EP1120280B1 - Method for increasing dot size on porous media printed with pigmented inks - Google Patents
Method for increasing dot size on porous media printed with pigmented inks Download PDFInfo
- Publication number
- EP1120280B1 EP1120280B1 EP20010300347 EP01300347A EP1120280B1 EP 1120280 B1 EP1120280 B1 EP 1120280B1 EP 20010300347 EP20010300347 EP 20010300347 EP 01300347 A EP01300347 A EP 01300347A EP 1120280 B1 EP1120280 B1 EP 1120280B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- base coat
- rewet
- applying
- coat
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Definitions
- present invention is directed generally to ink jet printing, and, more particularly, to printing on porous print media with pigment-based ink jet inks.
- Ink-jet receiving layers need to absorb the ink vehicle delivered during the printing process.
- the substrate provides no absorption capacity and as a result, the ink-receiving layer must be the sole absorbing material.
- an absorbent precoat has been described in the prior art that serves to increase the capacity of the coating, much as a substrate functions in paper-based ink-jet media.
- a top coat is applied to control surface properties such as gloss, tackiness, surface energy, and durability, as well as to function in concert with the adsorbent precoat.
- the top coat must be free of defects that would contribute to perceived irregularities or non-uniformities in the coating.
- U.S. Patent 5,275,867 describes a two-layer coating and a coating process where a top coat is laminated on the precoat.
- U.S. Patent 5,605,750 describes a three-layer coating and a coating process where the top coats are applied to the precoat by coating both fluids before drying in a multi-slot hopper or a slide hopper.
- U.S. Patent 5,576,088 describes a two layer coating and a coating process where a top coat is cast coated on a precoat. All these examples describe a process that involves specialized equipment and coatings engineered to be compatible with the processes. In addition, production efficiencies may be lower.
- a process is disclosed and claimed that allows the production of multi-layer coatings in which one or more top coats can be applied to a porous base coat to produce a uniform and defect-free coating layer.
- a process is provided in which a liquid is applied to the base coat prior to top coating such that the air in the base coat is removed prior to top coating.
- This process can occur in-line with a simple apparatus described therein.
- An added benefit of this method is that it also allows the possibility of adding functionality or performing chemistry to the coatings after the base coat is dried and before the top coat is applied in a single process.
- the wetting liquid may contain, but is not limited to, surfactants, pH modifiers, polymers, crosslinkers, pigments, and/or dye stabilizers.
- porous glossy print media examples include (1) a high quality glossy paper, Epson White Film S041072 (an opaque polyester) for use with Epson's Stylus printer and (2) Accuplot EGF Glossy White Film, available from Mile High Engineering Supply Company (Denver, CO).
- ink drop weight Ink drop weight, media coating weight, pigment/binder ratio in the media coating, particle size in the media coating, and surfactants in inks or media.
- media coating weight Ink drop weight, media coating weight, pigment/binder ratio in the media coating, particle size in the media coating, and surfactants in inks or media.
- the dot size increases compared to the current default dot size when printed with pigment-based inks in a Hewlett-Packard CP-2500 or CP-3500 printer.
- polymers suitable for use in the present invention include polyvinyl alcohol and polyvinyl acetate copolymer, polyvinyl pyrrolidone, and other water-soluble polymers such as polyamides, cellulose derivatives, and polethylene oxide.
- the colloidal silica or alumina dispersion have particle sizes in the range of about 1 to 300 nm.
- the process of the present invention is directed to applying at least one ink-receiving porous layer to a non-porous substrate.
- the process comprises:
- the base coat and the top coat disclosed and claimed in related application Serial No. 09/491,642 each comprise one or more pigments and one or more binders, which are polymeric compounds soluble or dispersible in the solvent in which the base coat and top coat are applied to the substrate.
- pigments include silica and alumina and its various hydrates, titania, carbonates (e.g., calcium carbonate, magnesium carbonate), glass beads, and organic pigments (e.g., plastic or polymer pigments such as cross-linked SBR latexes, micronized polyethylene or polypropylene wax, acrylic beads, and methacrylic beads).
- the pigment may be the same in both the base coat and top coat or different.
- the binder is a polymeric matrix which serves, among other things, to hold the pigment(s) in place.
- the binder can be water-soluble or water-dispersible.
- water-soluble binders include polyvinyl alcohol and its derivatives, polyvinyl pyrrolidone/polyvinyl acetate copolymer, cellulose derivatives, polyamides and polyethylene oxide.
- water-dispersed binders include styrene-butadiene latexes, polyacrylics, polyurethanes, and the like.
- the binder may be the same in both the base coat and top coat or different.
- the base coat and top coat are separately applied in solution to the substrate and allowed to dry.
- the substrate comprises non-permeable (non-air permeable) material, such as a film-based material, e.g., Mylar, or a resin-coated papers (e.g., photobase paper)
- non-permeable (non-air permeable) material such as a film-based material, e.g., Mylar, or a resin-coated papers (e.g., photobase paper)
- pores in the base coat are saturated, or nearly saturated, with a liquid, also called a rewetting solution herein, before the top coat solution is applied.
- a liquid also called a rewetting solution herein
- the pores in the base coat are saturated with liquid before the top coat solution is applied.
- a solvent that is compatible with the solvent in the top coating is believed to give the best adhesion between coating layers.
- the liquid may comprise one or more solvents.
- the liquid may be heated or chemically modified to increase the penetration rate in the precoat.
- the liquid is heated to any temperature below its boiling point (or the minimum boiling point if two or more solvents are used).
