GB2430435A - Ink-jet receiving layer - Google Patents
Ink-jet receiving layer Download PDFInfo
- Publication number
- GB2430435A GB2430435A GB0518173A GB0518173A GB2430435A GB 2430435 A GB2430435 A GB 2430435A GB 0518173 A GB0518173 A GB 0518173A GB 0518173 A GB0518173 A GB 0518173A GB 2430435 A GB2430435 A GB 2430435A
- Authority
- GB
- United Kingdom
- Prior art keywords
- polymer
- ink
- porous
- layer
- coated
- 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.)
- Withdrawn
Links
- 229920000642 polymer Polymers 0.000 claims abstract description 109
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 54
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 52
- 239000002904 solvent Substances 0.000 claims abstract description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- 238000000859 sublimation Methods 0.000 claims abstract description 17
- 230000008022 sublimation Effects 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 46
- 238000000576 coating method Methods 0.000 claims description 37
- 239000011248 coating agent Substances 0.000 claims description 35
- 239000011148 porous material Substances 0.000 claims description 34
- 239000013078 crystal Substances 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 13
- 238000007710 freezing Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000007641 inkjet printing Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 106
- 238000001878 scanning electron micrograph Methods 0.000 description 72
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 50
- 239000000976 ink Substances 0.000 description 23
- 239000000463 material Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 239000002861 polymer material Substances 0.000 description 16
- -1 polypropylene Polymers 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000006260 foam Substances 0.000 description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 9
- 108010010803 Gelatin Proteins 0.000 description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- 230000006911 nucleation Effects 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000609 methyl cellulose Polymers 0.000 description 6
- 239000001923 methylcellulose Substances 0.000 description 6
- 235000010981 methylcellulose Nutrition 0.000 description 6
- 239000002516 radical scavenger Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 230000012010 growth Effects 0.000 description 3
- 239000011236 particulate material Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000002061 vacuum sublimation Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 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
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001600 hydrophobic polymer Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- GUXJXWKCUUWCLX-UHFFFAOYSA-N 2-methyl-2-oxazoline Chemical compound CC1=NCCO1 GUXJXWKCUUWCLX-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 244000007835 Cyamopsis tetragonoloba Species 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium 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
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-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
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- FSBVERYRVPGNGG-UHFFFAOYSA-N dimagnesium dioxido-bis[[oxido(oxo)silyl]oxy]silane hydrate Chemical compound O.[Mg+2].[Mg+2].[O-][Si](=O)O[Si]([O-])([O-])O[Si]([O-])=O FSBVERYRVPGNGG-UHFFFAOYSA-N 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
- 239000003357 wound healing promoting agent Substances 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Ink Jet (AREA)
Abstract
An ink-jet receiver has a porous receiving layer formed upon a support. The layer is coated onto the support with a solution of polymer (e.g. a hydrophilic polymer and preferably polyvinyl alcohol) in a solvent (preferably water), the coated support is cooled (e.g. by immersion in liquid nitrogen) to cause crystallization of the solvent which is subsequently removed by sublimation to leave a porous polymer layer on the support.
Description
FOAMED POLYMER MATERIAL
FIELD OF THE INVENTION
The present invention relates to a method of manufacturing porous or foamed polymer materials. It is particularly concerned with methods of making thin layers of porous hydrophilic polymer material, which may be useful, when formed on a suitable support, as an ink-jet receiver. More particularly, the invention is concerned with the use of a polymer solvent such as water as a porogen. The invention further relates to a novel porous polymer material and to an ink-jet receiver comprising a layer of such a porous polymer material prepared according to the said method.
BACKGROUND OF THE INVENTION
Ink-jet receivers are generally classified in one of two categories according to whether the principal component material forms a layer that is "porous" or "non-porous" in nature. Many commercial photo-quality porous receivers are made using a relatively low level of a polymeric binder to lightly bind inorganic particles together to create a network of interstitial pores which absorb ink by capillary action. These receivers can appear to dry immediately after printing. However, relatively thick layers are usually required, sometimes as much as 50 urn, to provide sufficient fluid capacity. As the component materials are relatively dense, large masses of material are needed and the layers are often prone to cracking and brittleness.
Non-porous receivers are made up of polymeric layers that are capable of absorbing relatively large amounts of ink by molecular diffusion. The main problem with this type of receiver is that the diffusion process is relatively slow and the receivers can take a considerable time before they appear dry. Once dry, however, printed images on this type of receiver are typically more stable when subjected to light and ozone.
A porous polymer material may be a suitable material for use in an inkjet receiver. Methods for making porous polymer materials have been known for some time, although difficulties in conveniently making porous materials with suitable physical properties, without involving the use of significant quantities of volatile organic materials, particularly to create porosity, would be likely to prove disadvantageous in making inkjet receivers, especially in large scale manufacture. Some known methods of making porous polymer materials are described below.
Porous polymeric foams obtained by polymerising a polymerisable monomer in a high internal phase emulsion (HIPE) are known and their use as industrial filters, as supports in synthesis and cell growth and as absorbent materials for sanitary articles has been described.
WO-A-97/37745 describes a method of preparing a filter material, for use as a bag filter, for example, by impregnating a high internal phase emulsion, comprising a polymerisable monomer in the continuous phase, into a porous substrate, such as a felt material, and polymerising the polymerisable monomers to form a cured foam within the felt material. The filter material formed can comprise mean pore sizes of between about 1 and 100 m. The small pore size and high degree of porosity of the material formed results in a significant reduction in the pressure drop across the filter material.
US-A-58 17704 describes a HIPE-derived heterogeneous polymeric foam structure of interconnecting cells, obtained by polymerising polymerisable monomers from at least two distinct HIPEs in a mixture, for use to absorb and store liquids in sanitary articles.
