EP1346840A1 - Improved recording element for ink jet printing - Google Patents
Improved recording element for ink jet printing Download PDFInfo
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- EP1346840A1 EP1346840A1 EP02100283A EP02100283A EP1346840A1 EP 1346840 A1 EP1346840 A1 EP 1346840A1 EP 02100283 A EP02100283 A EP 02100283A EP 02100283 A EP02100283 A EP 02100283A EP 1346840 A1 EP1346840 A1 EP 1346840A1
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- European Patent Office
- Prior art keywords
- cationic
- ink jet
- jet recording
- recording element
- ink
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- 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.)
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Classifications
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- 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
- B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
- B41M5/506—Intermediate layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
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- 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
- B41M5/5236—Macromolecular coatings characterised by the use of natural gums, of proteins, e.g. gelatins, or of macromolecular carbohydrates, e.g. cellulose
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
Definitions
- the present invention relates to an improved recording element for ink jet printing.
- ink jet printing has become a technology of choice.
- a recent survey on progress and trends in ink jet printing technology is given by Hue P. Le in Journal of Imaging Science and Technology Vol. 42 (1), Jan/Febr 1998.
- tiny drops of ink fluid are projected directly onto an ink receptor surface without physical contact between the printing device and the receptor.
- the printing device stores the printing data electronically and controls a mechanism for ejecting the drops image-wise. Printing is accomplished by moving the print head across the paper or vice versa.
- Early patents on ink jet printers include US 3,739,393, US 3,805,273 and US 3,891,121.
- the jetting of the ink droplets can be performed in several different ways.
- a continuous droplet stream is created by applying a pressure wave pattern.
- This process is known as continuous ink jet printing.
- the droplet stream is divided into droplets that are electrostatically charged, deflected and recollected, and into droplets that remain uncharged, continue their way undeflected, and form the image.
- the charged deflected stream forms the image and the uncharged undeflected jet is recollected.
- several jets are deflected to a different degree and thus record the image (multideflection system).
- the ink droplets can be created “on demand” (“DOD” or “drop on demand” method) whereby the printing device ejects the droplets only when they are used in imaging on a receiver thereby avoiding the complexity of drop charging, deflection hardware, and ink recollection.
- DOD on demand
- the ink droplet can be formed by means of a pressure wave created by a mechanical motion of a piezoelectric transducer (so-called “piezo method”), or by means of discrete thermal pushes (so-called “bubble jet” method, or “thermal jet” method).
- Ink compositions for ink jet typically include following ingredients : dyes or pigments, water and/or organic solvents, humectants such as glycols, detergents, thickeners, polymeric binders, preservatives, etc.. It will be readily understood that the optimal composition of such an ink is dependent on the ink jetting method used and on the nature of the substrate to be printed.
- the ink compositions can be roughly divided in :
- the finished ink jet image is meant to be transparent, e.g. for use in overhead projection or for use in a medical diagnostic hardcopy, it is necessary to use a transparent polymeric film (which may contain a colorant depending on the application) as support for the ink jet recording element.
- a well-known polymeric film for use as support in many fields of technology and especially in different types of image recording is a polyester, such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- a problem when using such supports for ink receiving layers is the criticallity of the so-called "adhesion dry" property. This means that on further handling of the finished ink jet image, e.g.
- the ink receiver layer tends to get loose from the polyester support.
- the problem of the bad adhesion between the hydrophobic PET and the hydrophilic light-sensitive layer(s) is solved by providing the PET support with at least one and preferably two so-called subbing layers.
- this measure did not solve completely the problem of insufficient "adhesion dry" when typical ink receiver compositions are coated on a polyester support.
- the present invention seeks to remedy the problem of insufficient adhesion in dry state when subbed polyester is used as support for a typical ink receiver layer.
- the above-mentioned desired advantageous effect is realised by providing an ink jet recording material comprising a subbed polyester support, and an ink receiver layer containing a cationic compound, characterized in that between said support and said ink receiver layer there is an additional adhesion promoting layer present comprising a binder and a cationically modified silica.
- the support of the ink jet recording material used in accordance with the present invention is a transparent polyester support, e.g. a polyethylene terephthalate or polyethylene naphthalate support.
- PET Polyethylene terephthalate
- This support is coated on at least one side with a so-called subbing layer as is well known from photographic technology.
- the polyester is subbed with two subbing layers, a so-called latex subbing layer and a so-called gelatin subbing layer.
- An essential ingredient of the latex subbing layer is an adhesion promoting latex.
- a preferred class of latex polymers for this purpose are vinylidene chloride-containing copolymers having carboxyl functional groups.
- Illustrative of such polymers are (1) copolymers of vinylidene chloride and an unsaturated carboxylic acid such as acrylic or methacrylic acid, (2) copolymers of vinylidene chloride and a half ester of an unsaturated carboxylic acid such as the monomethylester of itaconic acid, (3) terpolymers of vinylidene chloride, itaconic acid and an alkyl acrylate or methacrylate such as ethyl acrylate or methyl methacrylate, and (4) terpolymers of vinylidene chloride, acrylonitrile or methacrylonitrile and an unsaturated carboxylic acid such as acrylic acid or methacrylic acid.
- the latex polymer is co(vinylidene chloride-methyl acrylate-itaconic acid ; 88 % / 10 % / 2 %).
- This copolymer is prepared by emulsion polymerization using 0.5 % MERSOLAT H (trade-mark of Bayer AG) as emulsifying agent. It is necessary to add extra surfactant, a so-called post-stabilizer, to the latex in order to assure a good stability on storage. An excellent storage stability is obtained when 4 % of ULTRAVON W, trade mark of Ciba-Geigy, or DOWFAX, trade mark of Dow, is used.
- colloidal silica As a further preferred ingredient of the coating solution of the latex subbing layer colloidal silica may be added.
- a preferred compound is KIESELSOL 100F (trade-mark of Bayer AG), average particle size 25-30 nm. The ratio of the amount of latex to silica is preferably about 80/20.
- the latex subbing layer may further contain surfactants and biocides. As already stated above, there is preferably also a so-called gelatin subbing layer on top of the latex subbing layer. Typically, this gelatin subbing layer contains a mixture of gelatin and colloidal silica.