- chemically modified is meant the addition of one or more surfactants, adhesion promoters, pH modifiers, polymers, crosslinkers, pigments, and/or dye stabilizers to the liquid.
- the chemically modified rewet solution thus serves to modify the properties of the base coat, top coat, the coating process, or the performance of the coatings as it relates to its use as a printing media.
- Any of the usual surfactants, pH modifiers, and/or crosslinkers may be used in the practice of the present invention.
- a suitable crosslinker added to the liquid is a borate or glyoxal. This process is especially useful for chemistries that are not compatible with the coating fluids or process.
- excess fluid on the surface of the base coat be removed before top coating. This can be accomplished by a nip, doctoring blade, or the like.
- FIG. 1 shows apparatus 10 disclosed in connection with the above-mentioned patent application, which is also useful in the process of the present invention.
- the apparatus 10 which is a conventional coater, comprises a container 12 for containing a rewetting solution 14.
- a web 16 comprises the non-absorbent substrate and a porous base coat thereon and the solution 14 is introduced onto the surface of the porous base coat by means of an applicator roller 18.
- a hold-down roller 20 urges the web 16 against the top of the applicator roller 18.
- the applicator roller 18 applies the liquid 14 to the web 16.
- the liquid 14 is metered onto the applicator roller 18 by a metering roller 22, provided with a doctor 24, or other suitable means.
- the excess rewet solution may be doctored off of the web.
- the rewet solution can be metered by a pump directly onto the moving web 16, thus eliminating the need for doctoring.
- the uptake of the liquid 14 depends on the speed of the web 16. It is desired to move the web 16 as fast as possible to maximize the coating efficiency.
- the dwell time of the rewet fluid is defined as the time interval between application of the rewet fluid and application of the coating.
- the dwell time thus determines the length of time available for the rewet solution to penetrate into the base coat.
- the dwell time can be modified by the web speed and web distance between the rewet station and the coating station.
- the length of time required to obtain adequate saturation of the base coat is determined by the design of the rewet station, the base coat properties, the top coat properties, and the rewet fluid properties. For this process to be effective, all of these parameters need to be accounted for when designing the coating process.
- That invention provides a number of advantages. First, it permits applying a top coat solution on porous base coats formed on non-porous substrates. Second, it permits incorporation of materials for either the base coat or the top coat that would otherwise be incompatible with each other. Third, it allows incompatible liquids to be coated in multilayer systems.
- a rewet solution is applied to the top coat.
- the apparatus depicted in FIG. 1 is suitably employed in the practice of the present invention.
- This rewet solution which is the second rewet solution employed (the first rewet solution being applied to the base coat layer), improves the top coating so that better dot gain is achieved on the coated media with pigment-based inks.
- a liquid containing a water-soluble polymer or dilute inorganic pigment dispersion, such as colloidal silica or colloidal alumina is applied onto a porous coated medium (e.g., photobased paper) with an applicator to deliver enough volume to fill all the pores in the coating.
- a metering device e.g., squeegee, towel, air knife
- the wetted coating is then dried with hot air.
- the thickness of the coating delivered by this process is estimated to be between 0.001 and 0.5 ⁇ m, and preferably no more than about 0.1 ⁇ m thick. If the coating is too thick, then the coating is likely to greatly decrease the rate of ink vehicle penetration, resulting in poor image quality.
- water-soluble polymers suitable for use in the present invention include polyvinyl alcohol and polyvinyl acetate copolymer (e.g., Airvol 523 from Air Products), polyvinyl pyrrolidone (e.g., Luviskol K30 and K90 from BASF) and other water-soluble polymers such as polyamides, cellulose derivatives, and polethylene oxide.
- concentration of the water-soluble polymer is in the range of about 0.1 to 5 wt% of the second rewet solution.
- colloidal alumina examples include Nyacol AL 20 and Nyacol AL20DW, both available from Akzo Nobel/Eka Chemicals.
- the range of concentration of the colloidal alumina is in the range of about 0.1 to 5 wt% of the second rewet soluction.
- Surface tension reducing agents such as water-miscible organic solvents (e.g., iso-propanol and 1-butanol, concentration in the range of 0.1 to 50 wt% of the total rewet solution), polymers (e.g., polyvinyl alcohol-polyvinyl acetate, concentration in the range of 0.01 to 0.5 wt% of the total rewet solution), or surfactants may be added to the second rewet solution to achieve better wetting and coating uniformity.
- water-miscible organic solvents e.g., iso-propanol and 1-butanol, concentration in the range of 0.1 to 50 wt% of the total rewet solution
- polymers e.g., polyvinyl alcohol-polyvinyl acetate, concentration in the range of 0.01 to 0.5 wt% of the total rewet solution
- surfactants may be added to the second rewet solution to achieve better wetting and coating uniformity.
- the concentration of the surfactants is in the range of about 0.01 to 5 wt% of the-second rewet solution.
- a cross-linking agent may be added to the second rewet solution to strengthen the top coat and the base coat.
- cross-linking agents that are suitably employed in the practice of the present invention include inorganic borates (e.g., sodium borate), glyoxal, and Tyzor, which is an organic titanate/zircronate available from E. I. Du Pont de Nemours Co.
- concentration of the cross-linking agent is in the range of about 0.1 to 10 wt% of the second rewet solution.
- All media were printed with-a Hewlett-Packard CP-2500 printer, employing a test plot.
- the dot size was measured by an image analysis instrument or a microscope.
- the control media was that described in related application Serial No. 09/491,642, that is, a porous print medium coated with a base coat, a first rewet solution, and a top coat.
- a base coat and a subsequent top coat were coated onto a glossy print medium.