WO-A-97/27240 describes a method of preparing foams from HIPEs by coating a HIPE continuously onto a continuous moving strip of relatively inert polymeric film, such as polypropylene, spooling the coated polymeric film and heat curing the HIPE on the coated, spooled film. The foam can then be unspoo led and removed from the polymeric film US-A-2001/0021726 discloses porous surface compositions and methods of retaining biological samples on the surface. The method relies upon the use of curable polymers. US-A-3794548 discloses the use of polyurethane as a porous polymer film. Polymer is heated causing volatilisation of solvents within the polymer resulting in a porous coating.
US-A-6228476 relates to a foam insulation sheet made using curable polymers.
WO-A-2004/090027 relates to a method of making a foamed hydrophilic polymer by foaming a solution of hydrophilic polymer, e.g. by the use of blowing agents, and treating the foamed solution with sufficient energy for a sufficiently short time (e.g. microwave radiation) that an open cell polymer foam is formed.
Ink-jet receivers having an ink-receiving layer comprising porous polymeric foams have been described in EP-A-13 88609 and EP-A-13 88560 where the porous polymeric ink-receiving layer is obtainable by coating a support with a hydrophilic polymer and a blowing agent and heating the coated support to activate the blowing agent and generate voids in the hydrophilic polymer layer.
Delaying or preventing activation of the blowing agents until after coating has been shown to improve the surface properties of the ink-receiving layer (EP-A- 1419828).
US-A-2003/0099693 describes a freeze-dried wafer composition, a light and highly porous structure, having stable crystalline particles of a wound healing agent or other pharmaceutically active compound. The wafer does not require barrier packaging to prevent water vapour ingress as water content provides the wafer material with flexibility and it has been found that in the presence of a high drug content, water vapour uptake is reduced and with a lower drug content water vapour uptake is increased, in both cases allowing a physically stable wound healing composition where the crystalline form of the drug is stabilised from polymorphic transition. The wafer, which is said to comprise of any suitable rapidly rehydratable polymer, preferably xantham gum, is formed by forming a suspension of polymers substrate (e.g. 5-10 mg/mI), a surfactant and an active ingredient (e.g. 1-30 mg/mi in water), shaping the suspension as desired using a mould and freeze-drying the shaped composition. The freeze-drying of polymers can produce shaped materials of highly porous nature. On freezing the shaped composition, crystals of ice form between polymer molecules, which may be removed by sublimation on application of a vacuum. According to this method, the solution is slowly cooled (e.g. to -55 C over 8 hours) causing crystallisation of ice and until the residual solution (after formation of ice crystals) forms a glass. A vacuum is then applied and sublimation takes place at a temperature below the Tg. Typically the freeze-drying process takes 25 hours or more.
WO-A-99/O 1166 describes a method of preparing a non-fibrous, porous material being swellable but not soluble in water and consisting of hydrophilic polymers and/or water-soluble medicaments. An aqueous solution of one or more hydrophilic polymers may be placed on the surface of a freeze plate, kept below the freezing point of water and the solution frozen. The water is then removed, e.g. by freeze-drying or solvent extraction, to reveal a porous material which may then be subjected to a dry heat treatment to cause crosslinking of the polymer to take place. Such a material provides a coherent gel with superior adsorption characteristics.
US-A-5847012 describes the preparation of highly uniform microporous foams for medical applications. An organic crystalline polymer is melted and combined with a selected solid crystalline fugitive (i.e. additive) compound (having a melting point above 25 C) to produce an isotropic solution.
Cooling under controlled conditions fosters solid-solid phase separation by simultaneous crystallisation of the fugitive compound and the polymer to produce a foam precursor comprising a fugitive compound dispersed through a matrix of polymer. The fugitive compound is then removed by sublimation to form a porous foam.
It is desirable to provide new methods of preparing ink-jet receivers that have the benefits of both the non-porous polymer receivers and of the porous receivers described above and to this end it is desirable to provide an improved method of making an ink-jet receiver comprising a porous hydrophilic polymer layer and to provide an improved ink-jet receiver comprising a porous hydrophilic polymer layer.
PROBLEM TO BE SOLVED BY THE INVENTION
It is therefore an object of the present invention to provide a method of making an ink-jet receiver comprising a porous hydrophilic polymer layer and to provide an improved ink-jet receiver comprising a porous polymer layer. It is a particular object to provide a method whereby a thin, highly porous ink-receiving hydrophilic polymeric layer is formed and whereby the degree of porosity and the pore size may be controlled.
It is a further object to provide a method of making a porous polymer material having a high degree of porosity in which the pore size is controllable.
The present inventors have found that by applying a coating of an aqueous solution of a hydrophilic polymer to a support, rapidly freezing the coated support so as to cause the formation of ice crystals in the coating and then removing the ice crystals by sublimation, an ink-jet receiver having a highly porous, hydrophilic polymeric ink-receiving layer is formed. The ink-jet receiver formed is capable of rapid uptake of ink, but also has beneficial properties associated with a non-porous hydrophilic polymer layer.
SUMMARY OF THE INVENTION
According to a first aspect of the present invention, therefore, there is provided a method of making an ink-jet receiver comprising a porous polymer layer, said method comprising the steps of providing a solution of the polymer in a polymer solvent; coating said polymer solution onto a support to form a coated support; exposing the coated support to a temperature below the freezing point of the polymer solvent to cause crystallisation of the polymer solvent forming crystals of the polymer solvent in a matrix of the polymer; and removing the crystals of the polymer solvent by sublimation to form a porous polymer layer.
In a second aspect of the invention, there is provided an ink-jet receiver obtainable by the above method.
In a third aspect of the inventions, there is provided a method of inkjet printing comprising the steps of providing an ink-jet printer responsive to digital data signals, providing an ink-jet receiver as defined above, providing an ink composition suitable for use with such a receiver and causing the ink-jet printer to print according to a desired image In a fourth aspect of the invention, there is provided a printed receiver obtainable by the above method of printing.