- a preferred compound is again KIESELSOL 300F (trade-mark of Bayer AG).
- a plasticizing compound can be used in order to avoid the formation of cracks in the dried layer due to the occurence of excessive shrinking of the layer during drying.
- Plasticizing agents are well-known in the art.
- Low-molecular weight compounds e.g. acetamide, glycerin
- polymeric latices e.g. polyethylacrylate, poly-n.-butylacrylate
- the gelatin subbing layer may contain one or more surfactants.
- Useful surfactants include : ULTRAVONTM W, an aryl sulfonate from CIBA-GEIGY, DOWFAX from Dow CO., and ARKOPALTM N060 (previously HOSTAPALTM W), a nonylphenylpolyethylene-glycol from HOECHST.
- the subbing layers may be present on just one side of the polyester support or they may also be present on the back side when the ink jet recording medium is provided with one or more backing layers, such as an anti-curl layer, or an electroconductive layer.
- the binder can be chosen from a list of compounds well-known in the art including hydroxyethyl cellulose; hydroxypropyl cellulose; hydroxyethylmethyl cellulose; hydroxypropyl methyl cellulose; hydroxybutylmethyl cellulose; methyl cellulose; sodium carboxymethyl cellulose; sodium carboxymethylhydroxethyl cellulose; water soluble ethylhydroxyethyl cellulose; cellulose sulfate; polyvinyl alcohol; vinylalcohol copolymers; polyvinyl acetate; polyvinylacetal; polyvinyl pyrrolidone; polyacrylamide; acrylamide/acrylic acid copolymer; poly(styrene), styrene copolymers; acrylic or methacrylic polymers; styrene/
- a preferred binder for the practice of the present invention is a polyvinylalcohol (PVA), a vinylalcohol copolymer or modified polyvinyl alcohol.
- PVA polyvinylalcohol
- the polyvinyl alcohol is a cationic type polyvinyl alcohol, such as the cationic polyvinyl alcohol grades from Kuraray, such as POVAL C506, POVAL C118, and from Nippon Goshei.
- cationic polyvinyl alcohol may be obtained by several routes:
- Silica as pigment in ink receiving elements is disclosed in numerous old and recent patents, e.g. US 4,892,591, US 4,902,568, EP 373573, EP 423829, EP 487350, EP 493100, EP 514633, etc..
- the silica, before cationic modification can be chosen from different types, such as crystalline silica, amorphous silica, precipitated silica, fumed silica, silica gel, spherical and non-spherical silica.
- the silica may contain minor amounts of metal oxides from the group Al, Zr, Ti.
- AEROSIL OX50 BET surface area 50 ⁇ 15 m 2 /g, average primary particle size 40 nm, SiO 2 content > 99.8%, Al 2 O 3 content ⁇ 0.08%
- AEROSIL MOX170 BET surface area 170 g/m 2 , average primary particle size 15 nm, SiO 2 content > 98.3%, Al 2 O 3 content 0.3-1.3%)
- AEROSIL MOX80 BET surface area 80 ⁇ 20 g/m 2 , average primary particle size 30 nm, SiO 2 content > 98.3%, Al 2 O 3 content 0.3-1.3%)
- other hydrophilic AEROSIL grades available from Degussa-Hüls AG, which may give aqueous dispersions with a small average particle size ( ⁇ 500 nm).
- Cationically modified silica can be prepared by following methods, without meaning to be limitative :
- the ratio cationized silica/binder in the adhesion promoting layer is preferably between 1:4 and 10:1.
- the thickness of the adhesion promoting layer is preferably comprised between 1 and 6 g/m 2 .
- the ink receiver layer contains a cationic compound.
- This can be a cationic inorganic pigment, or a cationic polymer, or a mixture of both.
- the ink receiver layer will further contain a binder which itself can be cationic or not.
- the cationic compound is a cationic polymer it can be a cationic film forming polymer, functioning as binder, such as cationic PVA, or it can be a non-film forming polymeric mordant, in which latter case a separate binder will usually be present which again can be cationic or not.
- cationic inorganic pigment means a substance composed of fine particles having a positive charge on their surfaces and therefore having adsorbability of acid substances such as acid dyes.
- Specific examples thereof include fine particles composed of oxides of metals such as magnesium, calcium, aluminum, zirconium, zinc, chromium, iron, copper, tin, lead and manganese.
- Those having a negative charge on their surfaces like silica may also be used if they are surface-treated to change the negative charge on the surface to a positive charge (as already explained above for the silica in the adhesion promoting layer).
- the cationic substance is chosen from crystalline boehmite, or ⁇ -AlO(OH), and cationized silica, and mixtures thereof.
- Boehmite is the most preferred cationic pigment since it allows a good transparency, meaning a low haze value, for the finished ink jet image.
- Useful types of boehmite include, in powder form, DISPERAL, DISPERAL HP14 and DISPERAL 40 from Sasol, MARTOXIN VPP2000-2 and GL-3 from Martinswerk GmbH.; liquid boehmite alumina systems, e.g. DISPAL 23N4-20, DISPAL 14N-25, DISPERAL AL25 from Sasol.
- Patents on alumina hydrate include EP 500021, EP 634286, US 5,624,428, EP 742108, US 6,238,047, EP 622244, EP 810101, etc..
- Other useful cationic inorganic pigments include aluminum oxide (alumina), e.g.
- ⁇ -Al 2 O 3 types such as NORTON E700, available from Saint-Gobain Ceramics & Plastics, Inc, ⁇ -Al 2 O 3 types, such as ALUMINUM OXID C from Degussa; other aluminum oxide grades, such as BAIKALOX CR15 and CR30 from Baikowski Chemie; DURALOX grades and MEDIALOX grades from Baikowski Chemie, BAIKALOX CR80, CR140, CR125, B105CR from Baikowski Chemie; CAB-O-SPERSE PG003 tradeamrk from Cabot, CATALOX GRADES and CATAPAL GRADES from from Sasol, such as PLURALOX HP14/150; colloidal Al 2 O 3 types, such as ALUMINASOL 100; ALUMINASOL 200, ALUMINASOL 220, ALUMINASOL 300, and ALUMINASOL 520 trademarks from Nissan Chemical Industries or NALCO 8676 trademark from ONDEO Nalco.