- the base coat and top coat had the composition listed in Table I below.
- a first rewet solution comprising heated water, was coated onto the base coat and excess was removed before applying the top coat.
- Compositions of Base Coat and Top Coat were coated onto a glossy print medium.
- compositions of Second Rewet Solution Containing Polymer Composition Concentration, wt% Control --- Airvol 523 (polyvinyl alcohol) 1% K90 (polyvinyl pyrrolidone) 1% K90 (polyvinyl pyrrolidone) 3% Compositions of Second Rewet Solution Containing Colloidal Dispersion.
- Coated media after drying of the second rewet solution, were printed with Hewlett-Packard ultraviolet (UV) pigment-based inks on an H-P DesignJet 2500CP printer.
- UV Hewlett-Packard ultraviolet
- FIGS. 3a-3b for compositions listed in Table II
- FIGS. 4a-4b for compositions listed in Table III
- All samples showed similar image quality (IQ) (bleed, gamut and area fill uniformity) to the control.
- the average dot size represents the average dot size of different colors. All materials are seen to have larger dot diameter than the default media ("None"). Some of the materials can also be used to enhance the media gloss (>11).
- Coating defects may occur during the rewet process due to the high surface tension of the dilute pigment dispersion.
- Various surface tension reducing agents such as iso-propanol (IPA), 1-butanol (BuOH), polyvinyl alcohol-polyvinyl acetate (e.g., Airvol 523), Surfynol (from Air Products), and Dynol (from Air Products) can be incorporated in the wash coat to achieve better wetting and uniformity. Examples and results are summarized in Table V. Dot Size Measurements and Gloss Measurements of Different Pigment Wash Coats with Addition of Surface Tension Reducing Agent Rewet Fluid Ave.
- the addition of the surface tension reducing agent provides a smoother coating of the rewet solution, without adversely affecting the dot size and the media gloss.
- a cross-linking agent that is known to cross link the top coat or the base coat can be added to the wash coat for adhesion or durability enhancement of the coating.
- cross-linking agents include glyoxal and Tyzor (available from du Pont). The results are summarized in Table VI. Dot Size Measurements and Gloss Measurements of Different Pigment Wash Coats with Addition of Various Cross-Linking Agents. Rewet Fluid Ave.
- cross-linking agent served to strengthen the top coat and the base coat, without adversely affecting the dot size and media gloss advantages provided by the second rewet solution of the present invention.
- the process of the present invention is expected to find use in thermal ink-jet printing onto porous glossy print media.
Landscapes
- Ink Jet (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
- present invention is directed generally to ink jet printing, and, more particularly, to printing on porous print media with pigment-based ink jet inks.
- Ink-jet receiving layers need to absorb the ink vehicle delivered during the printing process. When the ink-receiving layer is applied to non-absorbent substrate, the substrate provides no absorption capacity and as a result, the ink-receiving layer must be the sole absorbing material. To increase the absorbing capacity of the coating, an absorbent precoat has been described in the prior art that serves to increase the capacity of the coating, much as a substrate functions in paper-based ink-jet media.
- A top coat is applied to control surface properties such as gloss, tackiness, surface energy, and durability, as well as to function in concert with the adsorbent precoat. In addition, the top coat must be free of defects that would contribute to perceived irregularities or non-uniformities in the coating.
- U.S. Patent 5,275,867 describes a two-layer coating and a coating process where a top coat is laminated on the precoat. U.S. Patent 5,605,750 describes a three-layer coating and a coating process where the top coats are applied to the precoat by coating both fluids before drying in a multi-slot hopper or a slide hopper. U.S. Patent 5,576,088 describes a two layer coating and a coating process where a top coat is cast coated on a precoat. All these examples describe a process that involves specialized equipment and coatings engineered to be compatible with the processes. In addition, production efficiencies may be lower.
- In related application Serial No. 09/491,642, a process is disclosed and claimed that allows the production of multi-layer coatings in which one or more top coats can be applied to a porous base coat to produce a uniform and defect-free coating layer. Specifically, a process is provided in which a liquid is applied to the base coat prior to top coating such that the air in the base coat is removed prior to top coating. This process can occur in-line with a simple apparatus described therein. An added benefit of this method is that it also allows the possibility of adding functionality or performing chemistry to the coatings after the base coat is dried and before the top coat is applied in a single process. For example, the wetting liquid may contain, but is not limited to, surfactants, pH modifiers, polymers, crosslinkers, pigments, and/or dye stabilizers.
- Conventional glossy media have polymer-coated surfaces. The ink penetrates the coating via polymer swelling, which is slow. After the image is printed, the printed surface remains saturated with the vehicle and the dry time is long. With porous media, the ink vehicle quickly absorbs into the porous coating via capillary action and the dry time is short. As demand for faster ink-jet printing increases, faster dry time of the media becomes more important.
- Examples of porous glossy print media include (1) a high quality glossy paper, Epson White Film S041072 (an opaque polyester) for use with Epson's Stylus printer and (2) Accuplot EGF Glossy White Film, available from Mile High Engineering Supply Company (Denver, CO).
- However, the dot size of pigment-containing inks on porous media has always been low, which results in white spaces between dots, and the image appears to be streaky and non-uniform. Ink and media joint investigations have been made in an effort to increase the dot size. While increasing the dot size of dye-based inks on polymer-coated photopaper can be done by lowering the surface tension of the ink in most cases, such an approach shows little effect with pigment-based inks on porous media.
- In particular, in an attempt to improve dot size of pigment-based inks on coated porous print media, the following aspects have been examined: ink drop weight, media coating weight, pigment/binder ratio in the media coating, particle size in the media coating, and surfactants in inks or media. However, all of these experiments showed little effect on dot size.
