density and ink absorbency were evaluated. The black image density was measured using a densitometer (Macbeth RD918). Further, the ink absorptivity of the printing part was evaluated visually. The ink absorptivity was evaluated by numerical values of 1 to 5 according to the following criteria. If it is 3 or more, it is a level which is satisfactory practically. The results are shown in Table 2.
5: There is no blur at the boundary of each color, and uniform color development is obtained with each ink.
4: Although the boundary is slightly unclear, uniform color is obtained with each ink.
3: Despite the blurring at the boundary, a uniform color was obtained with each ink.
2: The blur of the boundary part is clearly seen, and the color development is uneven in some inks.
1: The ink overflows and the absorbency is poor.
本発明のように、平均二次粒子径６００ｎｍ以下のアルミナ水和物、親水性バインダー、ホウ酸、および水溶性の乳酸塩を含有するインク受理層を設けたインクジェット記録材料は、表面の光沢感に優れ、インク受理層表面にひび割れがないため、顔料インクのひび割れへの落ち込みがなく、高い発色を得ることが可能となる。支持体とインク受理層との間に、気相法シリカまたは平均二次粒子径が６００ｎｍ以下になるまで粉砕された湿式法シリカから構成される第二のインク受理層を設けたサンプル２〜７は、表面の光沢、インク吸収性が高くなり好ましい。サンプル２〜５の比較より、乳酸カルシウム、乳酸マグネシウム、乳酸アルミニウムを用いたサンプル２〜４は、顔料インクの発色が特に高く好ましい。また、第二のインク受理層に含有される気相法シリカおよび／または湿式法シリカのＢＥＴ法による比表面積が、第一のインク受理層に含有されるアルミナ水和物のＢＥＴ法による比表面積よりも小さいサンプル２〜５、７は、インク受理層表面のひび割れが全くなく、顔料インクの発色が良好である。 As in the present invention, an inkjet recording material provided with an ink receiving layer containing an alumina hydrate having an average secondary particle diameter of 600 nm or less, a hydrophilic binder, boric acid, and a water-soluble lactate has a glossy surface. In addition, since the surface of the ink receiving layer is free from cracks, the pigment ink does not fall into cracks, and high color development can be obtained. Samples 2 to 7 in which a second ink receiving layer composed of vapor-phase method silica or wet method silica pulverized to an average secondary particle size of 600 nm or less is provided between the support and the ink receiving layer. Is preferable because of high surface gloss and ink absorbability. Compared with Samples 2 to 5, Samples 2 to 4 using calcium lactate, magnesium lactate, and aluminum lactate are preferable because the color of the pigment ink is particularly high. The specific surface area by the BET method of the vapor phase silica and / or the wet method silica contained in the second ink receiving layer is the specific surface area by the BET method of the alumina hydrate contained in the first ink receiving layer. Samples 2 to 5 and 7 smaller than the above have no cracks on the surface of the ink receiving layer and the color of the pigment ink is good.
一方、インク受理層がホウ酸を含有しない比較サンプル１、２は、塗層のひび割れが顕著であり、顔料インクの発色が大きく劣る。インク受理層に水溶性金属塩を配合していない比較サンプル３、４は、顔料インクの発色に劣る。 On the other hand, Comparative Samples 1 and 2 in which the ink receiving layer does not contain boric acid have remarkable cracks in the coating layer, and the color of the pigment ink is greatly inferior. Comparative Samples 3 and 4 in which a water-soluble metal salt is not blended in the ink receiving layer are inferior in coloring of the pigment ink.
Claims (5)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2004082071A JP4279182B2 (en) | 2004-03-22 | 2004-03-22 | Inkjet recording material |
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| JP2004082071A JP4279182B2 (en) | 2004-03-22 | 2004-03-22 | Inkjet recording material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007261208A (en) * | 2006-03-29 | 2007-10-11 | Mitsubishi Paper Mills Ltd | Inkjet recording medium |
| WO2010098818A1 (en) * | 2009-02-27 | 2010-09-02 | Eastman Kodak Company | Inkjet media system with improved image quality |
| JP2010264600A (en) * | 2009-05-12 | 2010-11-25 | Canon Inc | Recording medium |
| JP2019116078A (en) * | 2017-12-27 | 2019-07-18 | キヤノン株式会社 | Ink jet recording medium, ink jet recording method and record |
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2004
- 2004-03-22 JP JP2004082071A patent/JP4279182B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007261208A (en) * | 2006-03-29 | 2007-10-11 | Mitsubishi Paper Mills Ltd | Inkjet recording medium |
| JP4536028B2 (en) * | 2006-03-29 | 2010-09-01 | 三菱製紙株式会社 | Inkjet recording medium |
| WO2010098818A1 (en) * | 2009-02-27 | 2010-09-02 | Eastman Kodak Company | Inkjet media system with improved image quality |
| US8092874B2 (en) | 2009-02-27 | 2012-01-10 | Eastman Kodak Company | Inkjet media system with improved image quality |
| CN102333659A (en) * | 2009-02-27 | 2012-01-25 | 伊斯曼柯达公司 | Inkjet media system with improved image quality |
| JP2012519093A (en) * | 2009-02-27 | 2012-08-23 | イーストマン コダック カンパニー | Inkjet media system with improved image quality |
| JP2010264600A (en) * | 2009-05-12 | 2010-11-25 | Canon Inc | Recording medium |
| JP2019116078A (en) * | 2017-12-27 | 2019-07-18 | キヤノン株式会社 | Ink jet recording medium, ink jet recording method and record |
| JP7027162B2 (en) | 2017-12-27 | 2022-03-01 | キヤノン株式会社 | Inkjet recording medium, inkjet recording method, and recorded material |
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