EP2785530A2 - Methods of improving sheet gloss - Google Patents

Methods of improving sheet gloss

Info

Publication number
EP2785530A2
EP2785530A2 EP11879159.9A EP11879159A EP2785530A2 EP 2785530 A2 EP2785530 A2 EP 2785530A2 EP 11879159 A EP11879159 A EP 11879159A EP 2785530 A2 EP2785530 A2 EP 2785530A2
Authority
EP
European Patent Office
Prior art keywords
dry parts
recording medium
calcium carbonate
base
pli
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
Application number
EP11879159.9A
Other languages
German (de)
French (fr)
Other versions
EP2785530A4 (en
EP2785530B1 (en
Inventor
Christopher Arend Toles
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hewlett Packard Development Co LP
Original Assignee
Hewlett Packard Development Co LP
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hewlett Packard Development Co LP filed Critical Hewlett Packard Development Co LP
Publication of EP2785530A2 publication Critical patent/EP2785530A2/en
Publication of EP2785530A4 publication Critical patent/EP2785530A4/en
Application granted granted Critical
Publication of EP2785530B1 publication Critical patent/EP2785530B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5218Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/0011Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5227Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52Macromolecular coatings
    • B41M5/5254Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present disclosure relates generally to methods of improving sheet gloss.
  • Recent trends in digital printing technology include utilizing inkjet inks in high-speed digital commercial or industrial printers.
  • Inkjet inks are often aqueous based inks, which contain a minor amount of colorant and a large amount of water and co-solvent(s).
  • a medium having suitable absorption properties As such, in high-speed digital inkjet printing, it is desirable to utilize a medium having suitable absorption properties.
  • the medium used inkjet printing determines, at least in part, the quality of the image printed thereon. When the absorption properties of the medium are poor, the quality of the resulting image is often poor as well.
  • an ink-receiving layer is included which improves the ink receptive properties of the medium.
  • Fig. 1 is a flow diagram illustrating an example of a method for improving sheet gloss.
  • Examples of the recording medium disclosed herein include one layer that functions as both an ink-receiving layer and a coating layer.
  • the single ink- receiving and coating layer imparts a high ink adsorption rate (i.e., fast absorption of the liquid component in the ink, e.g. water) and exhibits improvements in image qualities after printing, including reduced graininess, improved image gloss, low ink bleed, low mottle, high gamut, and high black optical density.
  • Examples of the recording medium disclosed herein are also subjected to a calendering process that utilizes specific pressure and temperature conditions, which are relatively high compared to standard calendering conditions.
  • the level of calendering disclosed herein unexpectedly results in the recording medium having desirable print quality (e.g., low ink bleed, etc.) as well as desirably high (>40) sheet gloss levels.
  • desirable print quality e.g., low ink bleed, etc.
  • desirably high (>40) sheet gloss levels e.g., high ink bleed, etc.
  • the single ink-receiving and coating layer disclosed herein achieved desirable gloss without a second layer (i.e., without an additional ink-receiving layer), and also provides desirable absorption after the calendering process is performed, which is in contrast to other recording sheets that suffer from poor absorption as a result of over calendering.
  • the recording medium includes a base.
  • the base is a supporting substrate upon which the single ink-receiving and coating layer is formed.
  • the base may be in the form of a sheet or a continuous web suitable for use in an inkjet printer.
  • the base is a base paper manufactured from cellulose fibers. More specifically, the base paper may be produced from chemical pulp, mechanical pulp, thermal mechanical pulp and/or the combination of chemical and mechanical pulp.
  • the base paper may also include additives, such as internal sizing agents and/or fillers. When utilized, the internal sizing agents are added to the pulp before it is converted into a paper web or substrate. Any suitable internal sizing agent may be selected, such as alkyl succinic anhydride, diketene, and rosin.
  • the base may be an uncoated raw base or a pre-coated base.
  • the pre-coated base includes a pre-coating that is established on the raw base.
  • the pre-coating may include any of a variety of inorganic pigment coatings applied in-line or offline using a size press, a gateroll press or any variety of blade coater.
  • a pre- coat may be from about 5 gsm to about 10 gsm of calcium carbonate with a binder, such as polyvinyl alcohol or latex.