- Thus, there is a need to provide increased dot size of pigment-based inks on porous glossy media, for improved print quality thereon.
- It is found that by rewetting coated media, such as film-based media (e.g., Mylar film) and resin-coated papers (e.g., photobase paper), with either a dilute polymer solution or a colloidal silica or colloidal alumina dispersion, the dot size increases compared to the current default dot size when printed with pigment-based inks in a Hewlett-Packard CP-2500 or CP-3500 printer. Examples of polymers suitable for use in the present invention include polyvinyl alcohol and polyvinyl acetate copolymer, polyvinyl pyrrolidone, and other water-soluble polymers such as polyamides, cellulose derivatives, and polethylene oxide. The colloidal silica or alumina dispersion have particle sizes in the range of about 1 to 300 nm.
- Specifically, the process of the present invention is directed to applying at least one ink-receiving porous layer to a non-porous substrate. The process comprises:
- (a) applying a porous base coat to a surface of the non-permeable substrate, the porous base coat comprising a plurality of pores;
- (b) applying a first rewet liquid to the porous base coat;
- (c) applying a porous top coat on the porous base coat; and
- (d) applying a second rewet liquid to the top coat, whereby the ink-receiving layer is printable with larger dots of a pigment-base ink than without the second rewet liquid.
-
- No previous efforts are known to increase the dot size on coated porous media printed with pigment inks.
-
- FIG. 1 illustrates apparatus useful in the practice of the present invention;
- FIG. 2, on coordinates of average dot size variation (in µm) as a function of silica concentration (in wt%), shows the effect of silica concentration (Nalco 2326) on dot size;
- FIG. 3a, on coordinates of dot size (in µm) under various conditions, is a plot of dot size for cyan (C), magenta (M), and black (K) as a function of different compositions of rewet liquid containing a colloidal silica in accordance with the present invention, compared with a control;
- FIG. 3b, on coordinates of dot size (in µm) under various conditions, is a plot of average dot size as a function of different compositions as in FIG. 3a;
- FIG. 4a, on coordinates of dot size (in µm) under various conditions, is a plot of dot size for cyan (C), magenta (M), and black (K) as a function of different compositions of rewet liquid containing a polymer in accordance with the present invention, compared with a control; and
- FIG. 4b, on coordinates of dot size (in µm) under various conditions, is a plot of average dot size as a function of different compositions as in FIG. 4a.
-
- Reference is made now in detail to a specific embodiment of the present invention, which illustrates the best mode presently contemplated by the inventor for practicing the invention. Alternative embodiments are also briefly described as applicable.
- The base coat and the top coat disclosed and claimed in related application Serial No. 09/491,642 each comprise one or more pigments and one or more binders, which are polymeric compounds soluble or dispersible in the solvent in which the base coat and top coat are applied to the substrate. Examples of pigments include silica and alumina and its various hydrates, titania, carbonates (e.g., calcium carbonate, magnesium carbonate), glass beads, and organic pigments (e.g., plastic or polymer pigments such as cross-linked SBR latexes, micronized polyethylene or polypropylene wax, acrylic beads, and methacrylic beads). The pigment may be the same in both the base coat and top coat or different.
- The binder is a polymeric matrix which serves, among other things, to hold the pigment(s) in place. The binder can be water-soluble or water-dispersible. Examples of water-soluble binders include polyvinyl alcohol and its derivatives, polyvinyl pyrrolidone/polyvinyl acetate copolymer, cellulose derivatives, polyamides and polyethylene oxide. Examples of water-dispersed binders include styrene-butadiene latexes, polyacrylics, polyurethanes, and the like. The binder may be the same in both the base coat and top coat or different.
- The base coat and top coat are separately applied in solution to the substrate and allowed to dry.
- The substrate comprises non-permeable (non-air permeable) material, such as a film-based material, e.g., Mylar, or a resin-coated papers (e.g., photobase paper)
- In the above-referenced application, pores in the base coat are saturated, or nearly saturated, with a liquid, also called a rewetting solution herein, before the top coat solution is applied. Preferably, the pores in the base coat are saturated with liquid before the top coat solution is applied. Also preferably, a solvent that is compatible with the solvent in the top coating is believed to give the best adhesion between coating layers.
- The liquid may comprise one or more solvents. The liquid may be heated or chemically modified to increase the penetration rate in the precoat.
- If heated, the liquid is heated to any temperature below its boiling point (or the minimum boiling point if two or more solvents are used).
- By "chemically modified" is meant the addition of one or more surfactants, adhesion promoters, pH modifiers, polymers, crosslinkers, pigments, and/or dye stabilizers to the liquid. The chemically modified rewet solution thus serves to modify the properties of the base coat, top coat, the coating process, or the performance of the coatings as it relates to its use as a printing media. Any of the usual surfactants, pH modifiers, and/or crosslinkers may be used in the practice of the present invention. For example, where the binder in the base coat is polyvinyl alcohol, a suitable crosslinker added to the liquid is a borate or glyoxal. This process is especially useful for chemistries that are not compatible with the coating fluids or process.
- It is also preferred that excess fluid on the surface of the base coat be removed before top coating. This can be accomplished by a nip, doctoring blade, or the like.