ADVANTAGEOUS EFFECT OF THE INVENTION
The method of the present invention provides a simple and effective way of forming highly porous polymer layer for an ink-jet receiver. It is particularly effective for providing a highly porous hydrophilic polymer ink- receiving layer. Such a hydrophilic polymer layer as an ink-receiving layer may be formed by coating an aqueous solution of one or more hydrophilic polymer and rapidly freezing the coated solution followed by sublimation of resultant ice crystals. Such a porous hydrophilic polymer layer has the advantages of being capable of rapid uptake of ink, or quick dry-time, but also of absorbing the ink, or the dye from the ink, into the polymer material, which may provide it with improved protection from environmental factors, such as light and ozone, over conventional porous receivers. A further advantage of the invention is the ability of generating very small pores in the porous material by rapidly cooling the coated solution. A still further advantage of the invention is the ability to control the degree of porosity, the pore size and the surface characteristics of the porous polymer layer.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 shows a cross-sectional Scanning Electron Micrograph (S EM) image at 1 250x magnification of a comparative coated support comprising a polyvinyl alcohol (PVA) layer on resin-coated paper, which was allowed to dry at room temperature after coating.
Figure 2 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 1 250x magnification of another comparative coated support comprising a polyvinyl alcohol (PVA) layer on resin-coated paper, which was dried at room temperature under vacuum.
Figure 3 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 1250x magnification of another comparative coated support comprising a polyvinyl alcohol (PVA) layer on resin-coated paper, which was allowed to dry at room temperature after coating before cryogenic cooling and freeze-drying.
Figure 4 shows a perspective view of a cross-sectional Scanning Electron Micrograph (SEM) image at 1 000x magnification of a coated support prepared according to the invention, which comprises a 24 jim coated thickness of a polyvinyl alcohol (PVA) layer on resin-coated paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 5 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 4000x magnification of the coated support of Figure 4.
Figure 6 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 125 Ox magnification of a coated support prepared according to the invention, which comprises a 100 m coated thickness of a polyvinyl alcohol (PVA) layer on resin-coated paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 7 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 5000x magnification of the coated support of Figure 6.
Figure 8 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 400x magnification of a coated support prepared according to the invention, which comprises a 200 jtm coated thickness of a polyvinyl alcohol (PVA) layer on resin-coated paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 9 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 2000x magnification of the coated support of Figure 8.
Figure 10 shows a cross-sectional Scanning Electron Micrograph (5 EM) image at 300x magnification of a coated support prepared according to the invention, which comprises a 400 tm coated thickness of a polyvinyl alcohol (PVA) layer on resin-coated paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 11 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 5000x magnification of the coated support of Figure 10.
Figure 12 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 500x magnification of a coated support prepared according to the invention, which comprises a 50 im coated thickness of a polyvinyl pyrrolidone (PVP) layer on resin-coated paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 13 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 5000x magnification of the coated support of Figure 12.
Figure 14 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 625x magnification of a coated support prepared according to the invention, which comprises a 50 jim coated thickness of a gelatin layer on resin- coated paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 15 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 2000x magnification of the coated support of Figure 14.
Figure 16 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 300x magnification of a coated support prepared according to the is invention, which comprises a 50 1.tm coated thickness of a methyl cellulose layer on resin-coated paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 17 shows a cross-sectional Scanning Electron Micrograph (SEM) image at I 250x magnification of the coated support of Figure 16.
Figure 18 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 2000x magnification of a coated support prepared according to the invention, which comprises a 50 j.Lm coated thickness of a PVA layer on raw paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 19 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 5000x magnification of the coated support of Figure 18.
Figure 20 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 1250x magnification of a coated support prepared according to the invention, which comprises a 50 jim coated thickness of a PVA layer on another raw paper, which was immersed in liquid nitrogen and then vacuum dried after coating.
Figure 21 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 5000x magnification of the coated support of Figure 20.
Figure 22 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 500x magnification of a coated support prepared according to the invention, which comprises a 50 tm coated thickness of a PVA layer on resin- coated paper, which was cooled in a domestic freezer at -5 C and then vacuum dried after coating.
Figure 23 shows a cross-sectional Scanning Electron Micrograph (SEM) image at 2000x magnification of the coated support of Figure 22.
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention allows an ink-jet receiver to be prepared which comprises a porous polymer layer, obtained by causing crystallisation of the polymer solvent through rapid reduction of the temperature of the environment around the coated polymer solution followed by vacuum sublimation. The polymer may be any suitable polymer for use in an ink-jet receiver. The porous polymer layer may be an image- receiving layer or, alternatively, the porous polymer layer may be a porous underlayer for the purpose of increasing the dry time of a non- porous image-receiving layer that may be coated thereon and/or to provide a sump for absorbing the carrier fluid from the ink. Preferably, however, the porous polymer layer provides the ink/image- receiving layer.