- cationic inorganic pigments include aluminum trihydroxides such as Bayerite, or ⁇ -Al(OH) 3 , such as PLURAL BT, available from Sasol, and Gibbsite, or ⁇ -Al(OH) 3 , such as MARTINAL grades from Martinswerk GmbH, MARTIFIN grades, such as MARTIFIN OL104, MARTIFIN OL 107 and MARTIFIN OL111 from Martinswerk GmbH , MICRAL grades, such as MICRAL 1440, MICRAL 1500; MICRAL 632; MICRAL 855; MICRAL 916; MICRAL 932; MICRAL 932CM; MICRAL 9400 from JM Huber company; HIGILITE grades, e.g.
- HIGILITE H42 or HIGILITE H43M from Showa Denka K.K. HYDRAL GRADES such as HYDRAL COAT 2, HYDRAL COAT 5 and HYDRAL COAT 7, HYDRAL 710 and HYDRAL PGA, from Alcoa Industrial Chemicals.
- HYDRAL GRADES such as HYDRAL COAT 2, HYDRAL COAT 5 and HYDRAL COAT 7, HYDRAL 710 and HYDRAL PGA, from Alcoa Industrial Chemicals.
- Another useful type of cationic pigment is zirconium oxide such as NALCO OOSS008 trademark of ONDEO Nalco, acetate stabilized ZrO 2 , ZR20/20, ZR50/20, ZR100/20 and ZRYS4 trademarks from Nyacol Nano Technologies.
- Useful mixed oxides are SIRAL grades from Sasol, colloidal metaloxides from Nalco such as Nalco 1056, Nalco TX10496, Nalco TX11678.
- the cationic compound present in the ink receiver layer is a cationic polymer it can be a cationic film forming binder such as a cationic polyvinyl alcohol, a cationic cellulose ether, a cationic polyurethane, and mixtures thereof.
- the cationic polymer can be a cationic mordant.
- a particularly suited compound is a poly(diallyldimethylammonium chloride) or, in short, a poly(DADMAC). These compounds are commercially available from several companies, e.g. Aldrich, Nalco, CIBA, Nitto Boseki Co., Clariant, BASF and EKA Chemicals.
- DADMAC copolymers such as copolymers with acrylamide, e.g NALCO 1470 trade mark of ONDEO Nalco or PAS-J-81, trademark of Nitto Boseki Co., such as copolymers of DADMAC with acrylates, such as Nalco 8190, trademark of ONDEO Nalco; copolymers of DADMAC with SO 2 , such as PAS-A-1 or PAS-92, trademarks of Nitto Boseki Co., copolymer of DADMAC with maleic acid, e.g.
- PAS-410 trademark of Nitto Boseki Co., copolymer of DADMAC with diallyl(3-chloro-2-hydroxypropyl)amine hydrochloride, eg. PAS-880, trademark of Nitto Boseki Co., dimethylamine-epichlorohydrine copolymers, e.g.
- Nalco 7135 trademark of ONDEO Nalco or POLYFIX 700, trade name of Showa High Polymer Co.
- other POLYFIX grades which could be used are POLYFIX 601, POLYFIX 301, POLYFIX 301A, POLYFIX 250WS, and POLYFIX 3000 ;
- NEOFIX E-117 trade name of Nicca Chemical Co., a polyoxyalkylene polyamine dicyanodiamine, and REDIFLOC 4150, trade name of EKA Chemicals, a polyamine;
- MADQUAT methacryloxyethyltrimethylammonium chloride
- CYPRO 514/515/516, SUPERFLOC 507/521/567 cationic acrylic polymers, such as ALCOSTAT 567, trademark of CIBA, cationic cellulose derivatives such as CELQUAT L-200, H-100, SC-240C, SC-230M, trade names of Starch & Chemical Co., and QUATRISOFT LM200, UCARE polymers JR125, JR400, LR400, JR30M, LR30M and UCARE polymer LK; fixing agents from Chukyo Europe: PALSET JK-512, PALSET JK512L, PALSET JK-182, PALSET JK-220, WSC-173, WSC-173L, PALSET JK-320, PALSET JK-320L and PALSET JK-350; polyethyleneimine and copolymers, e.g.
- LUPASOL trade name of BASF AG
- triethanolamine-titanium-chelate e.g. TYZOR, trade name of Du Pont Co.
- copolymers of vinylpyrrolidone such as VIVIPRINT 111, trade name of ISP, a methacrylamido propyl dimethylamine copolymer; with dimethylaminoethylmethacrylate such as COPOLYMER 845 and COPOLYMER 937, trade names of ISP
- vinylimidazole e.g.
- LUVIQUAT CARE, LUVITEC 73W, LUVITEC VP155 K18P, LUVITEC VP155 K72W, LUVIQUAT FC905, LUVIQUAT FC550, LUVIQUAT HM522, and SOKALAN HP56 all trade names of BASF AG; polyamidoamines, e.g. RETAMINOL and NADAVIN, trade marks of Bayer AG; phosphonium compounds such as disclosed in EP 609930 and other cationic polymers such as NEOFIX RD-5, trademark of Nicca Chemical Co.
- the ink receiving layer, the adhesion promoting layer, and the optional backing layer may further contain well-known conventional ingredi ⁇ nts, such as surfactants serving as coating aids, hardening agents, plasticizers, whitening agents and matting agents.
- surfactants may be incorporated in the layers of the recording element of the present invention. They can be any of the cationic, anionic, amphoteric, and non-ionic ones as described in JP-A 62-280068 (1987).
