EP1008457A1 - Ink-jet recording sheet with image-protecting layer - Google Patents
Ink-jet recording sheet with image-protecting layer Download PDFInfo
- Publication number
- EP1008457A1 EP1008457A1 EP99309809A EP99309809A EP1008457A1 EP 1008457 A1 EP1008457 A1 EP 1008457A1 EP 99309809 A EP99309809 A EP 99309809A EP 99309809 A EP99309809 A EP 99309809A EP 1008457 A1 EP1008457 A1 EP 1008457A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- ink
- jet recording
- recording sheet
- ink jet
- colloidal silica
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/02—Mixtures of base-materials and thickeners
-
- 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
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/061—Carbides; Hydrides; Nitrides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/061—Carbides; Hydrides; Nitrides
- C10M2201/0613—Carbides; Hydrides; Nitrides used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/06—Metal compounds
- C10M2201/062—Oxides; Hydroxides; Carbonates or bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/087—Boron oxides, acids or salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
- C10M2229/04—Siloxanes with specific structure
- C10M2229/0405—Siloxanes with specific structure used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/06—Groups 3 or 13
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/04—Molecular weight; Molecular weight distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/055—Particles related characteristics
- C10N2020/06—Particles of special shape or size
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
Definitions
- the present invention relates to a recording material that can be print on with ink containing water-soluble dye.
- the present invention relates to an ink jet recording sheet which provides a superior combination of ink absorbency, ink coloration, resistance of the recorded image to light, resistance of the recorded image to water and surface gloss.
- Ink jet recording is a method by which fine ink drops are jetted out using any kind of jetting method to form an image on a recording material. Since this method enables a recording apparatus to be operated at a high speed and the apparatus is generally inexpensive, the use of ink jet recording systems has been spreading rapidly. Moreover, the use of multicolor ink jet recording methods enables the formation of color images comparable to silver-salt films with high resolution and high quality. Digital images, for example those obtained by a digital camera, are increasingly printed with an ink jet printer. The recorded materials are more often being displayed or stored for considerably long period because of the high image quality. Therefore, it is desirable that the ink jet recording materials have good preservation characteristics, especially good light resistance, as well as high image quality.
- a process to add UV absorber such as benzophenones and benzotriazoles (Japanese Tokkai Sho 57-87988 and Japanese Tokkai Sho 63-222895, "Tokkai” means an "unexamined published patent application")
- a process to add antioxidant such as hindered amines (Japanese Tokkai Sho 61-146591)
- a process to add zinc oxide and cationic resins concurrently Japanese Patent Tokkai Hei 7-32725
- these additives are difficult to disperse evenly in the materials, these attempts did not provide a satisfactory improvement.
- the objective of this invention is to provide a recording material that can be recorded by ink with water-soluble dye, particularly to provide an ink jet recording sheet, which is superior in ink absorbency, ink coloration, light resistance, water resistance and surface gloss.
- One subject of the present invention is an ink jet recording sheet having on an ink-receiving support an image preserving layer comprising anionic colloidal silica and zinc oxide particulates with an average particle size of about 15 to 380 nm and having a 75 degree specular glossiness of at least about 25% at the surface.
- Another subject of the present invention is an ink jet recording sheet having on an ink-receiving support, in succession, an image preserving layer comprising an anionic colloidal silica and zinc oxide particulates with an average particle size of about 15 to 380 nm and a fixing layer comprising a cationic colloidal silica and a cationic polymer electrolyte.
- the support used in the present invention may be any of known supports capable of absorbing an ink containing a water-soluble dye, is preferably a support having an ink-receiving layer comprising a pigment and a binder on a base paper.
- the image preserving layer formed on the ink-receiving layer mentioned before comprises zinc oxide particulates with an average particle size of about 15 to 380 nm, preferably about 20 to 300 nm, which absorbs UV light, and anionic colloidal silica, which is compatible with said particulates and can provide a glossy surface property in order to obtain compatibility between the light resistance and the high quality of recorded image.
- Colloidal silica of this invention is the stabilized colloidal solution of silica to make its utilization easy, as described in Kagaku Binran (Chemical Reference Guide) published by Maruzen, Oct.15, 1986.
- the average particle size of zinc oxide particulates is less than 15 nm, the image-preserving layer is very closely packed and therefore has a poor ink absorbency, which not only makes it difficult to obtain images of high quality but also causes problems in cost and operability.
- the average particle size is larger than 380 nm, the transparency of the image-preserving layer becomes worse due to light scattering thereby reducing the recorded density.
- the average particle size of zinc oxide particulates is measured by using a scanning electron microscope.
- the colloidal silica which is necessary for glossy surface, needs to be anionic colloidal silica. Since the isoelectric point of anionic silica is usually around pH 2, the silica is negatively charged in the almost all range above pH 2, which is suitable for this invention. On the contrary, the colloidal silica that is reversely charged by having cations, for example, obtained by hydrolysis of metal salts, absorbed on the surface, has problems in operability due to poor compatibility with the zinc oxide particulates.
- the configuration of the anionic colloidal silica is preferably non-spherical shape, in which several particulates interlink as in a shape of beads or a ring.
- the coverage of the image-preserving layer be about 1 to 6 g/m 2 , preferably about 1.5 to 5 g/m 2 , on a dry solids basis.
- the coverage of the image-preserving layer is less than 1 g/m 2 , sufficient light resistance and surface gloss cannot be attained.
- the coverage is larger than 6 g/m 2 , the ink absorbency of the layer becomes poor and high quality images cannot be obtained.
- the content of the zinc oxide particulates in the image-preserving layer is desired to be about 2 to 25 parts by weight, preferably about 3 to 20 parts by weight based on the 100 parts by weight of the anionic colloidal silica.
- the content of the zinc oxide particulates is less than 2 parts by weight, sufficient light resistance cannot be attained.
- the content is larger than 25 parts by weight, the recorded density and the surface gloss become poor and high quality images cannot be obtained.
- the 75 degree specular glossiness of the image preserving layer needs to be at least about 25%, preferably at least about 30% at the surface, measured in accordance with JIS(Japanese Industrial Standards) P8142, in order to obtain sufficient reproducibility of image similar to a silver salt film.
- the base paper used for an ink-receiving support of the present invention can be made from various types of paper pulps.
- the pulp for paper include chemical pulp such as LBKP (hardwood bleached pulp) and NBKP(softwood bleached pulp), mechanical pulp such as GP(groundwood pulp) and TMP(thermo mechanical pulp), waste paper pulp and mixture thereof, but the pulp is not limited to those.
- additives such as fillers, sizing agents and paper reinforcing agents
- the additives are not limited to those and can be selected from known fillers and known additives as required.
- Starch or other surface-sizing agents can be size pressed or coated.
- antifoaming agents, pH regulators, pigments and coloring dyes for adjusting color, fluorescent pigments for improving visual whiteness and the like can be added as well.
- the coverage of the ink-receiving layer formed on the base paper be about 5-to-25 g/m 2 , preferably about 7 to 20 g/m 2 , on a dry solids basis.
- the coverage of the ink-receiving layer is less than 5 g/m 2 , the ink absorbency of the layer becomes poor which will cause bleeding of ink.
- the coverage is larger than 25 g/m 2 , the amount of absorbed ink becomes excessive thereby reducing the recording density and this will also degrade the quality of image.
- the ink-receiving layer comprises pigment and binder.
- white pigment such as light and heavy calcium carbonate, kaolin, clay, talc, titanium dioxide, zinc oxide, satin white, magnesium silicate, calcium silicate, aluminum silicate, aluminum hydroxide, alumina, quasi-boehmite, synthetic amorphous silica, magnesium carbonate, zeolite.
- synthetic amorphous silica is more preferred as a pigment for the ink-receiving layer because it provides a superior combination of ink coloration, ink absorbency and cost.
- the binder resin used for the ink-receiving layer can be selected from any resins that can bond strongly to the base paper and can form films when coated and dried. It is desirable to use starches such as oxidized starch, esterified starch, enzyme-modified starch and cationic starch; polyvinyl alcohol with various degrees of saponification and derivatives thereof; casein, soy proteins; cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose; styrene-acrylic resin; isobutylene-maleic anhydride resin; acrylic emulsion; vinyl acetate emulsion; vinylidene chloride emulsion; polyester emulsion; styrene-butadiene latex; acrylonitrile-butadiene latex and the like.