Since an ink to be applied may comprise of an aqueous or non- aqueous (i.e. organic solvent) carrier fluid, the selection of ink-jet receiver and, in particular, of polymer for use in the image-receiving layer, depends upon the use to which the ink-jet receiver is to be put, in terms of desired properties and the type of ink to be applied. Accordingly, the polymer may be a hydrophobic, hydrophilic or amphiphilic polymer or a mixture of two or more polymers from these classes of polymer. For example, one or more hydrophobic polymers may be used in conjunction with a suitable polymer solvent to generate a porous hydrophobic polymer layer on the support. This layer may be an image- receiving layer useful for absorbing the carrier fluid of an ink having an organic solvent as - 10 the carrier fluid. Preferably, however, the one or more polymers used according to the method of the invention are hydrophilic polymers and the solution thereof is an aqueous solution. Thereby, a porous hydrophilic polymer layer may be formed. Such a porous hydrophilic polymer layer is particularly useful as an image-receiving layer for use with aqueous based inks, by allowing rapid dry-time due to the porosity of the layer whilst being able to provide protection from environmental factors to dyes typically associated with non-porous receivers by absorbing the ink into the polymer material itself In a preferred embodiment of the invention, the one or more io polymer is one or more hydrophilic polymer, which is preferably a swellable hydrophilic polymer. Suitable such hydrophilic polymers include, for example, one or more of naturally occurring hydrophilic colloids and gums such as gelatin, albumin, guar, xantham, acacia and chitosan and their derivatives, functionalised proteins, functionalised gums and starches, cellulose ethers and their derivatives, such as methyl cellulose, hydroxyethyl cellulose, hydroxypropYl cellulose and carboxymethyl cellulose, polyvinyl oxazoline and polyvinyl methyloxazoline, polyoxides, polyethers, poly(ethylene imine), poly(acrylic acid), poly(methaCrylic acid), n-vinyl amides including polyacrylamide and polyvinyl pyrrolidone, polyethylene oxide and polyvinyl alcohol, its derivatives and copolymers. More preferably, the hydrophilic polymer is selected from one or more of gelatin, methyl cellulose, polyvinyl pyrrolidone and polyvinyl alcohol. It is preferred to utilise polymers that do not easily gel in the solvent used, especially where very small pore sizes (e.g. 1.tm or less) are desired. Most preferably, the hydrophilic polymer is polyvinyl alcohol.
The polymer solvent may be any suitable polymer solvent. Where, the polymer is a hydrophilic polymer, according to the preferred embodiment of the invention, the polymer solution may be, for example an alcohol, such as methanol, ethanol or propanol, but is preferably an aqueous solution. The solvent may be an aqueous alcohol or water, but most preferably is water.
In the description that follows, the "polymer solvent" and the "crystals of the polymer solvent" may be referred to as "water" and "ice crystals", which are generally preferred, but where the context allows, should be read as -11 - "water or other polymer solvent" and "ice crystals or crystals of the polymer solvent" respectively.
The polymer solution may be coated onto a support by any suitable coating method. For example, the solution may be coated onto a support by curtain coating, bead coating, extrusion coating, air knife coating, rod coating or blade coating.
The support may be any support suitable for use in an ink-jet receiver, such as paper, resin-coated paper, film base, acetate, polyethylene terephthalate (PET), a printing plate support, aluminium foil, latextreated polyester or any other suitable support.
The choice of hydrophilic polymer and the choice of solvent affect the polymer structure formed upon sublimation and thus affects the degree of porosity and the pore size in the resulting porous hydrophilic polymer layer. The choice of support can also affect the polymer structure formed upon sublimation, is for example, if the support absorbs water from the polymer solution coated upon it. Accordingly, in order to maximise the porosity of the porous hydrophilic polymer layer of the resulting ink-jet receiver, it is preferred to select an impermeable support such as a resin-coated paper as the support.
The preferred hydrophilic polymer and solvent according to this invention are PVA and water respectively.
A major factor affecting the pore size of the porous hydrophilic polymer layer formed according to a preferred aspect of the invention is the rate at which the coated support is cooled during the polymer solvent crystallisation step.
Typically, faster temperature drops result in smaller ice crystals and thus smaller pore sizes for the resultant porous hydrophilic polymer layer.
In order to obtain small pores, therefore, it is preferred to rapidly cool the coated support, by which it is meant rapidly ramping or stepping the temperature of the coated support to an exposure temperature, a temperature at which solvent crystals (e.g. ice crystals) form in the solution. The temperature may, for example, be rapidly reduced by ramping or stepwise reducing the temperature to the exposure temperature. Preferably, the rapid freezing of the - 12 - solution is effected by immediately subjecting the solution to the intended temperature of exposure.
Ideally, the coated support should be cooled at a rate that forms crystals, which after the sublimation step will leave pores of the desired size, whilst not damaging the structure of the material.
In order to achieve sub-micron pores, for example, whilst maintaining the integrity of the material, the coated support may be cooled by subjecting the coated support to an exposure temperature of-I 5 C or below, or - 30 C or below or even -50 C or below.
Any suitable method may be utilised to provide the exposure temperature to the environment of the coated support. In one embodiment, the rapid freezing step is effected by exposing the coated support to cryogenic temperatures, such as by immersing the coated support in a cryogenic liquid gas, such as liquid nitrogen.
Typically, the coated support is held at the exposure temperature for a sufficient amount of time to enable sufficient solvent crystal (e.g. ice crystal) nucleation and growth such that on removal of the (solvent crystals (e.g. ice) by sublimation, the remaining structure is an integral porous hydrophilic polymer layer. The time necessary to achieve sufficient solvent crystal (e.g. ice) nucleation and growth depends upon the temperature of exposure, the type of solvent, the concentration of the coated solution, the nature of the polymers and the polymer material. Typically, however, immersing a solution coated as a thin layer in liquid nitrogen for just a few seconds achieves the necessary nucleation and crystal growth to generate a highly porous hydrophilic polymer material with small pore sizes.
As mentioned above, the pore size obtained depends upon several factors. However, by immersing a coated solution of PVA at a concentration of weight percent in liquid nitrogen for a period of less than one minute and then removing the crystallised ice by vacuum sublimation, it is possible to obtain a polymer material having a sub-micron pore size.
According to a preferred embodiment of this aspect of the invention, the ink-jet receiver has a porous hydrophilic polymer layer having a - 13 mean pore size of from 0.01 to 10 j.Lm, more preferably from 0.01 tm to 5 tm, still more preferably from 0.01 or 0.02 to 1.tm. Preferably, when the porous hydrophilic polymer layer comprises the image-receiving layer, the mean pore size is 0.1 trn or less.