- surfactants are N-alkylamino acid salts, alkylether carboxylic acid salts, acylated peptides, alkylsulfonic acid salts, alkylbenzene and alkylnaphthalene sulfonic acid salts, sulfosuccinic acid salts, ⁇ -olefin sulfonic acid salts, N-acylsulfonic acid salts, sulfonated oils, alkylsulfonic acid salts, alkylether sulfonic acid salts, alkylallylethersulfonic acid salts, alkylamidesulfonic acid salts, alkylphosphoric acid salts, alkyletherphosphoric acid salts, alkylallyletherphosphoric acid salts, alkyl and alkylallylpolyoxyethylene ethers, alkylallylformaldehyde condensed acid salts, alkylallylethersulfonic acid salts, alkyl
- Useful cationic surfactants include N-alkyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, dodecyldimethylamine, tetradecyldimethylamine, ethoxylated alkyl guanidine-amine complex, oleamine hydroxypropyl bistrimonium chloride, oleyl imidazoline, stearyl imidazoline, cocamine acetate, palmitamine, dihydroxyethylcocamine, cocotrimonium chloride, alkyl polyglycolether ammonium sulphate, ethoxylated oleamine, lauryl pyridinium chloride, N-oleyl-1,3-diaminopropane, stearamidopropyl dimethylamine lactate, coconut fatty amide, oleyl hydroxyethyl imidazoline, isostearyl ethylimidonium ethosulphate, lauramidopropyl PEG-d
- These surfactants are commercially available from DuPont and 3M.
- the concentration of the surfactant component in the ink-receiving layer is typically in the range of 0.1 to 2 %, preferably in the range of 0.4 to 1.5 % and is most preferably 0.75 % by weight based on the total dry weight of the layer.
- the ink-receiving layer, the adhesion promoting layer, and the optional auxiliary layers may be crosslinked to provide such desired features as waterfastness and non-blocking characteristics.
- the crosslinking is also useful in providing abrasion resistance and resistance to the formation of fingerprints on the element as a result of handling.
- crosslinking agents also known as hardening agents - that will function to crosslink film forming binders. Hardening agents can be used individually or in combination and in free or in blocked form.
- a great many hardeners, useful for the present invention are known, including formaldehyde and free dialdehydes, such as succinaldehyde and glutaraldehyde, blocked dialdehydes, active esters, sulfonate esters, active halogen compounds, isocyanate or blocked isocyanates, polyfunctional isocyanates, melamine derivatives, s-triazines and diazines, epoxides, active olefins having two or more active bonds, carbodiimides, zirconium complexes, e.g.
- BACOTE 20 ZIRMEL 1000 or zirconium acetate, trademarks of MEL Chemicals, titanium complexes, such as TYZOR grades from DuPont, isoxazolium salts subsituted in the 3-position, esters of 2-alkoxy-N-carboxy-dihydroquinoline, N-carbamoylpyridinium salts, hardeners of mixed function, such as halogen-substituted aldehyde acids (e.g.
- mucochloric and mucobromic acids onium substituted acroleins and vinyl sulfones and polymeric hardeners, such as dialdehyde starches and copoly(acroleinmethacrylic acid), and oxazoline functional polymers, e.g. EPOCROS WS-500, and EPOCROS K-1000 series, and maleic anhydride copolymers, e.g. GANTREZ AN119
- boric acid is a preferred crosslinker.
- the ink-receiving layer, the adhesion promoting layer and the optional auxiliary layers comprise a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromophthalicanhydride, urea phosphate, triphenylphosphate, glycerolmonostearate, propylene glycol monostearate, tetramethylene sulfone, n-methyl-2-pyrrolidone, n-vinyl-2-pyrrolidone.
- a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride
- the different layers may also comprise ingredients to improve the lightfastness of the printed image, such as antioxidants, UV-absorbers, peroxide scavengers, singlet oxygen quenchers such as hindered amine light stabilizers, (HALS compounds) etc..Stilbene compounds are a preferred type of UV-absorber.
- the different layers can be coated onto the support by any conventional coating technique, such as dip coating, knife coating, extrusion coating, spin coating, slide hopper coating and curtain coating.
- the PET support used for the experiments carried on the front side a latex subbing layer comprising co(vinylidene chloride - methyl acrylate - itaconic acid ; 88%/10%/2%) and colloidal silica KIESELSOL F, trade name of Bayer AG, and a gelatin subbing layer comprising gelatin and KIESELSOL F.
- a latex subbing layer comprising co(vinylidene chloride - methyl acrylate - itaconic acid ; 88%/10%/2%) and colloidal silica KIESELSOL F, trade name of Bayer AG, and a gelatin subbing layer comprising gelatin and KIESELSOL F.
- an analogous latex subbing layer and furtheron an electroconductive backing layer comprising a poly(3,4-ethylenedioxythiophene)/polystyrene sulphonate electroconductive complex comprising a poly(3,4-ethylenedioxythiophene)/polystyrene s
- the ink receiver layer had following composition :
- Table 2 shows that 0.25 g/m 2 of cationized silica is sufficient to improve the adhesion.
Abstract
Description
Among non-impact printing techniques ink jet printing has become a popular technique because of its simplicity, convenience and low cost. Especially in those instances where a limited edition of the printed matter is needed ink jet printing has become a technology of choice. A recent survey on progress and trends in ink jet printing technology is given by Hue P. Le in Journal of Imaging Science and Technology Vol. 42 (1), Jan/Febr 1998.
In ink jet printing tiny drops of ink fluid are projected directly onto an ink receptor surface without physical contact between the printing device and the receptor. The printing device stores the printing data electronically and controls a mechanism for ejecting the drops image-wise. Printing is accomplished by moving the print head across the paper or vice versa. Early patents on ink jet printers include US 3,739,393, US 3,805,273 and US 3,891,121.
The jetting of the ink droplets can be performed in several different ways. In a first type of process a continuous droplet stream is created by applying a pressure wave pattern. This process is known as continuous ink jet printing. In a first embodiment the droplet stream is divided into droplets that are electrostatically charged, deflected and recollected, and into droplets that remain uncharged, continue their way undeflected, and form the image. Alternatively, the charged deflected stream forms the image and the uncharged undeflected jet is recollected. In this variant of continuous ink jet printing several jets are deflected to a different degree and thus record the image (multideflection system). According to a second process the ink droplets can be created "on demand" ("DOD" or "drop on demand" method) whereby the printing device ejects the droplets only when they are used in imaging on a receiver thereby avoiding the complexity of drop charging, deflection hardware, and ink recollection. In drop-on-demand the ink droplet can be formed by means of a pressure wave created by a mechanical motion of a piezoelectric transducer (so-called "piezo method"), or by means of discrete thermal pushes (so-called "bubble jet" method, or "thermal jet" method).