- FIG. 1
shows apparatus 10 disclosed in connection with the above-mentioned patent application, which is also useful in the process of the present invention. Theapparatus 10, which is a conventional coater, comprises acontainer 12 for containing arewetting solution 14. Aweb 16 comprises the non-absorbent substrate and a porous base coat thereon and thesolution 14 is introduced onto the surface of the porous base coat by means of anapplicator roller 18. A hold-downroller 20 urges theweb 16 against the top of theapplicator roller 18. Theapplicator roller 18 applies the liquid 14 to theweb 16. The liquid 14 is metered onto theapplicator roller 18 by ametering roller 22, provided with adoctor 24, or other suitable means. - In an alternate embodiment, the excess rewet solution may be doctored off of the web.
- In another alternative embodiment, the rewet solution can be metered by a pump directly onto the moving
web 16, thus eliminating the need for doctoring. - The uptake of the liquid 14 depends on the speed of the
web 16. It is desired to move theweb 16 as fast as possible to maximize the coating efficiency. - The dwell time of the rewet fluid is defined as the time interval between application of the rewet fluid and application of the coating. The dwell time thus determines the length of time available for the rewet solution to penetrate into the base coat. The dwell time can be modified by the web speed and web distance between the rewet station and the coating station. The length of time required to obtain adequate saturation of the base coat is determined by the design of the rewet station, the base coat properties, the top coat properties, and the rewet fluid properties. For this process to be effective, all of these parameters need to be accounted for when designing the coating process.
- That invention provides a number of advantages. First, it permits applying a top coat solution on porous base coats formed on non-porous substrates. Second, it permits incorporation of materials for either the base coat or the top coat that would otherwise be incompatible with each other. Third, it allows incompatible liquids to be coated in multilayer systems.
- In accordance with the present invention, a rewet solution is applied to the top coat. The apparatus depicted in FIG. 1 is suitably employed in the practice of the present invention. This rewet solution, which is the second rewet solution employed (the first rewet solution being applied to the base coat layer), improves the top coating so that better dot gain is achieved on the coated media with pigment-based inks.
- Specifically, a liquid containing a water-soluble polymer or dilute inorganic pigment dispersion, such as colloidal silica or colloidal alumina, is applied onto a porous coated medium (e.g., photobased paper) with an applicator to deliver enough volume to fill all the pores in the coating. A metering device, e.g., squeegee, towel, air knife) is used to remove excess liquid on the surface of the top coating. The wetted coating is then dried with hot air. The thickness of the coating delivered by this process is estimated to be between 0.001 and 0.5 µm, and preferably no more than about 0.1 µm thick. If the coating is too thick, then the coating is likely to greatly decrease the rate of ink vehicle penetration, resulting in poor image quality.
- Examples of water-soluble polymers suitable for use in the present invention include polyvinyl alcohol and polyvinyl acetate copolymer (e.g.,
Airvol 523 from Air Products), polyvinyl pyrrolidone (e.g., Luviskol K30 and K90 from BASF) and other water-soluble polymers such as polyamides, cellulose derivatives, and polethylene oxide. The concentration of the water-soluble polymer is in the range of about 0.1 to 5 wt% of the second rewet solution. - Examples of colloidal silica (silica sol) suitable for this application include Nalco 1140 (particle size D = 15 nm), Nalco 1034A (D = 20 nm), Nalco 1060 (D = 60 nm), Nalco 2326 (D = 5 nm), all available from Nalco Chemical Company; Nyalcol 2034DI (D = 20 nm), Nyacol 2040NH4 (D = 20 nm), and Nyacol 215 (D = 4 nm), all available from Akzo Nobel/Eka Chemicals; and Snowtex 40 (D = 10-20 nm), Snowtex N (D = 10-20 nm), Snowtex O (D = 11-14 nm), Snowtex OL (D = 40-50 nm), Snowtex OXS (D = 4-6 nm) Snowtex YL (D = 50-80 nm), and Snowtex ZL (D = 70-100 nm), all available from Nissan Chemical Industries, Ltd.
- Examples of pearl-like silica sol include Snowtex ST-PSM (D = 18-22 nm width, 100-200 nm length), available from Nissan Chemical Industries, Ltd.
- Examples of elongated silica sol include Snowtex OUP (D = 10 nm width, 50-100 nm length) and Snowtex UP (D = 5-20 nm width, 40-300 nm length), both available from Nissan Chemical Industries, Ltd.
- An example of an alumina-coated silica sol includes Snowtex C (D = 10-20 nm).2, available from Nissan Chemical Industries, Ltd.
- Examples of cationic silica include Nyacol IJ222 (D = 70 nm) and Nyacol IJ666 (D = 5 nm), both available from Akzo Nobel/Eka Chemicals.
- Experiments on
Nalco 2326 showed that the dot size of the printed ink increases linearly between 0 and 0.2 wt% of SiO2 and it remains unchanged above 0.2 wt%; see, FIG. 2. The range of silica concentration is between 0.05 to 5 wt%, preferably between 0.1 to 1 wt%. Among all the chemicals tested, 1 wt% silica rewet solution (1 wt% silica in water, e.g., Nalco 2326) showed significantly larger dot size (85 to 90 µm) than the default dot size (65 to 70 µm) obtained without use of the rewet solution of the present invention. - Examples of colloidal alumina include
Nyacol AL 20 and Nyacol AL20DW, both available from Akzo Nobel/Eka Chemicals. The range of concentration of the colloidal alumina is in the range of about 0.1 to 5 wt% of the second rewet soluction. - Surface tension reducing agents, such as water-miscible organic solvents (e.g., iso-propanol and 1-butanol, concentration in the range of 0.1 to 50 wt% of the total rewet solution), polymers (e.g., polyvinyl alcohol-polyvinyl acetate, concentration in the range of 0.01 to 0.5 wt% of the total rewet solution), or surfactants may be added to the second rewet solution to achieve better wetting and coating uniformity. Examples of surfactants that are suitably employed in the practice of the present invention include the Surfynols, which are acetylenic ethoxylated diols available from Air Products and the Dynols, which are non-ionic alkoxylated alkynols available from Air Products. The concentration of the surfactants is in the range of about 0.01 to 5 wt% of the-second rewet solution.