By the method of the present invention, a porosity of up to (and possibly more than) 98% can be achieved and the degree of porosity can be controlled by controlling the concentration of the polymer solution coated onto the support, and by the selection of the support used, assuming no significant evaporation takes place. Use of an image- receiving layer with a high degree of porosity means that less material is necessary to achieve the desired amount of ink-absorbance, thereby reducing cost and improving image density (greater amount of dye absorbed by a thinner layer). Table 1 illustrates the effect of porosity on the volume of material and layer thickness sufficient to absorb 25 ml/rn2 of ink, the values corresponding to estimated values of various types of ink- jet receivers mentioned in the comments column.
Table 1: Layer thickness and volume of rnateriai required to contain 25 mi/rn2 of ink for ink-receiving layers of a range of porosities.
Volume of Material Layer Thickness Comment Porosity (as %) (ml m2) (im) Close-packed particulate 25% 75.0 100.0 structures 30% 58.3 83.3 40% 37.5 62.5 Typical Commercial 50% 25.0 50.0 Receiver 60% 16.7 41.1 70% 10.7 35.7 Present invention 80% 6.3 31.3 Present invention 90% 2.8 27.8 - 14 Preferably, the ink-jet receiver prepared according to the invention has a porous hydrophilic polymer layer with a porosity of at least 60%, preferably at least 70 %, still more preferably from 75% to 98 % and most preferably from 80% to 95%, such as by 80-85%, thereby enabling less material to be utilised whilst maintaining sufficient physical robustness. As mentioned above, the porosity of the ink-jet receiver formed can be controlled by controlling the concentration of the polymer in the coated solution, which is exposed to the exposure temperature (referred to above).
The step of removing the crystals of the polymer solvent by 0 sublimation according to the method of the present invention typically involves manipulating conditions of temperature and pressure to obtain the phase transition directly from solid to vapour, as defined by, in this case, the phase diagram of water (or other solvent used). Sublimation of the ice crystals provides a porous hydrophilic polymer layer. Optionally, in order to improve the gloss of the surface of the porous
polymer layer (especially when utilised as the image-receiving layer or top layer of the ink-jet receiver), the coated support is allowed to melt slightly after step of crystallising the polymer solvent and before the step of removing the solvent crystals by sublimation. An extra step in the method of the invention may therefore be to allow the temperature of the coated support to slowly rise for a time sufficient to improve the gloss of the layer surface, e.g. until the surface of the support appears to melt. Alternatively, the gloss of the resultant porous polymer layer may be improved by applying additional heat to the coated support during the step of removing the solvent crystals by sublimation, until the surface of the support appears to melt slightly.
The method of the invention may, optionally, comprise the further step of allowing the coated support to dry slightly before crystallising the polymer solvent by exposing the coated support to reduced temperature environment, i.e. to the exposure temperature. In this way, the coated polymer solution becomes more concentrated in a controlled manner and the porosity can be varied.
The coating solution may comprise further components to improve the properties of the resultant ink-jet receiver or to aid formulation or coating.
- 15 - For example, the coating solution may comprise a surfactant to aid coating. Any suitable surfactant may be used. Typical surfactants for this purpose, where the polymer is a hydrophilic polymer, include for example, fluorosurfactants such as Lodyne S100 or Zonyl FSN, or a non- fluoro surfactants such as Olin 10G.
The coating solution may also comprise an active compound for improving the properties of the ink-jet receiver. For example, the solution may comprise one or more ozone scavenger, by which it is meant any component that actively inhibits or prevents colour fade in printed images or in pigments caused by or accelerated by ozone, hydrogen peroxide, formaldehyde, nitrogen oxides (NO), or other small gaseous molecules. It may be, for example, an ozone- specific scavenger, a hydrogen peroxide-specific scavenger or a formaldehyde- specific scavenger. The ozone scavenger may be either a catalytic or sacrificial scavenger, but is preferably catalytic. Suitable ozone scavengers that may be useful according to this aspect of the invention include, for example, complexes of metal ions of, for example, manganese, iron, zinc aluminium and titanium, and organic ozone scavengers such as dithio octane diol (DTOD). The solution may also comprise light stabilizers, such as hindered amines, etc. In order to improve the control of the rate of nucleation and therefore the size, number and dispersity of pores, the coating solution may further comprise one or more nucleation promoter, in solution or in suspension. For example, the coating solution may comprise an inorganic particulate in order to encourage nucleation of the polymer solvent in a regular and controlled manner throughout the coated layer. By including nucleation promoters in the coating solution, it may be possible to adjust (e.g. decrease) the rate of cooling and still achieve the desired pore size.
Suitable inorganic particulate materials for this purpose include any inorganic particulates useful in ink-jet receivers. For example, the inorganic particulate material used may be one or more of silica (e.g. colloidal silica), alumina (e.g. alumina sols, colloidal alumina, cationic aluminium oxide or hydrates thereof, pseudoboehmite, etc.), surface-treated cationic colloidal silica, magnesium silicate, aluminium silicate, magnesium carbonate, kaolin, talc, - 16 - calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, diatomaceous earth, calcium silicate, aluminium hydroxide, lithopone, zeolites (such as molecular sieves 3A, 4A, 5A and 13X), hydrated hallocyte and magnesium hydroxide. Preferably, the inorganic particulate material is a colloidal silica. Examples of suitable colloidal silicas include, for example, Nalco 1115 (4 nm), Ludox SM-30 (7 nm), Ludox LS-30 (12 nm), Ludox TM-40 (22 nm), Ludox AM (30 nm), Ludox TM-30 (50 nm) and Ludox PW-50 (- 80 nm), or a mixture thereof.
Depending upon the size and nature of the nucleating agent, the amount needed to achieve the desired effect may vary significantly and may be as little as 0.5 percent by weight of the amount of polymer used.