- starches such as oxidized starch, esterified starch, enzyme-modified starch and cationic starch; polyvinyl alcohol with various degrees of saponification and derivatives thereof; casein, soy
- a dye fixing agent that is cationic resin can be added to ink-receiving layer in order to impart water resistance property of the image.
- examples of such agents include dicyandiamide-alkylamine polycondensed material, dicyanodiamide-formaldehyde polycondensed material, polyethylene-imine derivatives, alkylamine(-ammonium)-epichlorohydrin polycondensed material, polymethacrylic acid quaternary ammonium salt derivatives, polydiallyl-dimethylammonium chloride, and other commercially available dye fixing agent. Mixtures of these can also be used without the loss of the advantage of the present invention.
- the fixing layer of the present invention comprises cationic colloidal silica and cationic polymer electrolyte and provide a good combination of light resistance, water resistance and surface gloss. Further, it is preferred that the configuration of the cationic colloidal silica is non-spherical shape, in which several particulates interlink as in a shape of beads or a ring.
- the fixing layer contains anionic colloidal silica or synthetic amorphous silica, problems are seen in operability due to the poor compatibility of the silica with the cationic polymer electrolyte.
- the coverage of the fixing layer be about 1 to 6 g/m 2 , preferably about 1.5 to 5 g/m 2 , on a dry solids basis.
- the coverage of the fixing layer is less than 1 g/m 2 , sufficient water resistance and surface gloss cannot be attained.
- the coverage is larger than 6 g/m 2 , the ink absorbency of the layer becomes poor and high quality images cannot be obtained.
- the content of the cationic polymer electrolyte in the fixing layer is desired to be about 2 to 25 parts by weight, preferably about 3 to 20 parts by weight based on the 100 parts by weight of the cationic colloidal silica.
- the content of the cationic polymer electrolyte is less than 2 parts by weight, the water resistance is sometimes insufficient.
- the content is larger than 25 parts by weight, the ink absorbency and light resistance sometimes degrades.
- the cationic polymer electrolyte of the present invention can be selected from dicyandiamide-alkylamine polycondensed material, dicyanodiamide-formaldehyde polycondensed material, polyethylene-imine derivatives, alkylamine (-ammonium)-epichlorohydrin polycondensed material, polymethacrylic acid quaternary ammonium salt derivatives, polydiallyl-dimethyl-ammonium chloride, other commercially available cationic polymer electrolyte and mixture thereof.
- the fixing layer comprising cationic colloidal silica and cationic polymer electrolyte as a top layer, it becomes possible to obtain compatibility between water resistance and quality of recorded images.
- the 75 degree specular glossiness is desirably at least about 30%, preferably at least about 35% at the surface of the fixing layer, measured in accordance with JIS(Japanese Industrial Standards) P8142.
- the ink-receiving layer may comprise hindered amine compounds of amino ether type having alkoxyl groups in order to impart light resistance.
- R 1 and R 2 of the formula (1) is preferably 6 to 10, and the alkyl group or carbonyl group of R 3 to R 6 is preferably a lower alkyl group with 1 to 4 carbons, more preferably methyl group.
- the hindered amine compound of the amino ether type having alkoxyl groups is preferably bis-(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)sebacate wherein R 1 is C 8 H 17 , R 2 is C 3 H 15 and R 3 to R 6 are methyl groups in the formula (1) (Tinuvin 123, manufactured by Ciba Specialty Chemicals, Inc.).
- Hindered amine compounds generally generate nitroxy radicals by reacting with hydroperoxide or triplet oxygen in the air, which further react to torn aminoethers by capturing polymer radicals generated by photodegradation of dyes contained in ink. Then the generated aminoethers react with peroxy radicals generated by a reaction between polymer radicals and oxygen in the air to regenerate nitroxy radicals. The aminoether also releases olefins, simultaneously generating hydroxylamine that react with the peroxy radicals to regenerate nitroxy radicals. This process is repeated to capture the radicals and hamper a chain reaction, thereby preventing the image from photodegrading.
- the hindered amine compounds of the present invention have an amino ether as part of their chemical structure, it is considered that peroxy radicals are immediately captured when generated. Thus the hindered amine compound is very effective in preventing photodegradation of image. While in the case of conventional hindered amine compounds unsubstituted or substituted by alkyl or acetyl groups, it is considered that there is a large energy barrier to producing aminoethers, which inhibit the effective prevention of photodegradation.
- the content of the hindered amine compounds in the ink-receiving layer is desired to be about 0.5 to 15 wt%, preferably about 2 to 8 wt%.
- the content of the compounds is less than 0.5 wt%, the addition of the compounds would not be effective, and when the content is larger than 15 wt%, the applicability in manufacturing becomes worse.
- the benzotriazole compounds of the present invention preferably include, for example, 2-(2-hydroxy-3,5-di-t-amylphenyl-2H-benzotriazole, iso-octyl-3,3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenylpropionate, 2-[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and the like.
- the content of the benzotriazole compounds in the ink-receiving layer is desired to be about 0.5 to 12 wt%, preferably about 2.5 to 8 wt%.
- the content of the benzotriazole compounds is less than 0.5 wt%, the addition of the compounds would not be effective, and when the content is larger than 12 wt%, it causes significant coloring in the applied layer.
- the coating compositions for the ink-receiving layers, image-preserving layers and fixing layers may contain various additives, such as an antifoaming agent, a surface-sizing agent, a pH-adjusting agent, other CV absorber, an antioxidant, a dye or coloring pigment for adjusting color phase, a fluorescent dye and mixture thereof without the loss of the effect of the present invention.
- various additives such as an antifoaming agent, a surface-sizing agent, a pH-adjusting agent, other CV absorber, an antioxidant, a dye or coloring pigment for adjusting color phase, a fluorescent dye and mixture thereof without the loss of the effect of the present invention.
- the method of coating the ink-receiving layers, image-preserving layers and fixing layers on base paper includes conventional coaters of various kinds, e.g., a blade coater, an air knife coater, a roll coater, a curtain coater, a bar coater, a gate roll coater and a gravure coater and the like. Further various calendering treatments such as a machine calender, a soft calender, and a super calender can be used solely or in combination for finishing the surface.
- the ink jet recording sheet of the present invention has on an ink-receiving support, in succession, an image preserving layer comprising zinc oxide particulates with a certain particular size to absorb UV light and anionic colloidal silica that is compatible with the particulates and a fixing layer comprising cationic colloidal silica to impart water resistance and surface gloss. Therefore, said ink jet recording sheet not only has superior ink-absorbency and ink coloration, but also has superior light resistance, water resistance and surface gloss, therefore the ink jet recording paper is of extremely high quality,
- the average primary particle size of colloidal silica is measured by BET method, the average secondary particle length of non-spherical cationic colloidal silica is measured by laser scattering method.
- the ink jet recording sheets in the following examples and comparative examples are evaluated by the following method. Unless otherwise noted, all "parts" are by weight in the following examples and comparative examples. The weight in the coating solution is based on dry basis, excluding water.
- the 75 degree specular glossiness is determined by using a qlossimeter, GM-26D (trade name, a product of Murakami Shikisai Kenkyujo), in accordance to JIS P8142.
- the predetermined solid pattern or image pattern is printed on the test sheet by an ink jet printer, Model PM750C (trade name, a product of Seiko Epson Corp.) and the various properties of the recorded sheet is evaluated by the following method:
- the reflection densities of the black solid areas are measured with a Macbeth densitometer, RD 915 (trade name, a product of Macbeth Limited).
- the recorded density of magenta ink is measured after being tested for 25 hours by Xenon Weather Meter SC700-WN (trade name, a product of Suga Test Machinery Limited), and evaluated the remaining recorded density compared with the density before the test according to the ranks mentioned below;
- the ink absorbency is evaluated by an extent of bleeding at the boundary between image areas of solid magenta and solid green (mixture of cyan and yellow) according to the ranks mentioned below;
- the recorded image is dried in the air for 1 day, then is immersed in a tap water at 20 degree C for 5 minutes and dried in the air again. Then the extent of change of recorded images is evaluated according to the ranks mentioned below;
- a slurry consisting of 93 parts of LBKP (hardwood bleached pulp) with a freeness of 440 ml, 7 parts of NBKP(softwood bleached pulp) with a freeness of 520 ml, 7 parts of talc, 1.5 parts of sulfuric acid band (aluminum sulfate), 0.4 parts of sizing agent and 0.02 parts of yield improver is prepared.
- Paper is manufactured from the slurry by a twin wire machine and pre-dried by a cylinder drier. Then the coating solution 1 below is applied to the paper by a two roll sizing press to have a total solid coverage cf both sides of 4 g/m 2 and is subjected to a machine calender treatment.