- Further, a cross-linking agent may be added to the second rewet solution to strengthen the top coat and the base coat. Examples of cross-linking agents that are suitably employed in the practice of the present invention include inorganic borates (e.g., sodium borate), glyoxal, and Tyzor, which is an organic titanate/zircronate available from E. I. Du Pont de Nemours Co. The concentration of the cross-linking agent is in the range of about 0.1 to 10 wt% of the second rewet solution.
- All media were printed with-a Hewlett-Packard CP-2500 printer, employing a test plot. The dot size was measured by an image analysis instrument or a microscope. The control media was that described in related application Serial No. 09/491,642, that is, a porous print medium coated with a base coat, a first rewet solution, and a top coat.
- A base coat and a subsequent top coat were coated onto a glossy print medium. The base coat and top coat had the composition listed in Table I below. Prior to coating the top coat, a first rewet solution, comprising heated water, was coated onto the base coat and excess was removed before applying the top coat.
Compositions of Base Coat and Top Coat. Base Coat (25 g/m2) Chemical wt% in Dry Film precipitated amorphous SiO2 77 polyvinyl alchohol - Gohsenol NH-26 (Nippon Gohsei) 23 Top Coat (20 g/m2) Chemical wt% in Dry Film alumina boehmite - Dispal 9N4 (Condea Vista) 89.4 modified polyvinyl alchohol Gohsefimer Z200 (Nippon Gohsei) 3 polyvinyl alcohol - Airvol 523 (Air Products) 1 cationic resin/polymer - Amres 8855 (Georgia-Pacific) 4 acetic acid (HOAc) 1.6 sucrose 1 - Following application of the top coat, then a coating of the second rewet solution was applied to the top coat, in accordance with the present invention. The compositions tested are listed in Tables II and III, below.
Compositions of Second Rewet Solution Containing Polymer. Composition Concentration, wt% Control --- Airvol 523 (polyvinyl alcohol) 1% K90 (polyvinyl pyrrolidone) 1% K90 (polyvinyl pyrrolidone) 3% Compositions of Second Rewet Solution Containing Colloidal Dispersion. Composition Concentration, wt% Control --- Nalco 1140 (SiO2) 1% Nalco 1140 (SiO2) 5% Nalco 1060 (SiO2) 5% Nalco 2326 (SiO2) 1% Nalco 2326 (SiO2) 5% Snowtex O (SiO2) 1% Snowtex O (SiO2) 5% Snowtex OL (SiO2) 1% Snowtex OL (SiO2) 5% Snowtex OXS (SiO2) 1% Snowtex OXS (SiO2) 5% - Coated media, after drying of the second rewet solution, were printed with Hewlett-Packard ultraviolet (UV) pigment-based inks on an H-P DesignJet 2500CP printer.
- The measurements of the dot size of the printed ink are shown in FIGS. 3a-3b (for compositions listed in Table II) and in FIGS. 4a-4b (for compositions listed in Table III) for a rewet liquid containing a polymer and a colloidal dispersion, respectively. All samples showed similar image quality (IQ) (bleed, gamut and area fill uniformity) to the control.
- Rewetting the media with a liquid containing a polymer increased the dot size slightly. However, rewetting the media with a liquid containing a colloidal silica showed a more significant effect on the dot size. Among all the silicas tested, Nalco 2326 (1 wt% silica) evidenced the most improvement, as shown in FIGS. 3a-3b. This increase in dot size also leads to slightly higher optical density in the print areas. In this case, the media gloss also increased from 10-12% to 25% at 20 degrees while the image gloss remained unchanged.
- Table IV summarizes the dot size measurements and gloss measurements of the pigment wash coat of the present invention.
Dot Size Measurements and Gloss Measurements. Rewet Fluid Ave. Dot Size (µm) Standard Deviation (µm) Media Gloss at 20 Degrees None 71.0 2.3 11 5 % Nalco 106078.2 2.5 4 1 % Nalco 114080.9 2.0 6 5 % Nalco 114082.4 2.1 15 1 % Nalco 232690.8 2.2 25 5 % Nalco 232687.5 2.1 28 1% Nalco IJ666 78.7 3.6 25 5% Nalco IJ666 74.6 2.8 29 5% Nalco AL20 76.1 1.8 36 1% Nalco AL20DW 76.5 2.7 26 1% Snowtex 40 81.2 1.9 20 5% Snowtex 40 83.1 1.6 16 1% Snowtex C 80.1 3.0 16 5% Snowtex C 79.9 1.1 26 1% Snowtex N 84.7 3.1 9 5% Snowtex N 83.6 3.0 22 1% Snowtex O 83.4 1.6 5 5% Snowtex O 81.4 1.7 11 1% Snowtex OL 78.2 2.2 6 5% Snowtex OL 79.0 2.4 2 1% Snowtex OXS 82.9 2.1 3 5% Snowtex OXS 79.8 2.2 8 1% Snowtex ST-PSM 80.6 2.5 6 5% Snowtex ST-PSM 82.3 3.3 23 - The average dot size represents the average dot size of different colors. All materials are seen to have larger dot diameter than the default media ("None"). Some of the materials can also be used to enhance the media gloss (>11).