Another benefit of the method of the invention is that the porous polymer receiving layer can be prepared without the need for a cross-linking agent and therefore a highly porous receiver can be prepared without the need to is compromise flexibility and swellability of the support. Nevertheless, in order to increase the core strength of the support, a small amount of a cross-linking agent can be included in the material. Optionally, depending upon the nature of the cross-linking agent, this can be activated to cross-link subsequent to removal of the solvent crystals by sublimation. More preferably, however, the ink-receiving layer is formed in the absence of a cross-linking agent.
In another aspect of the invention there is provided a method of making a low-density, highly porous, polymer material in three-dimensional shapes. The method comprising the steps of providing a solution or sol-gel, preferably solution, of one or more polymers, optionally shaping the solution, for example by placing it in a mould, rapidly freezing the solution to generate solvent crystals within the solidifying composition and removing the solvent crystals formed by subjecting the frozen solution to a vacuum sublimation or freeze drying step. Preferably, the polymer is a hydrophilic polymer and the solvent is water.
In a still further aspect, there is provided a porous low-density, highly porous, polymer (preferably hydrophilic) material in a three-dimensional shape obtainable by this method. - 17-
The preferred features referred to above for coatings of polymer solutions used in the formation of ink-jet receivers may also apply in the present aspect where appropriate in the context. This method provides a useful way of making low-density, highly porous hydrophilic polymer materials in a desired shape, which may find utility in a variety of applications.
The invention will now be illustrated, without limitation, by the
following Examples.
EXAMPLES
Comparative Exampici A 10 wt% aqueous solution of polyvinyl alcohol (PVA Gohsenol GH17R having a degree of saponification of 86.5-89 mol% and a viscosity of 27- 33 mPa, available from Nippon Gohsei company of Japan) was coated onto resin- is coated paper by a bar coating method (using a K-Control Coater, available from RK Print Coat Instruments Ltd., UK) to produce a wet layer about 50 m thick.
The coated support was allowed to dry in air at room temperature.
A cross-sectional Scanning Electron Micrograph (SEM) image at 1250x magnification was obtained and is shown in Figure 1. As can be seen from the Figure, a non-porous PVA layer was formed.
çQparative Example 2
A coating of a solution of PVA in water on a resin-coated support was prepared as in Comparative Example 1 to produce a wet layer about 100 im thick, but this time the coated support was dried by vacuum drying at room temperature.
A cross-sectional Scanning Electron Micrograph (SEM) image at Ox magnification was obtained and is shown in Figure 2. As can be seen from the Figure, a non-porous PVA layer was formed.
- 18 - Comparative Example 3 A coating of a solution of PVA in water on a resin- coated support was prepared as in Comparative Example 1 to produce a wet layre about 50.tm thick, but this time the coated support was first dried in air at room temperature and then immersed in liquid nitrogen and then vacuum dried (using an Edwards Modulyo Vacuum Freeze Dryer).
A cross-sectional Scanning Electron Micrograph (SEM) image at 1250x magnification was obtained. As can be seen from the Figure, a non- porous PVA layer was formed.
Example 4
A 10 wt% aqueous solution of PVA was coated onto resin-coated paper according to the method of Comparative Example 1 to produce a wet layer about 24 tm thick. The coated support was immersed in liquid nitrogen for several minutes until completely frozen and then immediately subjected to a vacuum drying step.
A perspective view of a cross-sectional Scanning Electron Micrograph (SEM) image at 1 000x magnification of the coated support is shown in Figure 4 and a cross-sectional Scanning Electron Micrograph (SEM) image at 4000x magnification is shown in Figure 5. As can be seen from the Figures, a porous PVA layer was formed.
Example 5
The method of Example 4 was repeated, except that a 100 m thick coated layer was produced.
Cross-sectional Scanning Electron Micrograph (SEM) images at 1250x magnification and 5000x magnification were obtained and are shown in Figures 6 and 7. As can be seen from the Figures, a porous PVA layer was obtained.
Example 6
The method of Example 4 was repeated, except that a 200 tm thick coated layer was produced.
Cross-sectional Scanning Electron Micrograph (SEM) image at 400x magnification and 2000x magnification were obtained and are shown in Figures 8 and 9. As can be seen from the Figures, a porous PVA layer was obtained.
Example 7
The method of Example 4 was repeated, except that a 400 m thick coated layer was produced.
Cross-sectional Scanning Electron Micrograph (SEM) images at 300x magnification and 5000x magnification were obtained and are shown in Figures 10 and 11. As can be seen from the Figures, a porous PVA layer was is obtained.
Example 8
A 10 wt% aqueous solution of polyvinyl pyrrolidone (PVP, available from SGS Depauw & Stokie, N.y. as PVP/K90) was coated onto resin- coated paper according to the method of Comparative Example I to produce a wet layer about 50 jtm thick. The coated support was immersed in liquid nitrogen for several minutes until completely frozen and then immediately subjected to a vacuum drying step.
Cross-sectional Scanning Electron Micrograph (SEM) images at 500x magnification and 5000x magnification were obtained and are shown in Figures 12 and 13. As can be seen from the Figures, a porous PVP layer was formed having pores formed in the range of from about 1 to 2 pm.
- 20 -
Example 9
A 10 wt% aqueous solution of gelatin (lime-processed, ossein gelatin) was coated onto resin-coated paper according to the method of Comparative Example 1 to produce a wet layer about 50tm thick. The coated support was chill set, then immersed in liquid nitrogen for several minutes until completely frozen and then immediately subjected to a vacuum drying step.
Cross-sectional Scanning Electron Micrograph (SEM) images at 625x magnification and 2000x magnification of the coated support were obtained and are shown in Figures 14 and 15. As can be seen from the Figures, a porous gelatin layer was formed having pores formed in the range of from about 2 to 4 pm.