Ink compositions for ink jet typically include following ingredients : dyes or pigments, water and/or organic solvents, humectants such as glycols, detergents, thickeners, polymeric binders, preservatives, etc.. It will be readily understood that the optimal composition of such an ink is dependent on the ink jetting method used and on the nature of the substrate to be printed. The ink compositions can be roughly divided in :
- water based ; the drying mechanism involves absorption, penetration and evaporation;
- oil based ; the drying involves absorption and penetration;
- solvent based ; the drying mechanism involves primarely evaporation;
- hot melt or phase change : the ink vehicle is liquid at the ejection temperature but solid at room temperature ; drying is replaced by solidification;
- UV-curable ; drying is replaced by polymerization.
- The ink-receiving layer should have a high ink absorbing capacity, so that the dots will not flow out and will not be expanded more than is necessary to obtain a high optical density.
- The ink-receiving layer should have a high ink absorbing speed (short ink drying time) so that the ink droplets will not feather if smeared immediately after applying.
- The ink dots that are applied to the ink-receiving layer should be substantially round in shape and smooth at their peripheries. The dot diameter must be constant and accurately controlled.
- The receiving layer must be readily wetted so that there is no "puddling", i.e. coalescence of adjacent ink dots, and an earlier absorbed ink drop should not show any "bleeding", i.e. overlap with neighbouring or later placed dots.
- Transparent ink-jet recording elements must have a low haze-value and be excellent in transmittance properties.
- After being printed the image must have a good resistance regarding water-fastness, light-fastness, and good endurance under severe conditions of temperature and humidity.
- The ink jet recording element may not show any curl or sticky behaviour if stacked before or after being printed.
- The ink jet recording element must be able to move smoothly through different types of printers.
The above-mentioned desired advantageous effect is realised by providing an ink jet recording material comprising a subbed polyester support, and an ink receiver layer containing a cationic compound, characterized in that between said support and said ink receiver layer there is an additional adhesion promoting layer present comprising a binder and a cationically modified silica.
In a most preferred embodiment the latex polymer is co(vinylidene chloride-methyl acrylate-itaconic acid ; 88 % / 10 % / 2 %). This copolymer is prepared by emulsion polymerization using 0.5 % MERSOLAT H (trade-mark of Bayer AG) as emulsifying agent. It is necessary to add extra surfactant, a so-called post-stabilizer, to the latex in order to assure a good stability on storage. An excellent storage stability is obtained when 4 % of ULTRAVON W, trade mark of Ciba-Geigy, or DOWFAX, trade mark of Dow, is used.
As a further preferred ingredient of the coating solution of the latex subbing layer colloidal silica may be added. A preferred compound is KIESELSOL 100F (trade-mark of Bayer AG), average particle size 25-30 nm. The ratio of the amount of latex to silica is preferably about 80/20.
The latex subbing layer may further contain surfactants and biocides.
As already stated above, there is preferably also a so-called gelatin subbing layer on top of the latex subbing layer. Typically, this gelatin subbing layer contains a mixture of gelatin and colloidal silica. A preferred compound is again KIESELSOL 300F (trade-mark of Bayer AG). A plasticizing compound can be used in order to avoid the formation of cracks in the dried layer due to the occurence of excessive shrinking of the layer during drying. Plasticizing agents are well-known in the art. Low-molecular weight compounds (e.g. acetamide, glycerin) as well as polymeric latices (e.g. polyethylacrylate, poly-n.-butylacrylate) can be used for this purpose. Furtheron the gelatin subbing layer may contain one or more surfactants. Useful surfactants include : ULTRAVON™ W, an aryl sulfonate from CIBA-GEIGY, DOWFAX from Dow CO., and ARKOPAL™ N060 (previously HOSTAPAL™ W), a nonylphenylpolyethylene-glycol from HOECHST.
The subbing layers may be present on just one side of the polyester support or they may also be present on the back side when the ink jet recording medium is provided with one or more backing layers, such as an anti-curl layer, or an electroconductive layer.
The binder can be chosen from a list of compounds well-known in the art including hydroxyethyl cellulose; hydroxypropyl cellulose; hydroxyethylmethyl cellulose; hydroxypropyl methyl cellulose; hydroxybutylmethyl cellulose; methyl cellulose; sodium carboxymethyl cellulose; sodium carboxymethylhydroxethyl cellulose; water soluble ethylhydroxyethyl cellulose; cellulose sulfate; polyvinyl alcohol; vinylalcohol copolymers; polyvinyl acetate; polyvinylacetal; polyvinyl pyrrolidone; polyacrylamide; acrylamide/acrylic acid copolymer; poly(styrene), styrene copolymers; acrylic or methacrylic polymers; styrene/acrylic copolymers; ethylene-vinylacetate copolymer; vinylmethyl ether/maleic acid copolymer; poly(2-acrylamido-2-methyl propane sulfonic acid); poly(diethylene triamine-co-adipic acid); polyvinyl pyridine; polyvinyl imidazole; polyimidazoline quaternized; polyethylene imine epichlorohydrin modified; polyethylene imine ethoxylated; poly(N,N-dimethyl-3,5-dimethylene piperidinium chloride; polyethylene oxide; polyurethane; melamine resins; gelatin; carrageenan; dextran; gum arabic; casein; pectin; albumin; starch; collagen derivatives; collodion and agar-agar.
A preferred binder for the practice of the present invention is a polyvinylalcohol (PVA), a vinylalcohol copolymer or modified polyvinyl alcohol. Most preferably, the polyvinyl alcohol is a cationic type polyvinyl alcohol, such as the cationic polyvinyl alcohol grades from Kuraray, such as POVAL C506, POVAL C118, and from Nippon Goshei. Furthermore cationic polyvinyl alcohol may be obtained by several routes:
Examples of such modifications are described in the following patents:
Cationically modified silica can be prepared by following methods, without meaning to be limitative :
The thickness of the adhesion promoting layer is preferably comprised between 1 and 6 g/m2.