- a base paper with a dry coverage of 157 g/m 2 and a smoothness of 35 seconds is obtained.
- the coating solution 2 below is coated on one surface of the obtained base paper by means of a Mayer bar so as to have a dry coverage of 13 g/m 2 .
- the paper is then subjected to a calendering machine with a linear pressure of 80 Kg/cm to produce an ink-receiving layer.
- an image-preserving layer is formed by coating the coating solution 3 below on the ink-receiving layer by means of a Mayer bar so as to have a dry coverage of 2 g/m 2 and then calendered at a linear pressure of 100 Kg/cm.
- An ink jet recording sheet with a dry coverage of 172 g/m 2 is obtained.
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that Fine Zinc Oxide (registered trade mark of Honjo Chemical) with an average particle size of 200 nm is used for zinc oxide particulates in the coating solution 3.
- Fine Zinc Oxide registered trade mark of Honjo Chemical
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that the content of the zinc oxide particulates is 15 parts in the coating solution 3.
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that the dry coverage of the coating solution 3 is 4.5 g/m 2 .
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that the dry coverage of the coating solution 3 is 10 g/m 2 .
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that the coating solution 2 is not applied.
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that Hydrozincite No.1 (registered trade mark of Sakai Chemical) with an average particle size of 520 nm is used for zinc oxide particulates in the coating solution 3.
- Hydrozincite No.1 registered trade mark of Sakai Chemical
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that FINEX-75 (a product of Sakai Chemical) with an average particle size of 10 nm is used for zinc oxide particulates in the coating solution 3.
- FINEX-75 a product of Sakai Chemical
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that the coating solution 3 is not applied.
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that the zinc oxide particulates is not formulated in the coating solution 3.
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that the colloidal silica is not formulated in the coating solution 3.
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that Synthetic amorphous silica, Fineseal X-37B(Tokuyama), is used for the colloidal silica in the coating solution 3.
- Example 1 The evaluation results for Examples 1 to 6 and Comparative examples 1 to 6 are summarized in Table 1 below.
- the ink jet recording sheets ranked by o ⁇ or ⁇ can be used without causing problems.
- Example 1 35.8 2.10 o ⁇ o ⁇
- Example 2 30.8 2.01 o ⁇ o ⁇
- Example 3 30.4 1.95 o ⁇ o ⁇
- Example 4 41.7 1.99 o ⁇ o ⁇
- Example 5 43.6 2.06 o ⁇ ⁇
- Example 6 30.5 1.98 o ⁇ ⁇ Comparative Example 1 19.4 1.62 ⁇ ⁇ Comparative Example 2 44.1 1.90 o ⁇ ⁇ Comparative Example 3 7.8 1.84 ⁇ o ⁇ Comparative Example 4 45.8 2.08 ⁇ ⁇ Comparative Example 5 8.3 1.60 ⁇ ⁇ Comparative Example 6 8.3 1.79 ⁇ o ⁇
- a slurry consisted of 93 parts of LSKP with a freeness of 440 ml (csf), 7 parts of NBKP with a freeness of 520 ml (csf), 7 parts of talc, 1.5 parts of sulfuric acid band, 0.4 parts of sizing agent and 0.02 parts of yield improver is prepared.
- a paper is manufactured from the slurry by a twin wire machine and pre-dried by a cylinder drier.
- oxidized starch is applied to the both sides of the paper by a two roll sizing press to have a total solid coverage of both sides of 4 g/m 2 , followed by a machine calender treatment.
- a base paper with a dry coverage of 160 g/m 2 and a smoothness of 35 seconds is obtained.
- the coating solution 4 below is coated on one surface of the obtained base paper by means of a Mayer bar so as to have a dry coverage of 16 g/m 2 .
- the paper is then subjected to a calendering machine with a linear pressure of 80 Kg/cm to form an ink-receiving layer.
- coating solutions 5 and 6 below are coated successively on the ink-receiving layer by means of a Mayer bar so as to have a dry coverage of 2 g/m 2 each to form a image-preserving layer and a fixing layer, and the paper is subjected to a calendering machine with a linear pressure of 100 Kg/cm.
- An ink jet-recording sheet with a dry coverage of 180 g/m 2 is obtained.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that the average particle size of the zinc oxide particulate is 200 nm in coating solution 5.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that the content of the zinc oxide particulates is 15 parts in coating solution 5.
- the ink jet recording sheet with a dry coverage of 182.5 g/m 2 is obtained in the same manner as in Example 7, except that the dry coverage of coating solution 5 is 4.5 g/m 2 .
- the ink jet recording sheet with a dry coverage of 188 g/m 2 is obtained in the same manner as in Example 7, except that the dry coverage of coating solution 5 is 10 g/m 2 .
- the ink jet recording sheet with a dry coverage of 164 g/m 2 is obtained in the same manner as in Example 7, except that coating solution 4 is not applied.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that spherical cationic colloidal silica Snowtex ⁇ with an average primary particle size of 10 to 20 nm (Nissan Chemical) is used for the non-spherical (beads type) cationic colloidal silica in coating solution 6.
- spherical cationic colloidal silica Snowtex ⁇ with an average primary particle size of 10 to 20 nm is used for the non-spherical (beads type) cationic colloidal silica in coating solution 6.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that zinc oxide particulates with an average particle size of 520 nm is used for zinc oxide particulates in coating solution 5.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that zinc oxide particulates with an average particle size of 10 nm is used for the zinc oxide particulates in coating solution 6.
- the ink jet recording sheet with a dry coverage of 178 g/m 2 is obtained in the same manner as in Example 7, except that coating solution 5 is not applied.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that the spherical anionic colloidal silica is not formulated in coating solution 5.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that the zinc oxide particulate is not formulated in coating solution 5.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that the non-spherical cationic colloidal silica is not formulated in coating solution 6.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that the cationic polymer electrolyte is not formulated in coating solution 6.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that synthetic amorphous silica with an average secondary particle size of 4 ⁇ m, Fineseal X-37B (Tokuyama), is used for the spherical anionic colloidal silica in coating solution 5.
- Example 7 The evaluation results for Examples 7 to 13 and Comparative examples 7 to 14 are summarized in Table 2 below.
- the ink jet recording sheets ranked by o ⁇ or ⁇ can be used without causing problems.
- Example 7 40.6 2.21 o ⁇ o ⁇ o ⁇
- Example 8 39.5 2.14 o ⁇ o ⁇ o ⁇ Example 9 36.0 2.01 o ⁇ o ⁇ o ⁇ Exmmple 10 43.9 2.20 o ⁇ o ⁇ o ⁇ Example 11 47.8 2.15 ⁇ ⁇ o ⁇ Example 12 37.2 1.97 o ⁇ ⁇ ⁇
- Example 13 46.1 2.06 ⁇ ⁇ o ⁇ Comparative Exemple 7 23.9 1.81 ⁇ ⁇ ⁇ Comparative Example 8 44.4 2.15 o ⁇ ⁇ o ⁇ Comparative Example 9 29.5 2.04 ⁇ o ⁇ o ⁇ Comparative
- the ink jet recording sheet of the present invention provides a superior combination of ink absorbency, ink coloration, light resistance, water resistance and surface gloss even when printed with an ink containing a water-soluble dye.
- the ink jet recording sheet is obtained in the same manner as in Example 1, except that coating solution 7 below is used instead of coating solution 2.
- the ink jet recording sheet is obtained in the same manner as in Example 14, except that the content of the hindered amine compound (Tinuvin 123) is 10 parts in the coating solution 7.
- the ink jet recording sheet is obtained in the same manner as in Example 14, except that the benzotriazole compound is omitted from coating solution 7.
- the ink jet recording sheet is obtained in the same manner as in Example 7, except that coating solution 7 is used for the coating solution 4.
- the ink jet recording sheet is obtained in the same manner as in Example 17, except that the content of the hindered amine compound (Tinuvin 123) is 10 parts in coating solution 7.
- the ink jet recording sheet is obtained in the same manner as in Example 17, except that the benzotriazole compound is omitted from coating solution 7.
- An ink jet recording sheet is obtained in the same manner as in Example 17, except that Tinuvin 144 (Ciba Specialty Chemicals, Inc.) of the formula (2) below is used instead of the hindered amine compound (Tinuvin 123) in coating solution 7. ,where R 2 is
- the ink jet recording sheet is obtained in the same manner as in Example 17, except that Tinuvin 292 (Ciba Specialty Chemicals, Inc.) of the formula (3) below is used for the hindered amine compound (Tinuvin 123) in coating solution 7. ,where R 2 is C 8 H 16 .