  • the single ink-receiving and coating layer is established directly on the base (i.e., on the raw base or on the pre-coating of the base). It is to be understood that this single layer is one layer that contains the coating composition disclosed herein.
  • the single layer may have any desirable thickness, and in some instances may include multiple sub-layers to achieve the desirable thickness. However, the single layer acts as both the ink-receiving layer and the coating layer, and thus the recording medium does not include any other layers on the single layer. As such, the single ink-receiving and coating layer is the outermost layer of the recording medium.
  • the single ink-receiving medium and coating layer is made up of an aqueous pigmented dispersion composition that includes both modified calcium carbonate (MCC) and precipitated calcium carbonate (PCC).
  • MCC modified calcium carbonate
  • PCC precipitated calcium carbonate
  • the modified calcium carbonate used herein refers to pre-existing calcium carbonate (ground or precipitated) which has been post-treated with phosphoric acid and CO 2 gas as well as a variety of other additives (such as soluble silicates) for the purpose of altering both the structure and the chemical composition of the original particle.
  • the post-treatment of the calcium carbonate results in a pigment particle made up of a shell of various calcium compounds surrounding a core of the original carbonate molecule.
  • Suitable MCC material may take the form of a slurry dispersion of structured calcium minerals, which include primarily calcium
  • Calcium phosphate includes compounds containing calcium ions together with phosphate ions, and may include octacalcium phosphate (Ca8H 2 (PO 4 )6-5H 2 O) or other forms of calcium phosphate.
  • octacalcium phosphate is OMYAJET® 5010 available from Omya Inc.
  • the amount of modified calcium carbonate pigment included in the composition ranges from about 15 dry parts to about 25 dry parts of the total dry parts of the composition. Precipitated calcium carbonate pigments may be obtained by calcining crude calcium oxide.
  • Precipitated calcium carbonate is commercially available, for example, under the tradename OPACARB® A40 (Minerals Technologies Inc.).
  • the amount of precipitated calcium carbonate used in the composition ranges from about 75 dry parts to about 85 dry parts.
  • the total amount of inorganic pigments present in the coating composition ranges from about 60 wt.% to about 90 wt.%.
  • Wt.% refers to dry weight percentage based on the total dry weight of the coating composition.
  • the composition excludes clay.
  • the composition disclosed herein develops desirable gloss (due, at least in part, to the calendering process) and maintains sufficient coating openness for adequate absorption without the use of clay.
  • clay such as calcined clay, kaolin clay, or other phyllosilicates, may be included. Clay(s), in some instances, may be added to further increase the gloss and/or increase the absorption rate. As an example, calcined clay may be desirable to further enhance the absorption rate of the single ink-receiving and coating layer.
  • the calcined clay(s) may be added in an amount ranging from about 0.5 dry parts to about 10 dry parts (based on the total parts of inorganic particles).
  • the uncalcined clay(s) may be added in an amount ranging from about 0.5 dry parts to about 5 dry parts (based on total parts of inorganic particles).
  • the coating composition disclosed herein may also include a polymeric co- pigment.
  • suitable polymeric co-pigments include plastic pigments (e.g., polystyrene, polymethacrylates, polyacrylates, copolymers thereof, and/or combinations thereof).
  • Suitable solid spherical plastic pigments are commercially available from The Dow Chemical Company, e.g., DPP 756A and HS 3020.
  • the amount of polymeric co-pigment in the coating composition may be in the range of 1 dry part to 10 dry parts based on 100 parts of inorganic pigments. In an example, the amount of polymeric co-pigment or plastic pigments ranges from about 3 dry parts to about 7 dry parts per 100 parts of inorganic pigments.
  • the coating composition also includes a binder.
  • the binder(s) may be hydrophilic or water-soluble binders such as polyvinyl alcohol (e.g., MOWIOL® 15- 98, Kuraray) and derivatives thereof (e.g. carboxylated polyvinyl alcohol, sulfonated polyvinyl alcohol, acetoacetylated polyvinyl alcohol, and mixtures thereof), polystyrene-butadiene, polyethylene-polyvinyacetate copolymers, starch, gelatin, casein, alginates, carboxycellulose materials, polyacrylic acid and derivatives thereof, polyvinyl pyrrolidone, casein, polyethylene glycol, polyurethanes (for example, a modified polyurethane resin dispersion), polyamide resins (for instance, an epichlorohydrin-containing polyamide), a polyvinyl pyrrolidone-vinyl acetate) copolymer, a polyvinyl acetate-
  • the binder is present in an amount sufficient to bind the inorganic pigments.