Example 10
A 2 wt% aqueous solution of methyl cellulose (available from is Aldrich Chemical Company - Cat. No. 27,442-9) was coated onto resin-coated paper according to the method of Comparative Example 1 to produce a wet layer about 50 tm thick. The coated support was immersed in liquid nitrogen for several minutes until completely frozen and then immediately subjected to a vacuum drying step.
Cross-sectional Scanning Electron Micrograph (SEM) images at 300x magnification and 1250x magnification were formed and are shown in Figures 16 and 17. As can be seen from the Figures, a porous methyl cellulose layer was formed having pores formed in the range of from about 5 to 10 jtm.
Examplii A 10 wt% aqueous solution of PVA was coated onto raw paper (Domtar Quantum #65; a standard photocopier paper) according to the method of Comparative Example 1 to produce a wet layer about 50 pm thick. The coated support was immersed in liquid nitrogen for several minutes until completely frozen and then immediately subjected to a vacuum drying step.
Cross-sectional Scanning Electron Micrograph (SEM) images at 2000x magnification and 5000x magnification were obtained and are shown in Figures 18 and 19. As can be seen from the Figures, a porous PVA layer was formed.
Example 12
A 10 wt% aqueous solution of PVA was coated onto raw paper 2, which was a standard photographic paper prior to applying a resin, according to the method of Comparative Example 1 to produce a wet layer about 50 pm thick.
The coated support was immersed in liquid nitrogen for several minutes until completely frozen and then immediately subjected to a vacuum drying step.
Cross-sectional Scanning Electron Micrograph (SEM) images at 1 250x magnification and 5000x magnification were obtained and are shown in Figures 20 and 21. As can be seen a porous PVA layer of sub-micron pore size was formed.
Example 13
A 10 wt% aqueous solution of PVA was coated onto resin-coated paper according to the method of Comparative Example 1 to produce a wet layer about 50 jim thick. The coated support was cooled in a domestic freezer at -5 C until completely frozen and then immediately subjected to a vacuum drying step.
Cross-sectional Scanning Electron Micrograph (SEM) images at 500x magnification and 2000x magnification were obtained and are shown in Figures 22 and 23. As can be seen from the Figures, a porous PVA layer was formed having pores formed in the range of from about 3 to 5 jim.
Example 14
The speed of ink uptake in the coated supports formed in the Comparative Examples 1 to 3 and in Examples 4 to 13 of the invention was assessed by applying a I p1 droplet of a cyan ink-jet ink, extracted from a commercially available ink-jet cartridge, onto the surface of each of the coated supports and observing the time taken for absorption. The absorption was rated as "slow" (s), "medium" (m) or "fast" (f) according to whether the ink droplet was absorbed in greater than 90 seconds, between 60 and 90 seconds or less than 60 - 22 - seconds respectively. The rate of ink uptake for each coated support is presented in Table 2, along with other information representative of the particular coated support and the porosity of each coating.
The layer porosity was calculated from a knowledge of the actual coated mass, determined gravimetrically, which was converted to actual coated volume by knowing the density of the coated material, together with the total thickness of the coated layer as measured by microscopic crosssection. Layer porosity was calculated as: Void Volume Porosiiy(%) xl 00 Total Volume where Total Volume was derived from the measurement of the Total Thickness of the coated layer and Void Volume was determined by subtracting the Actual Coated Volume from the Total Volume. -23 -
Table 2. The experimental details and results obtained.
Example Example Polymer Freezing Drying Exptl. Variation Ink Porosity No. Type process process uptake % Cl Comparative PVA None Evaporation Control S 0% C2 Comparative PVA None Vacuum-dry Vacuum-drying S 0% effect _____ _______ 03 Comparative PVA LN & Vacuum Evaporation LN & Vacuum S 0% after evap drying effects _______ __________ ________ drying __________ _____ ____ hI3UPA iM PJIV *i 1$2* E4 Invention PVA LN after ctg Vacuum- dry 24 m ctd F 94% thickness _____ _______ E5 Invention PVA LN after ctg Vacuum-dry 100 jim ctd F 80% thickness ____ _______ E6 Invention PVA LN after ctg Vacuum-dry 200 jim ctd F 82% thickness _____ _______ E7 Invention PVA LN after ctg Vacuum-dry 400 jim ctd F 58% thickness _____ _______ E8 Invention PVP LN after ctg Vacuum-dry Different F 87% ________ ____________ _________ polymer E9 Invention Gelatin LN after ctg Vacuum-dry Different F 88% ____________ _________ polymer ElO Invention Methyl LN after ctg Vacuum- dry Different F 93% Cellulose __________ polymer _____ _______ El 1 Invention PVA LN after ctg Vacuum-dry Different paper F 63% substrate I El2 Invention PVA LN after ctg Vacuum-dry Different Paper F 53% substrate 2 E13 Invention PVA Freezer after Vacuum-dry Slow freezing F 89% ctg effect Key: LN = Liquid Nitrogen PVA = Poly(vinyl alcohol), PVP = Poly(vinyl pyrrolidone); MC Methyl Cellulose F = Fast, M = Medium and S = Slow ink uptake As can be seen from the data in Table 2, the rate of ink absorption was significantly improved in the coated supports prepared accord to a method of the invention over those prepared in the Comparative Examples.
Claims (16)
- - 24 - CLAIMS: 1. A method of making an ink-jet receiver comprising aporous polymer layer, said method comprising the steps of providing a solution of the polymer in a polymer solvent; coating said polymer solution onto a support to form a coated support; exposing the coated support to a temperature below the freezing point of the polymer solvent to cause crystallisation of the polymer solvent io forming crystals of the polymer solvent in a matrix of the polymer; and removing the crystals of the polymer solvent by sublimation to form a porous polymer layer.
- 2. A method as claimed in Claim 1, wherein the one or more polymers are hydrophilic polymers and the polymer solution is an aqueous solution.