- Examples 14 to 19 that the light resistance is further improved by formulating Tinuvin 123, hindered amine compound of amino ether type having alkoxyl groups of formula (1), in the ink-receiving layer.
- the light resistance is further improved by formulating benzotriazole compound in the ink-receiving layer.
- comparative examples 15 and 16 formulating hindered amine compound of formula (2) or (3), there is not such improvement in light resistance as in examples 14 to 19.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
Abstract
Description
- The present invention relates to a recording material that can be print on with ink containing water-soluble dye. In particular, the present invention relates to an ink jet recording sheet which provides a superior combination of ink absorbency, ink coloration, resistance of the recorded image to light, resistance of the recorded image to water and surface gloss.
- Ink jet recording is a method by which fine ink drops are jetted out using any kind of jetting method to form an image on a recording material. Since this method enables a recording apparatus to be operated at a high speed and the apparatus is generally inexpensive, the use of ink jet recording systems has been spreading rapidly. Moreover, the use of multicolor ink jet recording methods enables the formation of color images comparable to silver-salt films with high resolution and high quality. Digital images, for example those obtained by a digital camera, are increasingly printed with an ink jet printer. The recorded materials are more often being displayed or stored for considerably long period because of the high image quality. Therefore, it is desirable that the ink jet recording materials have good preservation characteristics, especially good light resistance, as well as high image quality.
- Ordinary ink jet recording sheets, printed by an ink jet printer, are discolored by the UV light in the sunlight or fluorescent lamps. Therefore some countermeasures for this problem have been attempted to improve the long-term preservation properties of the sheet. Although some attempts utilized a pigment ink system with a pigment resistant to discoloration, in most instances it is attempted to improve the light resistance by using a dye ink system because dye ink system provide sharper images.
- As examples of means to improve the light resistance, for example, a process to add UV absorber such as benzophenones and benzotriazoles (Japanese Tokkai Sho 57-87988 and Japanese Tokkai Sho 63-222895, "Tokkai" means an "unexamined published patent application"), a process to add antioxidant such as hindered amines (Japanese Tokkai Sho 61-146591), a process to add zinc oxide and cationic resins concurrently (Japanese Tokkai Hei 7-32725) and the like have been disclosed. However, since these additives are difficult to disperse evenly in the materials, these attempts did not provide a satisfactory improvement.
- As a method to attain the high image quality by increasing the gloss of the recording sheet, for example, a process to use cationic colloidal silica (Japanese Tokkai Hei 6-92011) has been proposed, but this process can not provide a sufficient balance between the image quality and the image preservation.
- Moreover, a process to improve the water resistance of the recording layer by setting up a coating layer comprising a colloidal silica that couples like beads and a water-soluble polymer (Japanese Tokkai Hei 5-51469) have been proposed, but this process can not achieve sufficient water resistance and its light resistance is still insufficient.
- The objective of this invention is to provide a recording material that can be recorded by ink with water-soluble dye, particularly to provide an ink jet recording sheet, which is superior in ink absorbency, ink coloration, light resistance, water resistance and surface gloss.
- One subject of the present invention is an ink jet recording sheet having on an ink-receiving support an image preserving layer comprising anionic colloidal silica and zinc oxide particulates with an average particle size of about 15 to 380 nm and having a 75 degree specular glossiness of at least about 25% at the surface. Another subject of the present invention is an ink jet recording sheet having on an ink-receiving support, in succession, an image preserving layer comprising an anionic colloidal silica and zinc oxide particulates with an average particle size of about 15 to 380 nm and a fixing layer comprising a cationic colloidal silica and a cationic polymer electrolyte.
- The support used in the present invention may be any of known supports capable of absorbing an ink containing a water-soluble dye, is preferably a support having an ink-receiving layer comprising a pigment and a binder on a base paper.
- The image preserving layer formed on the ink-receiving layer mentioned before comprises zinc oxide particulates with an average particle size of about 15 to 380 nm, preferably about 20 to 300 nm, which absorbs UV light, and anionic colloidal silica, which is compatible with said particulates and can provide a glossy surface property in order to obtain compatibility between the light resistance and the high quality of recorded image.
- Colloidal silica of this invention is the stabilized colloidal solution of silica to make its utilization easy, as described in Kagaku Binran (Chemical Reference Guide) published by Maruzen, Oct.15, 1986.
- When the average particle size of zinc oxide particulates is less than 15 nm, the image-preserving layer is very closely packed and therefore has a poor ink absorbency, which not only makes it difficult to obtain images of high quality but also causes problems in cost and operability. On the other hand, when the average particle size is larger than 380 nm, the transparency of the image-preserving layer becomes worse due to light scattering thereby reducing the recorded density. The average particle size of zinc oxide particulates is measured by using a scanning electron microscope.
- Since the surfaces of the zinc oxide particulates, which are necessary to impart light resistance, are negatively charged, the colloidal silica, which is necessary for glossy surface, needs to be anionic colloidal silica. Since the isoelectric point of anionic silica is usually around pH 2, the silica is negatively charged in the almost all range above pH 2, which is suitable for this invention. On the contrary, the colloidal silica that is reversely charged by having cations, for example, obtained by hydrolysis of metal salts, absorbed on the surface, has problems in operability due to poor compatibility with the zinc oxide particulates.
- The configuration of the anionic colloidal silica is preferably non-spherical shape, in which several particulates interlink as in a shape of beads or a ring.
- It is desirable that the coverage of the image-preserving layer be about 1 to 6 g/m2, preferably about 1.5 to 5 g/m2, on a dry solids basis. When the coverage of the image-preserving layer is less than 1 g/m2, sufficient light resistance and surface gloss cannot be attained. On the other hand, when the coverage is larger than 6 g/m2, the ink absorbency of the layer becomes poor and high quality images cannot be obtained.
- The content of the zinc oxide particulates in the image-preserving layer is desired to be about 2 to 25 parts by weight, preferably about 3 to 20 parts by weight based on the 100 parts by weight of the anionic colloidal silica. When the content of the zinc oxide particulates is less than 2 parts by weight, sufficient light resistance cannot be attained. On the other hand, when the content is larger than 25 parts by weight, the recorded density and the surface gloss become poor and high quality images cannot be obtained.
- Further, the 75 degree specular glossiness of the image preserving layer needs to be at least about 25%, preferably at least about 30% at the surface, measured in accordance with JIS(Japanese Industrial Standards) P8142, in order to obtain sufficient reproducibility of image similar to a silver salt film.
- The base paper used for an ink-receiving support of the present invention can be made from various types of paper pulps. Examples of the pulp for paper include chemical pulp such as LBKP (hardwood bleached pulp) and NBKP(softwood bleached pulp), mechanical pulp such as GP(groundwood pulp) and TMP(thermo mechanical pulp), waste paper pulp and mixture thereof, but the pulp is not limited to those.
- Various additives, such as fillers, sizing agents and paper reinforcing agents, can be added to the base paper, but the additives are not limited to those and can be selected from known fillers and known additives as required. Starch or other surface-sizing agents can be size pressed or coated. Further, antifoaming agents, pH regulators, pigments and coloring dyes for adjusting color, fluorescent pigments for improving visual whiteness and the like can be added as well.
- It is desirable that the coverage of the ink-receiving layer formed on the base paper be about 5-to-25 g/m2, preferably about 7 to 20 g/m2, on a dry solids basis. When the coverage of the ink-receiving layer is less than 5 g/m2, the ink absorbency of the layer becomes poor which will cause bleeding of ink. On the other hand, when the coverage is larger than 25 g/m2, the amount of absorbed ink becomes excessive thereby reducing the recording density and this will also degrade the quality of image.
- The ink-receiving layer comprises pigment and binder. For pigment, white pigment, such as light and heavy calcium carbonate, kaolin, clay, talc, titanium dioxide, zinc oxide, satin white, magnesium silicate, calcium silicate, aluminum silicate, aluminum hydroxide, alumina, quasi-boehmite, synthetic amorphous silica, magnesium carbonate, zeolite, is preferred. Among these, synthetic amorphous silica is more preferred as a pigment for the ink-receiving layer because it provides a superior combination of ink coloration, ink absorbency and cost.