  • the total amount of binder is present in an amount ranging from about 5 to about 20 parts based on 100 parts of inorganic pigments.
  • the coating composition includes from about 3 dry parts to about 10 dry parts of a latex binder and from about 2 dry parts to about 7 dry parts of a polyvinyl alcohol binder.
  • the coating composition may also include other coating additives such as calcium chloride, surfactants, rheology modifiers, defoamers, optical brightening agents, sheet color adjusting agents, biocides, pH controlling agents, dyes (e.g., violet dye), and other additives for further enhancing the properties of the coating.
  • the total amount of coating additives may be in the range of 0 to about 10 parts based on 100 parts of inorganic pigments.
  • the coating composition includes from about 8 dry parts to about 10 dry parts of calcium chloride (CaC ), from about 0.3 dry parts to about 0.4 dry parts of a defoaming agent (e.g.,
  • AGITANTM 103, Munzing from about 0.004 dry parts to about 0.006 dry parts of a sheet color adjusting agent (e.g., CATERENTM Violet 79732, Clariant), and from about 0.4 dry parts to about 0.6 dry parts of an optical brightening agent (e.g., TINOPAL®, BASF Corp.).
  • a sheet color adjusting agent e.g., CATERENTM Violet 79732, Clariant
  • an optical brightening agent e.g., TINOPAL®, BASF Corp.
  • Water is added to the inorganic pigments and other components in order to form the coating composition.
  • the amount of water added may depend, at least in part, on the desirable solids percentage for the final coating composition. In an example, enough water is added to obtain composition including from about 40% solids to about 55% solids.
  • the composition is established directly on the base to form the recording medium.
  • the coating composition may be applied to one or both opposing sides of the base.
  • the double-side coated recording medium has a sandwich structure, i.e., both sides of the supporting base are coated with the same coating, and both sides may be printed with images or text.
  • the coat weight of the single ink-receiving and coating layer may be in the range of about 4 gsm (grams per square meter) to 45 gsm per side. In an example, the coat weight of the single ink-receiving and coating layer may be in the range of about 4.5 gsm to about 30 gsm per side.
  • the coating composition of the present disclosure may be applied to the base using any one of a variety of suitable coating methods, such as blade coating, jet blade coating, air knife coating, metering rod coating, curtain coating, or another suitable technique.
  • suitable coating methods such as blade coating, jet blade coating, air knife coating, metering rod coating, curtain coating, or another suitable technique.
  • both sides of the base may be coated during a single manufacture pass, or alternatively, each side may be coated in separate passes.
  • the coated base is then subjected to a drying process to remove water and other volatile components from the ink-receiving and coating layer and the base.
  • the drying means includes, but is not limited to, infrared (IR) dryers, hot surface rolls, and hot air flotation dryers.
  • the recording medium is calendered to increase glossiness (reference numeral 102 in Fig. 1 ).
  • Calendering may be accomplished using an on-line or an off-line calender machine, which may be a soft-nip calender or a supercalender.
  • the rolls e.g., a stainless steel roll positioned against a cotton-filled backing roll
  • the calendering process disclosed herein is performed at a pressure ranging from about 1200 PLI (pressure per linear inch) to about 1500 PLI (i.e., about 3000 psi (pressure per square inch) to about 3500 psi) and at a temperature ranging from about 85°C to about 95°C.
  • the calendering process is performed for a number of passes ranging from 2 to 5 (reference numeral 104 in Fig. 1 ). This calendering process unexpectedly results in desirable sheet gloss (>40), while not sacrificing printability and print quality. In particular, it has been found that the calendering process disclosed herein does not negatively impact the printability because the process does not close up the structure of the coating.
  • composition was generated utilizing the components shown in Table 1 The composition had a total solids amount of 44.5 wt%. Table 1
  • the composition was coated on a pre-coated offset base via blade coating to form a recording medium having a single ink receiving and coating layer on the pre-coated base.