The term "cationic inorganic pigment" as used in the present invention means a substance composed of fine particles having a positive charge on their surfaces and therefore having adsorbability of acid substances such as acid dyes. Specific examples thereof include fine particles composed of oxides of metals such as magnesium, calcium, aluminum, zirconium, zinc, chromium, iron, copper, tin, lead and manganese.
Those having a negative charge on their surfaces like silica may also be used if they are surface-treated to change the negative charge on the surface to a positive charge (as already explained above for the silica in the adhesion promoting layer).
Preferably the cationic substance is chosen from crystalline boehmite, or γ-AlO(OH), and cationized silica, and mixtures thereof. Boehmite is the most preferred cationic pigment since it allows a good transparency, meaning a low haze value, for the finished ink jet image. Useful types of boehmite include, in powder form, DISPERAL, DISPERAL HP14 and DISPERAL 40 from Sasol, MARTOXIN VPP2000-2 and GL-3 from Martinswerk GmbH.; liquid boehmite alumina systems, e.g. DISPAL 23N4-20, DISPAL 14N-25, DISPERAL AL25 from Sasol. Patents on alumina hydrate include EP 500021, EP 634286, US 5,624,428, EP 742108, US 6,238,047, EP 622244, EP 810101, etc.. Other useful cationic inorganic pigments include aluminum oxide (alumina), e.g. α-Al2O3 types, such as NORTON E700, available from Saint-Gobain Ceramics & Plastics, Inc, γ-Al2O3 types, such as ALUMINUM OXID C from Degussa; other aluminum oxide grades, such as BAIKALOX CR15 and CR30 from Baikowski Chemie; DURALOX grades and MEDIALOX grades from Baikowski Chemie, BAIKALOX CR80, CR140, CR125, B105CR from Baikowski Chemie; CAB-O-SPERSE PG003 tradeamrk from Cabot, CATALOX GRADES and CATAPAL GRADES from from Sasol, such as PLURALOX HP14/150; colloidal Al2O3 types, such as ALUMINASOL 100; ALUMINASOL 200, ALUMINASOL 220, ALUMINASOL 300, and ALUMINASOL 520 trademarks from Nissan Chemical Industries or NALCO 8676 trademark from ONDEO Nalco.
Other useful cationic inorganic pigments include aluminum trihydroxides such as Bayerite, or α-Al(OH)3, such as PLURAL BT, available from Sasol, and Gibbsite, or γ-Al(OH)3, such as MARTINAL grades from Martinswerk GmbH, MARTIFIN grades, such as MARTIFIN OL104, MARTIFIN OL 107 and MARTIFIN OL111 from Martinswerk GmbH , MICRAL grades, such as MICRAL 1440, MICRAL 1500; MICRAL 632; MICRAL 855; MICRAL 916; MICRAL 932; MICRAL 932CM; MICRAL 9400 from JM Huber company; HIGILITE grades, e.g. HIGILITE H42 or HIGILITE H43M from Showa Denka K.K., HYDRAL GRADES such as HYDRAL COAT 2, HYDRAL COAT 5 and HYDRAL COAT 7, HYDRAL 710 and HYDRAL PGA, from Alcoa Industrial Chemicals.
Another useful type of cationic pigment is zirconium oxide such as NALCO OOSS008 trademark of ONDEO Nalco, acetate stabilized ZrO2, ZR20/20, ZR50/20, ZR100/20 and ZRYS4 trademarks from Nyacol Nano Technologies.
Useful mixed oxides are SIRAL grades from Sasol, colloidal metaloxides from Nalco such as Nalco 1056, Nalco TX10496, Nalco TX11678.
Other useful cationic compounds include DADMAC copolymers such as copolymers with acrylamide, e.g NALCO 1470 trade mark of ONDEO Nalco or PAS-J-81, trademark of Nitto Boseki Co., such as copolymers of DADMAC with acrylates, such as Nalco 8190, trademark of ONDEO Nalco; copolymers of DADMAC with SO2, such as PAS-A-1 or PAS-92, trademarks of Nitto Boseki Co., copolymer of DADMAC with maleic acid, e.g. PAS-410, trademark of Nitto Boseki Co., copolymer of DADMAC with diallyl(3-chloro-2-hydroxypropyl)amine hydrochloride, eg. PAS-880, trademark of Nitto Boseki Co., dimethylamine-epichlorohydrine copolymers, e.g. Nalco 7135, trademark of ONDEO Nalco or POLYFIX 700, trade name of Showa High Polymer Co.; other POLYFIX grades which could be used are POLYFIX 601, POLYFIX 301, POLYFIX 301A, POLYFIX 250WS, and POLYFIX 3000 ; NEOFIX E-117, trade name of Nicca Chemical Co., a polyoxyalkylene polyamine dicyanodiamine, and REDIFLOC 4150, trade name of EKA Chemicals, a polyamine; MADAME (methacrylatedimethylaminoethyl = dimethylaminoethyl methacrylate) or MADQUAT (methacryloxyethyltrimethylammonium chloride) modified polymers, e.g. ROHAGIT KL280, ROHAGIT 210, ROHAGIT SL144, PLEX 4739L, PLEX 3073 from Röhm, DIAFLOC KP155 and other DIAFLOC products from Diafloc Co., and BMB 1305 and other BMB products from EKA chemicals; cationic epichlorohydrin adducts such as POLYCUP 171 and POLYCUP 172, trade names from Hercules Co.; from Cytec industries : CYPRO products, e.g. CYPRO 514/515/516, SUPERFLOC 507/521/567; cationic acrylic polymers, such as ALCOSTAT 567, trademark of CIBA, cationic cellulose derivatives such as CELQUAT L-200, H-100, SC-240C, SC-230M, trade names of Starch & Chemical Co., and QUATRISOFT LM200, UCARE polymers JR125, JR400, LR400, JR30M, LR30M and UCARE polymer LK; fixing agents from Chukyo Europe: PALSET JK-512, PALSET JK512L, PALSET JK-182, PALSET JK-220, WSC-173, WSC-173L, PALSET JK-320, PALSET JK-320L and PALSET JK-350; polyethyleneimine and copolymers, e.g. LUPASOL, trade name of BASF AG; triethanolamine-titanium-chelate, e.g. TYZOR, trade name of Du Pont Co.; copolymers of vinylpyrrolidone such as VIVIPRINT 111, trade name of ISP, a methacrylamido propyl dimethylamine copolymer; with dimethylaminoethylmethacrylate such as COPOLYMER 845 and COPOLYMER 937, trade names of ISP; with vinylimidazole, e.g. LUVIQUAT CARE, LUVITEC 73W, LUVITEC VP155 K18P, LUVITEC VP155 K72W, LUVIQUAT FC905, LUVIQUAT FC550, LUVIQUAT HM522, and SOKALAN HP56, all trade names of BASF AG; polyamidoamines, e.g. RETAMINOL and NADAVIN, trade marks of Bayer AG; phosphonium compounds such as disclosed in EP 609930 and other cationic polymers such as NEOFIX RD-5, trademark of Nicca Chemical Co.