- The binder resin used for the ink-receiving layer can be selected from any resins that can bond strongly to the base paper and can form films when coated and dried. It is desirable to use starches such as oxidized starch, esterified starch, enzyme-modified starch and cationic starch; polyvinyl alcohol with various degrees of saponification and derivatives thereof; casein, soy proteins; cellulose derivatives such as carboxymethyl cellulose and hydroxymethyl cellulose; styrene-acrylic resin; isobutylene-maleic anhydride resin; acrylic emulsion; vinyl acetate emulsion; vinylidene chloride emulsion; polyester emulsion; styrene-butadiene latex; acrylonitrile-butadiene latex and the like.
- A dye fixing agent that is cationic resin can be added to ink-receiving layer in order to impart water resistance property of the image. Examples of such agents include dicyandiamide-alkylamine polycondensed material, dicyanodiamide-formaldehyde polycondensed material, polyethylene-imine derivatives, alkylamine(-ammonium)-epichlorohydrin polycondensed material, polymethacrylic acid quaternary ammonium salt derivatives, polydiallyl-dimethylammonium chloride, and other commercially available dye fixing agent. Mixtures of these can also be used without the loss of the advantage of the present invention.
- The fixing layer of the present invention comprises cationic colloidal silica and cationic polymer electrolyte and provide a good combination of light resistance, water resistance and surface gloss. Further, it is preferred that the configuration of the cationic colloidal silica is non-spherical shape, in which several particulates interlink as in a shape of beads or a ring. When the fixing layer contains anionic colloidal silica or synthetic amorphous silica, problems are seen in operability due to the poor compatibility of the silica with the cationic polymer electrolyte.
- It is desirable that the coverage of the fixing layer be about 1 to 6 g/m2, preferably about 1.5 to 5 g/m2, on a dry solids basis. When the coverage of the fixing layer is less than 1 g/m2, sufficient water resistance and surface gloss cannot be attained. On the other hand, when the coverage is larger than 6 g/m2, the ink absorbency of the layer becomes poor and high quality images cannot be obtained.
- The content of the cationic polymer electrolyte in the fixing layer is desired to be about 2 to 25 parts by weight, preferably about 3 to 20 parts by weight based on the 100 parts by weight of the cationic colloidal silica. When the content of the cationic polymer electrolyte is less than 2 parts by weight, the water resistance is sometimes insufficient. On the other hand, when the content is larger than 25 parts by weight, the ink absorbency and light resistance sometimes degrades.
- The cationic polymer electrolyte of the present invention can be selected from dicyandiamide-alkylamine polycondensed material, dicyanodiamide-formaldehyde polycondensed material, polyethylene-imine derivatives, alkylamine (-ammonium)-epichlorohydrin polycondensed material, polymethacrylic acid quaternary ammonium salt derivatives, polydiallyl-dimethyl-ammonium chloride, other commercially available cationic polymer electrolyte and mixture thereof.
- By applying the fixing layer comprising cationic colloidal silica and cationic polymer electrolyte as a top layer, it becomes possible to obtain compatibility between water resistance and quality of recorded images. In order to get a reproducibility of images comparable to silver-salt films, the 75 degree specular glossiness is desirably at least about 30%, preferably at least about 35% at the surface of the fixing layer, measured in accordance with JIS(Japanese Industrial Standards) P8142.
- Further, the ink-receiving layer may comprise hindered amine compounds of amino ether type having alkoxyl groups in order to impart light resistance. Suitable hindered amine compounds are represented by formula (1) below: wherein R1 is CnH2n+1 (n= 1 to 14), R2 is CnH2n (n= 1 to 14) and R3 to R6 are each an alkyl group or carbonyl group. Benzotriazole compounds may be used together to improve the light resistance further.
- The n in R1 and R2 of the formula (1) is preferably 6 to 10, and the alkyl group or carbonyl group of R3 to R6 is preferably a lower alkyl group with 1 to 4 carbons, more preferably methyl group.
- The hindered amine compound of the amino ether type having alkoxyl groups is preferably bis-(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)sebacate wherein R1 is C8H17, R2 is C3H15 and R3 to R6 are methyl groups in the formula (1) (Tinuvin 123, manufactured by Ciba Specialty Chemicals, Inc.).
- Hindered amine compounds generally generate nitroxy radicals by reacting with hydroperoxide or triplet oxygen in the air, which further react to torn aminoethers by capturing polymer radicals generated by photodegradation of dyes contained in ink. Then the generated aminoethers react with peroxy radicals generated by a reaction between polymer radicals and oxygen in the air to regenerate nitroxy radicals. The aminoether also releases olefins, simultaneously generating hydroxylamine that react with the peroxy radicals to regenerate nitroxy radicals. This process is repeated to capture the radicals and hamper a chain reaction, thereby preventing the image from photodegrading.
- Since the hindered amine compounds of the present invention have an amino ether as part of their chemical structure, it is considered that peroxy radicals are immediately captured when generated. Thus the hindered amine compound is very effective in preventing photodegradation of image. While in the case of conventional hindered amine compounds unsubstituted or substituted by alkyl or acetyl groups, it is considered that there is a large energy barrier to producing aminoethers, which inhibit the effective prevention of photodegradation.
- The content of the hindered amine compounds in the ink-receiving layer is desired to be about 0.5 to 15 wt%, preferably about 2 to 8 wt%. When the content of the compounds is less than 0.5 wt%, the addition of the compounds would not be effective, and when the content is larger than 15 wt%, the applicability in manufacturing becomes worse.
- The benzotriazole compounds of the present invention preferably include, for example, 2-(2-hydroxy-3,5-di-t-amylphenyl-2H-benzotriazole, iso-octyl-3,3-(2H-benzotriazole-2-yl)-5-t-butyl-4-hydroxyphenylpropionate, 2-[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and the like.
- The content of the benzotriazole compounds in the ink-receiving layer is desired to be about 0.5 to 12 wt%, preferably about 2.5 to 8 wt%. When the content of the benzotriazole compounds is less than 0.5 wt%, the addition of the compounds would not be effective, and when the content is larger than 12 wt%, it causes significant coloring in the applied layer.
- The coating compositions for the ink-receiving layers, image-preserving layers and fixing layers may contain various additives, such as an antifoaming agent, a surface-sizing agent, a pH-adjusting agent, other CV absorber, an antioxidant, a dye or coloring pigment for adjusting color phase, a fluorescent dye and mixture thereof without the loss of the effect of the present invention.
- The method of coating the ink-receiving layers, image-preserving layers and fixing layers on base paper includes conventional coaters of various kinds, e.g., a blade coater, an air knife coater, a roll coater, a curtain coater, a bar coater, a gate roll coater and a gravure coater and the like. Further various calendering treatments such as a machine calender, a soft calender, and a super calender can be used solely or in combination for finishing the surface.
- The ink jet recording sheet of the present invention has on an ink-receiving support, in succession, an image preserving layer comprising zinc oxide particulates with a certain particular size to absorb UV light and anionic colloidal silica that is compatible with the particulates and a fixing layer comprising cationic colloidal silica to impart water resistance and surface gloss. Therefore, said ink jet recording sheet not only has superior ink-absorbency and ink coloration, but also has superior light resistance, water resistance and surface gloss, therefore the ink jet recording paper is of extremely high quality,
- The present invention will now be illustrated in more detail by reference to the following examples, but it should be understood that these examples are not to be construed as limiting the scope of the present invention in any way.
- The average primary particle size of colloidal silica is measured by BET method, the average secondary particle length of non-spherical cationic colloidal silica is measured by laser scattering method. The ink jet recording sheets in the following examples and comparative examples are evaluated by the following method. Unless otherwise noted, all "parts" are by weight in the following examples and comparative examples. The weight in the coating solution is based on dry basis, excluding water.
- The 75 degree specular glossiness is determined by using a qlossimeter, GM-26D (trade name, a product of Murakami Shikisai Kenkyujo), in accordance to JIS P8142.
- The predetermined solid pattern or image pattern is printed on the test sheet by an ink jet printer, Model PM750C (trade name, a product of Seiko Epson Corp.) and the various properties of the recorded sheet is evaluated by the following method:
- As to the densities of recorded images, the reflection densities of the black solid areas are measured with a Macbeth densitometer, RD 915 (trade name, a product of Macbeth Limited).
- The recorded density of magenta ink is measured after being tested for 25 hours by Xenon Weather Meter SC700-WN (trade name, a product of Suga Test Machinery Limited), and evaluated the remaining recorded density compared with the density before the test according to the ranks mentioned below;
- o ○ : Percentage of remaining recorded density is more than 90%.
- ○ : Percentage of remaining recorded density is 70 to 90%.