  • the composition was coated at 7 gsm on 90 gsm of the pre- coated base.
  • the recording medium was calendered according the examples disclosed herein using a heated 2 roll calender from Independent Machine Co., Fairfield, NJ.
  • the recording medium was calendered at 3000 psi ( ⁇ 1286 PLI) and at about 90°C for 2 passes.
  • the sheet gloss level of the calendered recording medium was measured at a 75° measurement angle using a Micro gloss 75, which is a gloss meter available from BYK-Gardner.
  • the sheet gloss in this example was 60, which was well above a suitable sheet gloss level of 40.
  • a print was generated using the recording medium generated in Example 1 .
  • Standard ink for a T300 webpress printer was utilized, and the ink was printed using a testbed printer that approximates the general webpress print conditions with drying.
  • the print was tested for gamut, black optical density (KOD), image gloss, and black-to-yellow ink bleed. These results are shown in Table 2.
  • Bleed was tested using an Image Analyzer from QEA Inc., and was also visually evaluated after printing. The bleed measurement was 4 mils, which is well below an acceptable level of less than 10 mils of color to color bleed. Color gamut and black optical density (KOD) were measured using an X-Rite 938
  • compositions (A and B) were generated utilizing the components shown in Table 3. Each of the compositions had a total solids amount of 44.5 wt%. Table 3
  • composition A and composition B were coated on a respective uncoated base via blade coating to form, respectively, recording medium A and recording medium B, each having a single ink receiving and coating layer on the uncoated base.
  • the respective compositions were coated at 7 gsm on 56 gsm of the respective uncoated bases.
  • Recording medium A and recording medium B were calendered according the examples disclosed herein using a heated 2 roll calender from Independent Machine Co., Fairfield, NJ. Recording medium A was calendered at 3500 psi
  • Recording medium B was calendered at 3500 psi (-1500 PLI) and at about 90°C for 3 passes.
  • the sheet gloss level of the calendered recording mediums A and B was measured at a 75° measurement angle using a Micro gloss 75, which is a gloss meter available from BYK-Gardner.
  • the sheet gloss for both recording medium A and recording medium B was 51 , which was well above a suitable sheet gloss level of 40. It is believed that the higher latex amount in recording medium B also improved the sheet gloss, thus requiring less calendering passes.
  • ranges provided herein include the stated range and any value or sub-range within the stated range.
  • a range from about 75 parts to about 85 parts should be interpreted to include not only the explicitly recited limits of about 75 parts to about 85 parts, but also to include individual values, such as 76 parts, 80 parts, 82.5 parts, etc., and sub-ranges, such as from about 77 parts to about 83 parts, from about 80 parts to about 84 parts, etc.
  • “about” is utilized to describe a value, this is meant to encompass minor variations (up to +/- 10%) from the stated value.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
  • Paper (AREA)

Abstract

Methods of improving sheet gloss are disclosed herein. A composition is established directly on a base to form a recording medium, where the composition includes modified calcium carbonate and precipitated calcium carbonate. The recording medium is exposed to a calendering process at a pressure ranging from about 1200 pressure per linear inch (PLI) to about 1500 PLI and at a temperature ranging from about 85C to about 95C. The calendering process is performed for a number of passes ranging from 2 to 5.

Description

METHODS OF IMPROVING SHEET GLOSS
BACKGROUND
The present disclosure relates generally to methods of improving sheet gloss.
Recent trends in digital printing technology include utilizing inkjet inks in high-speed digital commercial or industrial printers. Inkjet inks are often aqueous based inks, which contain a minor amount of colorant and a large amount of water and co-solvent(s). As such, in high-speed digital inkjet printing, it is desirable to utilize a medium having suitable absorption properties. The medium used in inkjet printing determines, at least in part, the quality of the image printed thereon. When the absorption properties of the medium are poor, the quality of the resulting image is often poor as well. In many instances, an ink-receiving layer is included which improves the ink receptive properties of the medium.
BRIEF DESCRIPTION OF THE DRAWING
Features and advantages of examples of the present disclosure will become apparent by reference to the following detailed description and drawing.