Useful cationic surfactants include N-alkyl dimethyl ammonium chloride, palmityl trimethyl ammonium chloride, dodecyldimethylamine, tetradecyldimethylamine, ethoxylated alkyl guanidine-amine complex, oleamine hydroxypropyl bistrimonium chloride, oleyl imidazoline, stearyl imidazoline, cocamine acetate, palmitamine, dihydroxyethylcocamine, cocotrimonium chloride, alkyl polyglycolether ammonium sulphate, ethoxylated oleamine, lauryl pyridinium chloride, N-oleyl-1,3-diaminopropane, stearamidopropyl dimethylamine lactate, coconut fatty amide, oleyl hydroxyethyl imidazoline, isostearyl ethylimidonium ethosulphate, lauramidopropyl PEG-dimoniumchloride phosphate, palmityl trimethylammonium chloride, and cetyltrimethylammonium bromide.
Especially useful are the fluorocarbon surfactants as described in e.g. US-P 4,781,985, having a structure of : F(CF2)4-9CH2CH2SCH2CH2N+R3X- wherein R is a hydrogen or an alkyl group; and in US-P 5,084,340, having a structure of:
CF3(CF2)mCH2CH2O(CH2CH2O)nR wherein m = 2 to 10; n = 1 to 18; R is hydrogen or an alkyl group of 1 to 10 carbon atoms. These surfactants are commercially available from DuPont and 3M. The concentration of the surfactant component in the ink-receiving layer is typically in the range of 0.1 to 2 %, preferably in the range of 0.4 to 1.5 % and is most preferably 0.75 % by weight based on the total dry weight of the layer.
In the practice of this invention boric acid is a preferred crosslinker.
The ink-receiving layer, the adhesion promoting layer and the optional auxiliary layers comprise a plasticizer such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol, glycerol monomethylether, glycerol monochlorohydrin, ethylene carbonate, propylene carbonate, tetrachlorophthalic anhydride, tetrabromophthalicanhydride, urea phosphate, triphenylphosphate, glycerolmonostearate, propylene glycol monostearate, tetramethylene sulfone, n-methyl-2-pyrrolidone, n-vinyl-2-pyrrolidone.
The different layers may also comprise ingredients to improve the lightfastness of the printed image, such as antioxidants, UV-absorbers, peroxide scavengers, singlet oxygen quenchers such as hindered amine light stabilizers, (HALS compounds) etc..Stilbene compounds are a preferred type of UV-absorber.
The different layers can be coated onto the support by any conventional coating technique, such as dip coating, knife coating, extrusion coating, spin coating, slide hopper coating and curtain coating.
poly(3,4-ethylenedioxythiophene)/polystyrene sulphonate electroconductive complex.
- 25 g/m2 of boehmite pigment, DISPERAL HP 14/2, trade mark of Sasol Co.;
- 2 g/m2 of cationic polyvinyl alcohol, GOHSEFIMER K210, from Nippon Goshei Co.;
- 0.2 g/m2 of boric acid as crosslinker.
When seeking to improve the adhesion, following adhesion promoting layers were coated between the subbed PET and the described ink receiver layer :
Sample No. | adhesion dry evaluation |
1 | - |
2 | - |
3 | - |
4 | ++ |
g/m2 of silica/P3 | Evaluation adhesion dry |
0 | - |
0.25 | + |
0.5 | + |
1 | ++ |
2 | ++ |
Claims (14)
- An ink jet recording material comprising a subbed polyester support, and an ink receiver layer containing a cationic compound, characterized in that between said support and said ink receiver layer there is an additional adhesion promoting layer present comprising a binder and a cationically modified silica.
- An ink jet recording material according to claim 1 wherein said silica is cationically modified by subjecting it to a surface treatment with a cationic inorganic compound.
- An ink jet recording element according to claim 2 wherein said cationic inorganic compound, by which said silica is modified, is pseudo-boehmite.
- An ink jet recording element according to claim 1 wherein said silica is cationically modified by subjecting it to a surface treatment with an organic compound having both an amino group or quaternary group thereof or a quaternary phosphonium group, and a functional group having reactivity to a silanol group on the surface of silica.
- An ink jet recording element according to claim 1 wherein said silica is cationically modified by polymerization of a cationic or amino functional monomer in the presence of silica.
- An ink jet recording element according to any of claims 1 to 5 wherein the binder in said adhesion promoting layer is cationic polyvinyl alcohol.
- An ink jet recording element according to any of claims 1 to 6 wherein the cationically modified silica/binder ratio in said adhesion promoting layer is between 1:4 and 10:1.
- An ink jet recording element according to any of claims 1 to 7 wherein the thickness of said adhesion promoting layer is comprised between 1 and 6 g/m2.
- An ink jet recording element according to any of claims 1 to 8 wherein the cationic compound present in the ink receiver layer is a cationic inorganic pigment.