- Δ : Percentage of remaining recorded density is 50 to 70%.
- × : Percentage of remaining recorded density is less than 50%.
-
- The ink absorbency is evaluated by an extent of bleeding at the boundary between image areas of solid magenta and solid green (mixture of cyan and yellow) according to the ranks mentioned below;
- o ○ : No bleeding is observed at the boundaries.
- ○ ; Almost no bleeding is observed at the boundaries.
- Δ : Some bleeding is observed at the boundaries.
- × : Significant bleeding is observed at the boundaries.
-
- The recorded image is dried in the air for 1 day, then is immersed in a tap water at 20 degree C for 5 minutes and dried in the air again. Then the extent of change of recorded images is evaluated according to the ranks mentioned below;
- o ○ : No change is observed.
- ○ : Slight change is observed.
- Δ : Some change is observed.
- × : Most of the image bleed.
-
- A slurry consisting of 93 parts of LBKP (hardwood bleached pulp) with a freeness of 440 ml, 7 parts of NBKP(softwood bleached pulp) with a freeness of 520 ml, 7 parts of talc, 1.5 parts of sulfuric acid band (aluminum sulfate), 0.4 parts of sizing agent and 0.02 parts of yield improver is prepared. Paper is manufactured from the slurry by a twin wire machine and pre-dried by a cylinder drier. Then the coating solution 1 below is applied to the paper by a two roll sizing press to have a total solid coverage cf both sides of 4 g/m2 and is subjected to a machine calender treatment. A base paper with a dry coverage of 157 g/m2 and a smoothness of 35 seconds is obtained.
-
- Water soluble polymer: oxidized starch MS#3600(Nihon Shokuhin Kakou) 100 parts
- Surface sizing agent: Hamacoat S-200L(Misawa Ceramics) 2 parts
- Antifoaming agent: Nopco 8034L (Sun-Nopco) 0.1 parts
- Water 900 parts
- The coating solution 2 below is coated on one surface of the obtained base paper by means of a Mayer bar so as to have a dry coverage of 13 g/m2. The paper is then subjected to a calendering machine with a linear pressure of 80 Kg/cm to produce an ink-receiving layer. Then an image-preserving layer is formed by coating the coating solution 3 below on the ink-receiving layer by means of a Mayer bar so as to have a dry coverage of 2 g/m2 and then calendered at a linear pressure of 100 Kg/cm. An ink jet recording sheet with a dry coverage of 172 g/m2 is obtained.
-
- Synthetic amorphous silica: Fineseal X-37B(Tokuyama) 100 parts
- Water soluble polymer: PVA-117(Kurarey Co., Ltd.) 15 parts
- Dye fixing agent: PAS-H-10L(Nitto Boseki) 5 parts
- Antifoaming agent: SN defoamer 480(Sun-Nopco) 0.1 parts
- Water 550 parts
-
- Non-spherical anionic colloidal silica: Snowtex UP with an average primary particle size of 10 to 20 nm and an average secondary particle length of 50 to 300 nm (Nissan Chemical) 100 parts
- Zinc oxide particulates: FINEX-50 with an average particle size of 20 nm(Sakai Chemical) 5 parts
- Antifoaming agent: KM-72F(Shin-Etsu Chemical) 0.1 parts
- Water 420 parts
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that Fine Zinc Oxide (registered trade mark of Honjo Chemical) with an average particle size of 200 nm is used for zinc oxide particulates in the coating solution 3.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that the content of the zinc oxide particulates is 15 parts in the coating solution 3.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that the dry coverage of the coating solution 3 is 4.5 g/m2.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that the dry coverage of the coating solution 3 is 10 g/m2.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that the coating solution 2 is not applied.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that Hydrozincite No.1 (registered trade mark of Sakai Chemical) with an average particle size of 520 nm is used for zinc oxide particulates in the coating solution 3.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that FINEX-75 (a product of Sakai Chemical) with an average particle size of 10 nm is used for zinc oxide particulates in the coating solution 3.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that the coating solution 3 is not applied.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that the zinc oxide particulates is not formulated in the coating solution 3.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that the colloidal silica is not formulated in the coating solution 3.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that Synthetic amorphous silica, Fineseal X-37B(Tokuyama), is used for the colloidal silica in the coating solution 3.
- The evaluation results for Examples 1 to 6 and Comparative examples 1 to 6 are summarized in Table 1 below. The ink jet recording sheets ranked by o ○ or ○ can be used without causing problems.
75 degree specular glossiness (%) ink jet recording properties recorded density light resistance ink absorbency Example 1 35.8 2.10 o ○ o ○ Example 2 30.8 2.01 o ○ o ○ Example 3 30.4 1.95 o ○ o ○ Example 4 41.7 1.99 o ○ o ○ Example 5 43.6 2.06 o ○ ○ Example 6 30.5 1.98 o ○ ○ Comparative Example 1 19.4 1.62 Δ ○ Comparative Example 2 44.1 1.90 o ○ Δ Comparative Example 3 7.8 1.84 × o ○ Comparative Example 4 45.8 2.08 × ○ Comparative Example 5 8.3 1.60 Δ ○ Comparative Example 6 8.3 1.79 Δ o ○ - A slurry consisted of 93 parts of LSKP with a freeness of 440 ml (csf), 7 parts of NBKP with a freeness of 520 ml (csf), 7 parts of talc, 1.5 parts of sulfuric acid band, 0.4 parts of sizing agent and 0.02 parts of yield improver is prepared. Then a paper is manufactured from the slurry by a twin wire machine and pre-dried by a cylinder drier. Then oxidized starch is applied to the both sides of the paper by a two roll sizing press to have a total solid coverage of both sides of 4 g/m2, followed by a machine calender treatment. A base paper with a dry coverage of 160 g/m2 and a smoothness of 35 seconds is obtained.
- Then the coating solution 4 below is coated on one surface of the obtained base paper by means of a Mayer bar so as to have a dry coverage of 16 g/m2. The paper is then subjected to a calendering machine with a linear pressure of 80 Kg/cm to form an ink-receiving layer. To form an image preserving layer, coating solutions 5 and 6 below are coated successively on the ink-receiving layer by means of a Mayer bar so as to have a dry coverage of 2 g/m2 each to form a image-preserving layer and a fixing layer, and the paper is subjected to a calendering machine with a linear pressure of 100 Kg/cm. An ink jet-recording sheet with a dry coverage of 180 g/m2 is obtained.
-
- Synthetic amorphous silica: Fineseal X-37B with an average secondary particle size of 4 µm (Tokuyama) 100 parts
- Polyvinyl alcohol: PVA-117(Kurarey Co., Ltd.) 20 parts
- Dye fixing agent(quaternary ammonium salt type polymer) 5 parts
- Water 550 parts
-
- Spherical anionic colloidal silica: Snowtex 20 with an average primary particle size of 10 to 20 nm (Nissan Chemical) 100 parts
- Zinc oxide particulates with an average particle size of 20 nm 5 parts
- Water 420 parts
-
- Non-spherical (beads type) cationic colloidal silica: Snowtex OUP with an average primary particle size of 10 to 20 nm and secondary particle length of 50 to 300 nm (Nissan Chemical) 100 parts
- Cationic polymer electrolyte (quaternary ammonium salt type polymer) 5 parts
- Water 550 parts
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that the average particle size of the zinc oxide particulate is 200 nm in coating solution 5.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that the content of the zinc oxide particulates is 15 parts in coating solution 5.
- The ink jet recording sheet with a dry coverage of 182.5 g/m2 is obtained in the same manner as in Example 7, except that the dry coverage of coating solution 5 is 4.5 g/m2.
- The ink jet recording sheet with a dry coverage of 188 g/m2 is obtained in the same manner as in Example 7, except that the dry coverage of coating solution 5 is 10 g/m2.
- The ink jet recording sheet with a dry coverage of 164 g/m2 is obtained in the same manner as in Example 7, except that coating solution 4 is not applied.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that spherical cationic colloidal silica Snowtex ○ with an average primary particle size of 10 to 20 nm (Nissan Chemical) is used for the non-spherical (beads type) cationic colloidal silica in coating solution 6.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that zinc oxide particulates with an average particle size of 520 nm is used for zinc oxide particulates in coating solution 5.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that zinc oxide particulates with an average particle size of 10 nm is used for the zinc oxide particulates in coating solution 6.