- Coating defects (e.g., fisheyes) may occur during the rewet process due to the high surface tension of the dilute pigment dispersion. Various surface tension reducing agents, such as iso-propanol (IPA), 1-butanol (BuOH), polyvinyl alcohol-polyvinyl acetate (e.g., Airvol 523), Surfynol (from Air Products), and Dynol (from Air Products) can be incorporated in the wash coat to achieve better wetting and uniformity. Examples and results are summarized in Table V.
Dot Size Measurements and Gloss Measurements of Different Pigment Wash Coats with Addition of Surface Tension Reducing Agent Rewet Fluid Ave. Dot Size (µm) Standard Deviation (µm) Media Gloss at 20 Degrees None 71.0 2.3 11 1 % Nalco 1134A+ 1% IPA82.2 1.9 8 1% Nalco 1134A+ 81.1 2.2 9 1 % BuOH 1% Nalco 1134A + 0.1 % Airvol 52381.5 2.6 5 1 % Nalco 2326 + 1% IPA85.2 2.3 14 1 % Nalco 2326 + 1% BuOH87.2 2.8 25 1 % Nalco 2326 + 0.2% Dynol 60486.7 2.0 8 1 % Nalco 2326 + 0.2% Surfynol 50491.8 2.2 18 1 % Nalco 2326 + 0.1% Airvol 52387.9 3.1 4 1% Nyacol 2034DI + 1% BuOH 79.6 2.9 7 1% Nyacol 2040NH4 + 1% BuOH 80.6 3.2 8 1% Nyacol 215 + 1% BuOH 77.2 3.7 4 1% Nyacol IJ222 + 1% BuOH 80.1 3.5 21 1% Snowtex C + 1% IPA 81.1 1.5 21 1% Snowtex C + 1% BuOH 80.4 1.8 20 1% Snowtex C + 0.1 % Airvol 52381.5 2.0 20 1% Snowtex OUP + 1% BuOH 75.4 2.0 5 1% Snowtex UP + 1% BuOH 77.2 2.7 5 1% Snowtex YL + 1% BuOH 77.6 2.6 2 1% Snowtex ZL + 1% BuOH 79.2 3.0 3 - The addition of the surface tension reducing agent provides a smoother coating of the rewet solution, without adversely affecting the dot size and the media gloss.
- A cross-linking agent that is known to cross link the top coat or the base coat can be added to the wash coat for adhesion or durability enhancement of the coating. Examples of such cross-linking agents include glyoxal and Tyzor (available from du Pont). The results are summarized in Table VI.
Dot Size Measurements and Gloss Measurements of Different Pigment Wash Coats with Addition of Various Cross-Linking Agents. Rewet Fluid Ave. Dot Size (µm) Standard Deviation (µm) Media Gloss at 20 Degrees None 71.0 2.3 11 1 % Nalco 2326 + 0.5% glyoxal, 1% BuOH82.2 1.9 8 1 % Nalco 2326 + 1% glyoxal, 1% BuOH81.1 2.2 9 1 % Nalco 2326 + 1% Tyzor LA, 1% BuOH81.5 2.6 5 - The addition of the cross-linking agent served to strengthen the top coat and the base coat, without adversely affecting the dot size and media gloss advantages provided by the second rewet solution of the present invention.
- The process of the present invention is expected to find use in thermal ink-jet printing onto porous glossy print media.
Claims (10)
- A process for applying at least one ink-receiving layer to a non-porous substrate, said process comprising:(a) applying a porous base coat to a surface of said non-porous substrate, said porous base coat comprising a plurality of pores;(b) applying a first rewet liquid to said porous base coat;(c) applying a top coat on said porous base coat; and(d) applying a second rewet liquid to said top coat,
- The process of Claim 1 wherein said base coat and said top coat each independently comprise at least one pigment, at least one binder, and at least one solvent.
- The process of Claim 1 wherein said first rewet liquid contains a solvent that is compatible with said at least one solvent of said top coat.
- The process of Claim 1 wherein said second rewet liquid comprises a solution containing at least one species selected from the group consisting of a water-soluble polymer, colloidal silica, and colloidal alumina.
- The process of Claim 4 wherein said solution is aqueous-based and (a) wherein said water-soluble polymer is selected from the group consisting of polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyamides, cellulose derivatives, and polyethylene oxide, present in a concentration of about 0.1 to 5 wt%, (b) wherein said colloidal silica solution comprises about 0.1 to 5 wt% colloidal silica in water, and (c) wherein said colloidal alumina solution comprises about 0.1 to 5 wt% colloidal alumina in water.
- The process of Claim 4 wherein said second rewet liquid further comprises at least one species selected from the group consisting of surface tension reducing agents and cross-linking agents.
- The process of Claim 6 wherein said surface tension reducing agent is selected from the group consisting of water-miscible organic solvents, polymers, and surfactants and wherein said cross-linking agent is selected from the group consisting of borates, glyoxal, and organic titanates/zirconates.
- The process of Claim 7 wherein said water-miscible organic solvent is selected from the group consisting of iso-propanol, and 1-butanol, wherein said polymer comprises a copolymer of polyvinyl alcohol and polyvinyl acetate, and wherein said surfactant is selected from the group consisting of acetylenic ethoxylated diols and non-ionic alkoxylated alkynols.
- The process of Claim 7 wherein said surface tension reducing agent is added to said second rewet liquid to a concentration in the range of 0.1 to 50 wt% for said water-miscible organic solvent or 0.01 to 0.5 wt% for said polymer or 0.01 to 5 wt% for said surfactant or wherein said cross-linking agent is added to said second rewet liquid to a concentration in the range of 1 to 10 wt%.