- An ink jet recording element according to claim 9 wherein said cationic pigment is chosen from the group consisting of aluminum oxides, aluminum hydroxides, alumina hydrates, aluminum silicates, and cationically modified silicas.
- An ink jet recording element according to claim 10 wherein said cationic pigment is boehmite.
- An ink jet recording element according to any of claims 1 to 8 wherein the cationic compound present in the ink receiver layer is a cationic polymer.
- An ink jet recording element according to claim 12 wherein said cationic polymer is cationic polyvinyl alcohol.
- An ink jet recording element according to claim 12 wherein said cationic polymer is poly(diallyldimethylammonium chloride).
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP20020100283 EP1346840B1 (en) | 2002-03-21 | 2002-03-21 | Improved recording element for ink jet printing |
DE2002605081 DE60205081T2 (en) | 2002-03-21 | 2002-03-21 | Improved recording material for inkjet printing |
US10/357,078 US6887536B2 (en) | 2002-03-21 | 2003-02-03 | Recording element for ink jet printing |
JP2003073659A JP2004025836A (en) | 2002-03-21 | 2003-03-18 | Improved recording element for ink jet printing |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP20020100283 EP1346840B1 (en) | 2002-03-21 | 2002-03-21 | Improved recording element for ink jet printing |
Publications (2)
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EP1346840A1 true EP1346840A1 (en) | 2003-09-24 |
EP1346840B1 EP1346840B1 (en) | 2005-07-20 |
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ID=27771930
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Application Number | Title | Priority Date | Filing Date |
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EP20020100283 Expired - Fee Related EP1346840B1 (en) | 2002-03-21 | 2002-03-21 | Improved recording element for ink jet printing |
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EP (1) | EP1346840B1 (en) |
JP (1) | JP2004025836A (en) |
DE (1) | DE60205081T2 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1826019A1 (en) | 2006-02-21 | 2007-08-29 | ILFORD Imaging Switzerland GmbH | Recording sheet for ink jet printing |
WO2012009196A1 (en) * | 2010-07-12 | 2012-01-19 | Carestream Health, Inc. | Transparent ink-jet recording film |
WO2012047822A1 (en) * | 2010-10-08 | 2012-04-12 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
WO2012047943A1 (en) * | 2010-10-08 | 2012-04-12 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
WO2012064678A1 (en) * | 2010-11-12 | 2012-05-18 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
WO2012068320A3 (en) * | 2010-11-19 | 2012-11-08 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
CN114269982A (en) * | 2019-07-22 | 2022-04-01 | 惠普发展公司,有限责任合伙企业 | Fabric coating composition |
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EP0732219A2 (en) * | 1995-03-15 | 1996-09-18 | Canon Kabushiki Kaisha | Printing medium, and ink-jet printing process and image-forming process using the same |
US5660928A (en) * | 1995-06-28 | 1997-08-26 | Kimberly-Clark Worldwide, Inc. | Substrate for ink jet printing having a dual layer ink-receptive coating |
EP1080935A2 (en) * | 1999-09-03 | 2001-03-07 | FERRANIA S.p.A. | Ink-jet print receiving sheet comprising a high-boiling organic solvent and an non-ionic surfactant |
-
2002
- 2002-03-21 EP EP20020100283 patent/EP1346840B1/en not_active Expired - Fee Related
- 2002-03-21 DE DE2002605081 patent/DE60205081T2/en not_active Expired - Fee Related
-
2003
- 2003-03-18 JP JP2003073659A patent/JP2004025836A/en active Pending
Patent Citations (3)
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EP0732219A2 (en) * | 1995-03-15 | 1996-09-18 | Canon Kabushiki Kaisha | Printing medium, and ink-jet printing process and image-forming process using the same |
US5660928A (en) * | 1995-06-28 | 1997-08-26 | Kimberly-Clark Worldwide, Inc. | Substrate for ink jet printing having a dual layer ink-receptive coating |
EP1080935A2 (en) * | 1999-09-03 | 2001-03-07 | FERRANIA S.p.A. | Ink-jet print receiving sheet comprising a high-boiling organic solvent and an non-ionic surfactant |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2007200670B2 (en) * | 2006-02-21 | 2009-02-12 | Rex-Tone Industries Ltd | Recording sheet for ink printing |
US8053043B2 (en) | 2006-02-21 | 2011-11-08 | Ilford Imaging Switzerland Gmbh | Recording sheet for ink jet printing |
EP1826019A1 (en) | 2006-02-21 | 2007-08-29 | ILFORD Imaging Switzerland GmbH | Recording sheet for ink jet printing |
US8470415B2 (en) | 2010-07-12 | 2013-06-25 | Carestream Health, Inc. | Transparent ink-jet recording film |
WO2012009196A1 (en) * | 2010-07-12 | 2012-01-19 | Carestream Health, Inc. | Transparent ink-jet recording film |
CN102985264A (en) * | 2010-07-12 | 2013-03-20 | 卡尔斯特里姆保健公司 | Transparent ink-jet recording film |
WO2012047822A1 (en) * | 2010-10-08 | 2012-04-12 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
WO2012047943A1 (en) * | 2010-10-08 | 2012-04-12 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
US8481132B2 (en) | 2010-10-08 | 2013-07-09 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
US8481131B2 (en) | 2010-10-08 | 2013-07-09 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
WO2012064678A1 (en) * | 2010-11-12 | 2012-05-18 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
US8470416B2 (en) | 2010-11-12 | 2013-06-25 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
WO2012068320A3 (en) * | 2010-11-19 | 2012-11-08 | Carestream Health, Inc. | Transparent ink-jet recording films, compositions, and methods |
CN114269982A (en) * | 2019-07-22 | 2022-04-01 | 惠普发展公司,有限责任合伙企业 | Fabric coating composition |
US20220136170A1 (en) * | 2019-07-22 | 2022-05-05 | Hewlett-Packard Development Company, L.P. | Fabric coating compositions |
Also Published As
Publication number | Publication date |
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DE60205081D1 (en) | 2005-08-25 |
JP2004025836A (en) | 2004-01-29 |
EP1346840B1 (en) | 2005-07-20 |
DE60205081T2 (en) | 2006-05-24 |
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