Fig. 1 is a flow diagram illustrating an example of a method for improving sheet gloss.
DETAILED DESCRIPTION
Examples of the recording medium disclosed herein include one layer that functions as both an ink-receiving layer and a coating layer. The single ink- receiving and coating layer imparts a high ink adsorption rate (i.e., fast absorption of the liquid component in the ink, e.g. water) and exhibits improvements in image qualities after printing, including reduced graininess, improved image gloss, low ink bleed, low mottle, high gamut, and high black optical density. Examples of the recording medium disclosed herein are also subjected to a calendering process that utilizes specific pressure and temperature conditions, which are relatively high compared to standard calendering conditions. The level of calendering disclosed herein unexpectedly results in the recording medium having desirable print quality (e.g., low ink bleed, etc.) as well as desirably high (>40) sheet gloss levels. The single ink-receiving and coating layer disclosed herein achieved desirable gloss without a second layer (i.e., without an additional ink-receiving layer), and also provides desirable absorption after the calendering process is performed, which is in contrast to other recording sheets that suffer from poor absorption as a result of over calendering.
The recording medium includes a base. The base is a supporting substrate upon which the single ink-receiving and coating layer is formed. The base may be in the form of a sheet or a continuous web suitable for use in an inkjet printer. In one example, the base is a base paper manufactured from cellulose fibers. More specifically, the base paper may be produced from chemical pulp, mechanical pulp, thermal mechanical pulp and/or the combination of chemical and mechanical pulp. The base paper may also include additives, such as internal sizing agents and/or fillers. When utilized, the internal sizing agents are added to the pulp before it is converted into a paper web or substrate. Any suitable internal sizing agent may be selected, such as alkyl succinic anhydride, diketene, and rosin. Any suitable filler may also be selected, such as calcium carbonate, talc, clay, kaolin, titanium dioxide and combinations thereof. Examples of substrates other than base paper include cloth, nonwoven fabric, felt, and synthetic (non-cellulosic) papers. The base may be an uncoated raw base or a pre-coated base. The pre-coated base includes a pre-coating that is established on the raw base. The pre-coating may include any of a variety of inorganic pigment coatings applied in-line or offline using a size press, a gateroll press or any variety of blade coater. As an example, a pre- coat may be from about 5 gsm to about 10 gsm of calcium carbonate with a binder, such as polyvinyl alcohol or latex.
The single ink-receiving and coating layer is established directly on the base (i.e., on the raw base or on the pre-coating of the base). It is to be understood that this single layer is one layer that contains the coating composition disclosed herein. The single layer may have any desirable thickness, and in some instances may include multiple sub-layers to achieve the desirable thickness. However, the single layer acts as both the ink-receiving layer and the coating layer, and thus the recording medium does not include any other layers on the single layer. As such, the single ink-receiving and coating layer is the outermost layer of the recording medium.
The single ink-receiving medium and coating layer is made up of an aqueous pigmented dispersion composition that includes both modified calcium carbonate (MCC) and precipitated calcium carbonate (PCC).
The modified calcium carbonate used herein refers to pre-existing calcium carbonate (ground or precipitated) which has been post-treated with phosphoric acid and CO2 gas as well as a variety of other additives (such as soluble silicates) for the purpose of altering both the structure and the chemical composition of the original particle. The post-treatment of the calcium carbonate results in a pigment particle made up of a shell of various calcium compounds surrounding a core of the original carbonate molecule. Suitable MCC material may take the form of a slurry dispersion of structured calcium minerals, which include primarily calcium
carbonate (CaCOs), calcium phosphate and/or calcium silicate (Ca2SiO4). Calcium phosphate includes compounds containing calcium ions together with phosphate ions, and may include octacalcium phosphate (Ca8H2(PO4)6-5H2O) or other forms of calcium phosphate. An example of octacalcium phosphate is OMYAJET® 5010 available from Omya Inc. The amount of modified calcium carbonate pigment included in the composition ranges from about 15 dry parts to about 25 dry parts of the total dry parts of the composition. Precipitated calcium carbonate pigments may be obtained by calcining crude calcium oxide. Water is added to obtain calcium hydroxide, and then carbon dioxide is passed through the solution to precipitate the desired calcium carbonate. Precipitated calcium carbonate is commercially available, for example, under the tradename OPACARB® A40 (Minerals Technologies Inc.). In an example, the amount of precipitated calcium carbonate used in the composition ranges from about 75 dry parts to about 85 dry parts.