- A method for increasing dot size of a pigment-based ink printed on an ink-receiving layer applied to a non-permeable substrate, employing said method of Claim 1, comprising:(a) applying said porous base coat to said surface of said non-permeable substrate, said porous base coat comprising at least one pigment and at least one binder and further comprising a plurality of pores;(b) applying said first rewet liquid to said porous base coat to form a liquid-coated base coat and to ensure saturation of said pores;(c) applying said top coat on said liquid-coated base coat, said top coat comprising at least one pigment and at least one binder; and(d) applying said second rewet liquid to said top coat,
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/491,642 US6475612B1 (en) | 2000-01-27 | 2000-01-27 | Process for applying a topcoat to a porous basecoat |
US491642 | 2000-01-27 | ||
US545934 | 2000-04-10 | ||
US09/545,934 US6451379B1 (en) | 2000-01-27 | 2000-04-10 | Increasing dot size on porous media printed with pigmented inks |
Publications (3)
Publication Number | Publication Date |
---|---|
EP1120280A2 EP1120280A2 (en) | 2001-08-01 |
EP1120280A3 EP1120280A3 (en) | 2001-09-05 |
EP1120280B1 true EP1120280B1 (en) | 2005-06-29 |
Family
ID=27050509
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20010300347 Expired - Lifetime EP1120280B1 (en) | 2000-01-27 | 2001-01-16 | Method for increasing dot size on porous media printed with pigmented inks |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1120280B1 (en) |
JP (1) | JP3973841B2 (en) |
DE (1) | DE60111655T2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7585553B2 (en) | 2002-05-24 | 2009-09-08 | Hewlett-Packard Development Company, L.P. | Inkjet media coating with improved lightfastness, scratch resistance, and image quality |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4849286A (en) * | 1987-12-14 | 1989-07-18 | James River Graphics, Inc. | Transparent plotter film |
ATE125491T1 (en) * | 1989-11-14 | 1995-08-15 | Canon Kk | METHOD FOR PRODUCING RECORDING MATERIAL. |
JPH04214393A (en) * | 1990-12-12 | 1992-08-05 | Nisshinbo Ind Inc | Sublimate type thermal transfer image receiving paper |
US6465086B1 (en) * | 1997-05-15 | 2002-10-15 | Oji Paper Co., Ltd. | Ink jet recording material and process for producing same |
WO1998052765A1 (en) * | 1997-05-23 | 1998-11-26 | Nashua Corporation | Glossy ink jet paper |
-
2001
- 2001-01-16 DE DE2001611655 patent/DE60111655T2/en not_active Expired - Lifetime
- 2001-01-16 EP EP20010300347 patent/EP1120280B1/en not_active Expired - Lifetime
- 2001-01-29 JP JP2001019837A patent/JP3973841B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP1120280A2 (en) | 2001-08-01 |
DE60111655T2 (en) | 2006-05-04 |
EP1120280A3 (en) | 2001-09-05 |
DE60111655D1 (en) | 2005-08-04 |
JP2001246842A (en) | 2001-09-11 |
JP3973841B2 (en) | 2007-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6451379B1 (en) | Increasing dot size on porous media printed with pigmented inks | |
EP0983867B1 (en) | Ink-jet recording element containing colloidal silica | |
WO2017019324A1 (en) | Printing on water-impermeable substrates with water-based inks | |
JP2009528192A (en) | Inkjet recording element | |
JPH10193776A (en) | Ink jet recording paper | |
CN100348427C (en) | Ink-jet recording medium preparation method | |
US20020009576A1 (en) | Specialty microporous films and laminated media with applications in ink jet and digital printing | |
EP1120280B1 (en) | Method for increasing dot size on porous media printed with pigmented inks | |
JP2944143B2 (en) | Ink jet recording medium | |
JP3088147B2 (en) | Recording material | |
JP5027673B2 (en) | Inkjet recording medium | |
JP3716561B2 (en) | Ink jet recording paper and method for producing the same | |
JPH08252969A (en) | Recording medium and image forming method using the medium | |
CN1868758B (en) | Recording sheet for ink jet printing | |
JP3784183B2 (en) | Ink-jet recording sheet with ink-receiving layer and coating liquid for forming ink-receiving layer | |
JPH02117880A (en) | Recording material and recording method | |
JP2005343108A (en) | Inkjet recording sheet for pigment ink | |
EP1193079B1 (en) | Lightfastness improvements of inkjet print media through the addition of photoinitiators | |
JPH1120301A (en) | Ink jet recording paper | |
JP3757562B2 (en) | Inkjet recording paper | |
JP3503016B2 (en) | Inkjet recording paper | |
JP4915038B2 (en) | Inkjet recording method | |
JPH0216078A (en) | Ink jet recording method | |
JP3755198B2 (en) | Inkjet recording medium | |
JP2002225252A (en) | Surface treatment method for recorded material, recorded material and surface treatment device using the method |
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 |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR Kind code of ref document: A2 Designated state(s): DE FR GB |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17P | Request for examination filed |
Effective date: 20020221 |
|
AKX | Designation fees paid |
Free format text: DE FR GB |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 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: 60111655 Country of ref document: DE Date of ref document: 20050804 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: 20060330 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: 732E Free format text: REGISTERED BETWEEN 20120329 AND 20120404 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20121224 Year of fee payment: 13 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20121226 Year of fee payment: 13 Ref country code: FR Payment date: 20130305 Year of fee payment: 13 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60111655 Country of ref document: DE |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20140116 |
|
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: 20140801 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20140930 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 60111655 Country of ref document: DE Effective date: 20140801 |
|
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: 20140131 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20140116 |