- The ink jet recording sheet with a dry coverage of 178 g/m2 is obtained in the same manner as in Example 7, except that coating solution 5 is not applied.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that the spherical anionic colloidal silica is not formulated in coating solution 5.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that the zinc oxide particulate is not formulated in coating solution 5.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that the non-spherical cationic colloidal silica is not formulated in coating solution 6.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that the cationic polymer electrolyte is not formulated in coating solution 6.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that synthetic amorphous silica with an average secondary particle size of 4 µm, Fineseal X-37B (Tokuyama), is used for the spherical anionic colloidal silica in coating solution 5.
- The evaluation results for Examples 7 to 13 and Comparative examples 7 to 14 are summarized in Table 2 below. The ink jet recording sheets ranked by o ○ or ○ can be used without causing problems.
75 degree specular gloseiness (%) ink jet recording properties recorded density light resistance ink absorbency water resistance Example 7 40.6 2.21 o ○ o ○ o ○ Example 8 39.5 2.14 o ○ o ○ o ○ Example 9 36.0 2.01 o ○ o ○ o ○ Exmmple 10 43.9 2.20 o ○ o ○ o ○ Example 11 47.8 2.15 ○ ○ o ○ Example 12 37.2 1.97 o ○ ○ ○ Example 13 46.1 2.06 ○ ○ o ○ Comparative Exemple 7 23.9 1.81 Δ ○ ○ Comparative Example 8 44.4 2.15 o ○ Δ o ○ Comparative Example 9 29.5 2.04 × o ○ o ○ Comparative Example 10 can not be measured because of weakness of image-preserving layer Comparative Example 11 43.2 1.89 × o ○ o ○ Comparative Example 12 20.5 1.92 o ○ Δ ○ Comparative Example 13 41.5 2.00 o ○ ○ Δ Comparative Example 14 19.2 1.79 Δ o ○ ○ - It is obvious from Tables 1 and 2 that the ink jet recording sheet of the present invention provides a superior combination of ink absorbency, ink coloration, light resistance, water resistance and surface gloss even when printed with an ink containing a water-soluble dye.
- The ink jet recording sheet is obtained in the same manner as in Example 1, except that coating solution 7 below is used instead of coating solution 2.
-
- Synthetic amorphous silica: Fineseal X-37B(Tokuyama) 100 parts
- Water soluble polymer: PVA-117(Kurarey Co., Ltd.) 15 parts
- Dye fixing agent: PAS-H-10L(Nitto Boseki) 5 parts
- Hindered amine compound: bis-(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)sebacate (Tinuvin 123, manufactured by Ciba Specialty Chemicals, Inc.) 3 parts
- Benzotriazole compound: Tinuvin 900 (Ciba Specialty Chemicals Inc.) 10 parts
- Antifoaming agent: SN defoamer 480 (Sun-Nopco) 0.1 parts
- Water 550 parts
- The ink jet recording sheet is obtained in the same manner as in Example 14, except that the content of the hindered amine compound (Tinuvin 123) is 10 parts in the coating solution 7.
- The ink jet recording sheet is obtained in the same manner as in Example 14, except that the benzotriazole compound is omitted from coating solution 7.
- The ink jet recording sheet is obtained in the same manner as in Example 7, except that coating solution 7 is used for the coating solution 4.
- The ink jet recording sheet is obtained in the same manner as in Example 17, except that the content of the hindered amine compound (Tinuvin 123) is 10 parts in coating solution 7.
- The ink jet recording sheet is obtained in the same manner as in Example 17, except that the benzotriazole compound is omitted from coating solution 7.
-
-
- It is obvious from Examples 14 to 19 that the light resistance is further improved by formulating Tinuvin 123, hindered amine compound of amino ether type having alkoxyl groups of formula (1), in the ink-receiving layer. The light resistance is further improved by formulating benzotriazole compound in the ink-receiving layer. On the other hand, in comparative examples 15 and 16, formulating hindered amine compound of formula (2) or (3), there is not such improvement in light resistance as in examples 14 to 19.
Claims (11)
- An ink jet recording sheet having on an ink-receiving support an image preserving layer comprising anionic colloidal silica and zinc oxide particulates with an average particle size of about 15 to 380 nm, wherein said sheet has a 75 degree specular glossiness of at least about 25 % at the surface.
- An ink jet recording sheet having on an ink-receiving support, in succession, an image preserving layer comprising anionic colloidal silica and zinc oxide particulates with an average particle size of about 15 to 380 nm and a fixing layer comprising cationic colloidal silica and cationic polymer electrolyte.
- An ink jet recording sheet as in Claim 1 or 2, wherein the amount of said zinc oxide particulates is about 2 to 25 parts by weight based on 100 parts by weight of said anionic colloidal silica.
- An ink jet recording sheet as in Claim 2 or Claim 3 as appended thereto, wherein the configuration of said anionic colloidal silica in the fixing layer is non-spherical shape, in which several particulates interlink.
- An ink jet recording sheet as in any one of Claims 1-4, wherein the 75 degree specular glossiness is at least about 30% at the surface.
- An ink jet recording sheet as in Claim 3, or Claim 4 or 5 as appended thereto wherein the coverage of said image-preserving layer is about 1 to 6 g/m2 on a dry solids basis.
- An ink jet recording sheet as in Claim 5 as appended to Claims 2 and 4, wherein the coverage of said image-preserving layer is about 1 to 6 g/m2 on a dry solids basis and the coverage of said fixing layer is about 1 to 6 g/m2 on a dry solids basis.
- An ink jet recording sheet as in any one of Claims 1-7, wherein said ink-receiving support has an ink-receiving layer comprising at least a pigment and a binder on a base paper.
- An ink jet recording sheet as in Claim 8, wherein the coverage of said ink-receiving layer is about 5 to 25 g/m2 on a dry solids basis.
- An ink jet recording sheet as in Claim 10, wherein said ink-receiving layer further comprises a benzotriazole compound.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10343037A JP2000169873A (en) | 1998-12-02 | 1998-12-02 | Silicone grease composition |
JP34303798 | 1998-12-08 | ||
JP05060899A JP3300680B2 (en) | 1999-02-26 | 1999-02-26 | Inkjet recording paper |
JP5060899 | 1999-02-26 | ||
JP06855399A JP3377464B2 (en) | 1999-03-15 | 1999-03-15 | Inkjet recording paper |
JP6855399 | 1999-03-15 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1008457A1 true EP1008457A1 (en) | 2000-06-14 |
EP1008457B1 EP1008457B1 (en) | 2003-07-30 |
Family
ID=27738855
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99309809A Expired - Lifetime EP1008457B1 (en) | 1998-12-02 | 1999-12-07 | Ink-jet recording sheet with image-protecting layer |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP1008457B1 (en) |
DE (1) | DE69909947T2 (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1174279A1 (en) * | 2000-07-19 | 2002-01-23 | Nippon Paper Industries Co., Ltd. | Ink-jet recording material containing ultraviolet ray-absorber |
GB2371769A (en) * | 2001-02-02 | 2002-08-07 | Ilford Imaging Uk Ltd | Recording material and method |
KR20030029462A (en) * | 2001-10-03 | 2003-04-14 | 소니 가부시끼 가이샤 | Optical information medium |
WO2003070477A1 (en) * | 2002-02-19 | 2003-08-28 | 3M Innovative Properties Company | Image receptive material comprising cationically charged inorganic particles |
WO2003080357A1 (en) * | 2002-03-19 | 2003-10-02 | W.R. Grace & Co.-Conn. | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
WO2003089248A1 (en) * | 2002-04-17 | 2003-10-30 | W. R. Grace & Co.-Conn. | Coating composition colloidal silica and glossy ink jet recording sheets prepared therefrom |
EP1407891A1 (en) * | 2002-10-08 | 2004-04-14 | Hewlett-Packard Development Company, L.P. | Porous ink-jet printed media sealed by interpolymer complex |
WO2003080733A3 (en) * | 2002-03-19 | 2005-04-21 | Grace W R & Co | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
US6902780B2 (en) | 2002-03-19 | 2005-06-07 | W. R. Grace & Co.-Conn | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
EP1580017A1 (en) * | 2002-11-27 | 2005-09-28 | Mitsubishi Paper Mills Limited | Ink-jet recording material |
WO2006002780A2 (en) | 2004-06-25 | 2006-01-12 | Ferrania Technologies S.P.A | Ink-jet recording material |