- 3. A method as claimed in Claim 1 or Claim 2, wherein the polymer solvent is water.
- 4. A method as claimed in any one of the preceding claims, wherein the polymer solution comprises polymer in an amount of from 80 to 98% by weight.
- 5. A method as claimed in any one of the preceding claims, wherein the porous polymer layer has a porosity of from 80 to 98%.
- 6. A method as claimed in any one of the preceding claims, wherein the step of exposing the coated support to a temperature below the freezing point cools the coated support sufficiently rapidly that upon removal of the polymer crystals formed thereby, the porous polymer layer has a mean pore size of 1 tm or less.
- 7. A method as claimed in Claim 6, wherein the porous polymer layer has a mean pore size of 0.1 jim or less.
- 8. A method as claimed in any one of the preceding claims, which method further comprises, after the crystals of the polymer solvent have formed, the step of raising the temperature until the surface of the frozen coated support begins to melt before removing the crystals of the polymer solvent.
- 9. A method as claimed in any one of the preceding claims, wherein the step of exposing the coated support to a temperature below the freezing point of the polymer solvent comprises treating the coated support with or immersing the coated support in liquid nitrogen
- 10. A method as claimed in any one of the preceding claims, wherein the step of removing the crystals of the polymer solvent comprises subjecting the coated support to a freeze-drying step.
- ii. A method as claimed in any one of the preceding claims, wherein the polymer is polyvinyl alcohol and the polymer solvent is water.
- 12. An ink-jet receiver comprising a porous polymer layer, said receiver being obtainable by any one of the preceding claims.
- 13. An ink-jet receiver as claimed in Claim 12, wherein the porous polymer layer has a porosity of from 80-98%.
- 14. An ink-jet receiver as claimed in Claim 12 or Claim 13 having a porous polymer layer with a mean pore size of I jim or less.
- 15. An ink-jet receiver as claimed in Claim 1 4wherein the mean pore size is 0.1 jim or less.- 26 -
- 16. A method of ink-jet printing comprising the steps of providing an ink- jet printer responsive to digital data signals, providing an ink-jet receiver as defined in any one of Claims 12 to 15, providing an ink composition suitable for use with such a receiver and causing the ink-jet printer to print according to a desired image.17 A printed receiver obtainable by the method defined in Claim 16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0518173A GB2430435A (en) | 2005-09-07 | 2005-09-07 | Ink-jet receiving layer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0518173A GB2430435A (en) | 2005-09-07 | 2005-09-07 | Ink-jet receiving layer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB0518173D0 GB0518173D0 (en) | 2005-10-12 |
| GB2430435A true GB2430435A (en) | 2007-03-28 |
Family
ID=35220984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0518173A Withdrawn GB2430435A (en) | 2005-09-07 | 2005-09-07 | Ink-jet receiving layer |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2430435A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105467682A (en) * | 2016-01-15 | 2016-04-06 | 京东方科技集团股份有限公司 | Film structure, producing method of film structure, display substrate, backlight source and display device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1392575A (en) * | 1972-02-16 | 1975-04-30 | Polysar Ltd | Solid microporous polymer layers |
| US5847012A (en) * | 1993-08-13 | 1998-12-08 | Smith & Nephew, Inc. | Microporous polymeric foams and microtextured surfaces |
| WO1999003685A1 (en) * | 1997-07-14 | 1999-01-28 | Minnesota Mining And Manufacturing Company | Ink-jet printable microporous film |
| EP0940427A1 (en) * | 1998-03-06 | 1999-09-08 | Imation Corp. | Method of preparing a microporous film, and image accepting member |
| US6136872A (en) * | 1998-11-20 | 2000-10-24 | Shell Oil Company | Freeze-dried polystyrene-polysiloxane foams |
| EP1160273A1 (en) * | 1998-10-12 | 2001-12-05 | Yupo Corporation | Porous resin film |
-
2005
- 2005-09-07 GB GB0518173A patent/GB2430435A/en not_active Withdrawn
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1392575A (en) * | 1972-02-16 | 1975-04-30 | Polysar Ltd | Solid microporous polymer layers |
| US5847012A (en) * | 1993-08-13 | 1998-12-08 | Smith & Nephew, Inc. | Microporous polymeric foams and microtextured surfaces |
| US5969020A (en) * | 1993-08-13 | 1999-10-19 | Poly-Med, Inc. | Microporous polymeric foams and microtextured surfaces |
| WO1999003685A1 (en) * | 1997-07-14 | 1999-01-28 | Minnesota Mining And Manufacturing Company | Ink-jet printable microporous film |
| EP0940427A1 (en) * | 1998-03-06 | 1999-09-08 | Imation Corp. | Method of preparing a microporous film, and image accepting member |
| US20040058135A1 (en) * | 1998-03-06 | 2004-03-25 | Kodak Polychrome Graphics, Llc | Microporous film and image accepting member |
| EP1160273A1 (en) * | 1998-10-12 | 2001-12-05 | Yupo Corporation | Porous resin film |
| US6136872A (en) * | 1998-11-20 | 2000-10-24 | Shell Oil Company | Freeze-dried polystyrene-polysiloxane foams |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105467682A (en) * | 2016-01-15 | 2016-04-06 | 京东方科技集团股份有限公司 | Film structure, producing method of film structure, display substrate, backlight source and display device |
| WO2017121122A1 (en) * | 2016-01-15 | 2017-07-20 | 京东方科技集团股份有限公司 | Film layer structure, manufacturing method thereof, display substrate, backlight and display device |
| US10347835B2 (en) | 2016-01-15 | 2019-07-09 | Boe Technology Group Co., Ltd. | Layer structure, manufacturing method thereof, display substrate, backlight and display device |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0518173D0 (en) | 2005-10-12 |
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