US7255909B2 (en) | 2002-02-19 | 2007-08-14 | 3M Innovative Properties Company | Security laminate |
US7648744B2 (en) | 2004-08-06 | 2010-01-19 | 3M Innovative Properties Company | Tamper-indicating printable sheet for securing documents of value and methods of making the same |
US7658980B2 (en) | 2004-08-06 | 2010-02-09 | 3M Innovative Properties Company | Tamper-indicating printable sheet for securing documents of value and methods of making the same |
US7862868B2 (en) | 2005-01-19 | 2011-01-04 | Ferrania Technologies, S.P.A. | Ink-jet recording material |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1854798A3 (en) | 2000-09-19 | 2007-11-28 | Bristol-Myers Squibb Company | Fused heterocyclic succinimide compounds and analogs thereof, modulators of nuclear hormone receptor function |
US20040087548A1 (en) | 2001-02-27 | 2004-05-06 | Salvati Mark E. | Fused cyclic succinimide compounds and analogs thereof, modulators of nuclear hormone receptor function |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4460637A (en) * | 1981-12-24 | 1984-07-17 | Mitsubushi Paper Mills, Ltd. | Ink jet recording sheet |
EP0275711A1 (en) * | 1986-12-29 | 1988-07-27 | Canon Kabushiki Kaisha | Recording medium and ink jet recording method by use thereof |
EP0500021A1 (en) * | 1991-02-19 | 1992-08-26 | Asahi Glass Company Ltd. | Recording film and recording method |
EP0663300A1 (en) * | 1993-12-28 | 1995-07-19 | New Oji Paper Co., Ltd. | Ink jet recording sheet |
-
1999
- 1999-12-07 DE DE69909947T patent/DE69909947T2/en not_active Expired - Fee Related
- 1999-12-07 EP EP99309809A patent/EP1008457B1/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4460637A (en) * | 1981-12-24 | 1984-07-17 | Mitsubushi Paper Mills, Ltd. | Ink jet recording sheet |
EP0275711A1 (en) * | 1986-12-29 | 1988-07-27 | Canon Kabushiki Kaisha | Recording medium and ink jet recording method by use thereof |
EP0500021A1 (en) * | 1991-02-19 | 1992-08-26 | Asahi Glass Company Ltd. | Recording film and recording method |
EP0663300A1 (en) * | 1993-12-28 | 1995-07-19 | New Oji Paper Co., Ltd. | Ink jet recording sheet |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1174279A1 (en) * | 2000-07-19 | 2002-01-23 | Nippon Paper Industries Co., Ltd. | Ink-jet recording material containing ultraviolet ray-absorber |
US6677006B2 (en) | 2000-07-19 | 2004-01-13 | Nippon Paper Industries Co., Ltd. | Ink-jet recording material |
GB2371769A (en) * | 2001-02-02 | 2002-08-07 | Ilford Imaging Uk Ltd | Recording material and method |
EP1304691A3 (en) * | 2001-10-03 | 2004-04-28 | Sony Corporation | Optical information medium |
KR20030029462A (en) * | 2001-10-03 | 2003-04-14 | 소니 가부시끼 가이샤 | Optical information medium |
EP1304691A2 (en) * | 2001-10-03 | 2003-04-23 | Sony Corporation | Optical information medium |
US7080391B2 (en) | 2001-10-03 | 2006-07-18 | Sony Corporation | Optical information medium |
US6951027B2 (en) * | 2001-10-03 | 2005-09-27 | Sony Corporation | Optical information medium |
SG108875A1 (en) * | 2001-10-03 | 2005-02-28 | Sony Corp | Optical information medium |
US7255909B2 (en) | 2002-02-19 | 2007-08-14 | 3M Innovative Properties Company | Security laminate |
WO2003070477A1 (en) * | 2002-02-19 | 2003-08-28 | 3M Innovative Properties Company | Image receptive material comprising cationically charged inorganic particles |
WO2003080357A1 (en) * | 2002-03-19 | 2003-10-02 | W.R. Grace & Co.-Conn. | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
US7622170B2 (en) | 2002-03-19 | 2009-11-24 | W. R. Grace & Co.-Conn. | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
WO2003080733A3 (en) * | 2002-03-19 | 2005-04-21 | Grace W R & Co | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
US6893691B2 (en) | 2002-03-19 | 2005-05-17 | W. R. Grace & Co.-Conn. | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
CN100408345C (en) * | 2002-03-19 | 2008-08-06 | 格雷斯公司 | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
US6902780B2 (en) | 2002-03-19 | 2005-06-07 | W. R. Grace & Co.-Conn | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
CN100343074C (en) * | 2002-03-19 | 2007-10-17 | 格雷斯公司 | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
US6896942B2 (en) | 2002-04-17 | 2005-05-24 | W. R. Grace & Co. -Conn. | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
WO2003089248A1 (en) * | 2002-04-17 | 2003-10-30 | W. R. Grace & Co.-Conn. | Coating composition colloidal silica and glossy ink jet recording sheets prepared therefrom |
CN100351100C (en) * | 2002-04-17 | 2007-11-28 | 格雷斯公司 | Coating composition comprising colloidal silica and glossy ink jet recording sheets prepared therefrom |
US6833169B2 (en) | 2002-10-08 | 2004-12-21 | Hewlett-Packard Development Company, L.P. | Porous ink-jet printed media sealed by interpolymer complex |
EP1407891A1 (en) * | 2002-10-08 | 2004-04-14 | Hewlett-Packard Development Company, L.P. | Porous ink-jet printed media sealed by interpolymer complex |
EP1580017A4 (en) * | 2002-11-27 | 2006-08-16 | Mitsubishi Paper Mills Ltd | Ink-jet recording material |
EP1580017A1 (en) * | 2002-11-27 | 2005-09-28 | Mitsubishi Paper Mills Limited | Ink-jet recording material |
WO2006002780A2 (en) | 2004-06-25 | 2006-01-12 | Ferrania Technologies S.P.A | Ink-jet recording material |
US7648744B2 (en) | 2004-08-06 | 2010-01-19 | 3M Innovative Properties Company | Tamper-indicating printable sheet for securing documents of value and methods of making the same |
US7658980B2 (en) | 2004-08-06 | 2010-02-09 | 3M Innovative Properties Company | Tamper-indicating printable sheet for securing documents of value and methods of making the same |
US7862868B2 (en) | 2005-01-19 | 2011-01-04 | Ferrania Technologies, S.P.A. | Ink-jet recording material |
Also Published As
Publication number | Publication date |
---|---|
EP1008457B1 (en) | 2003-07-30 |
DE69909947D1 (en) | 2003-09-04 |
DE69909947T2 (en) | 2004-02-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1008457B1 (en) | Ink-jet recording sheet with image-protecting layer | |
EP1016546B1 (en) | Ink-jet recording paper containing silica layers and method for its' manufacture | |
US6391428B1 (en) | Ink jet recording sheet | |
EP1174279B1 (en) | Ink-jet recording material containing ultraviolet ray-absorber | |
CA2605780A1 (en) | Coated multipurpose paper, process and compositions thereof | |
EP1036666B1 (en) | Ink-jet recording sheet containing aluminium and magnesium salts | |
EP1122084B2 (en) | Ink-jet recording material suitable for pigment ink | |
EP2066840A1 (en) | Multi-functional paper for enhanced printing performance | |
KR20060042134A (en) | Ink jet recording sheet | |
US6652931B1 (en) | Recording material for ink-jet recording | |
US6977100B2 (en) | Ink-jet recording material suitable for pigment ink | |
US20050237372A1 (en) | Cast Coated Inkjet Paper | |
WO2003076203A1 (en) | Ink jet recording sheet | |
JPH0324908B2 (en) | ||
JP2006272939A (en) | Manufacturing method of inkjet recording sheet | |
EP1334838B1 (en) | Ink-jet recording medium | |
WO2005032834A1 (en) | Recording medium | |
EP1675727B1 (en) | Recording medium | |
JP2000280607A (en) | Ink jet recording sheet | |
EP1677989A1 (en) | Recording medium | |
WO2005032836A1 (en) | Recording medium | |
JP2011213010A (en) | Inkjet recording paper | |
WO2005032835A1 (en) | Recording medium | |
WO2006011798A1 (en) | Inj jet recording medium | |
JP2000168226A (en) | Ink jet recording paper |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE FR GB |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 20000830 |
|
AKX | Designation fees paid |
Free format text: DE FR GB |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Designated state(s): DE FR GB |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 69909947 Country of ref document: DE Date of ref document: 20030904 Kind code of ref document: P |
|
ET | Fr: translation filed | ||
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20040504 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20081212 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20081205 Year of fee payment: 10 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20081203 Year of fee payment: 10 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20091207 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20100831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091231 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100701 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20091207 |