The total amount of inorganic pigments present in the coating composition ranges from about 60 wt.% to about 90 wt.%. "Wt.%" as used herein refers to dry weight percentage based on the total dry weight of the coating composition.
In an example, the composition excludes clay. The composition disclosed herein develops desirable gloss (due, at least in part, to the calendering process) and maintains sufficient coating openness for adequate absorption without the use of clay. However, in another example, clay, such as calcined clay, kaolin clay, or other phyllosilicates, may be included. Clay(s), in some instances, may be added to further increase the gloss and/or increase the absorption rate. As an example, calcined clay may be desirable to further enhance the absorption rate of the single ink-receiving and coating layer. In an example in which calcined clay(s) is/are added, for example, to provide additional porosity, the calcined clay(s) may be added in an amount ranging from about 0.5 dry parts to about 10 dry parts (based on the total parts of inorganic particles). In another example in which uncalcined clay(s) is/are added, for example, to boost gloss, the uncalcined clay(s) may be added in an amount ranging from about 0.5 dry parts to about 5 dry parts (based on total parts of inorganic particles).
The coating composition disclosed herein may also include a polymeric co- pigment. Examples of suitable polymeric co-pigments include plastic pigments (e.g., polystyrene, polymethacrylates, polyacrylates, copolymers thereof, and/or combinations thereof). Suitable solid spherical plastic pigments are commercially available from The Dow Chemical Company, e.g., DPP 756A and HS 3020. The amount of polymeric co-pigment in the coating composition may be in the range of 1 dry part to 10 dry parts based on 100 parts of inorganic pigments. In an example, the amount of polymeric co-pigment or plastic pigments ranges from about 3 dry parts to about 7 dry parts per 100 parts of inorganic pigments.
The coating composition also includes a binder. The binder(s) may be hydrophilic or water-soluble binders such as polyvinyl alcohol (e.g., MOWIOL® 15- 98, Kuraray) and derivatives thereof (e.g. carboxylated polyvinyl alcohol, sulfonated polyvinyl alcohol, acetoacetylated polyvinyl alcohol, and mixtures thereof), polystyrene-butadiene, polyethylene-polyvinyacetate copolymers, starch, gelatin, casein, alginates, carboxycellulose materials, polyacrylic acid and derivatives thereof, polyvinyl pyrrolidone, casein, polyethylene glycol, polyurethanes (for example, a modified polyurethane resin dispersion), polyamide resins (for instance, an epichlorohydrin-containing polyamide), a polyvinyl pyrrolidone-vinyl acetate) copolymer, a polyvinyl acetate-ethylene) copolymer, a polyvinyl alcohol-ethylene oxide) copolymer, styrene acrylate copolymer, resin latex, styrene butadiene latex (e.g., STYRONAL® D628, BASF Corp.), or a poly(butadiene-styrene-acrylonitrile) latex (e.g., XZ96750 , Styron Corp.), or the like, or mixtures thereof. In general, the binder is present in an amount sufficient to bind the inorganic pigments. In some examples, the total amount of binder is present in an amount ranging from about 5 to about 20 parts based on 100 parts of inorganic pigments. In an example, the coating composition includes from about 3 dry parts to about 10 dry parts of a latex binder and from about 2 dry parts to about 7 dry parts of a polyvinyl alcohol binder.
The coating composition may also include other coating additives such as calcium chloride, surfactants, rheology modifiers, defoamers, optical brightening agents, sheet color adjusting agents, biocides, pH controlling agents, dyes (e.g., violet dye), and other additives for further enhancing the properties of the coating. The total amount of coating additives may be in the range of 0 to about 10 parts based on 100 parts of inorganic pigments. In an example, the coating composition includes from about 8 dry parts to about 10 dry parts of calcium chloride (CaC ), from about 0.3 dry parts to about 0.4 dry parts of a defoaming agent (e.g.,
AGITAN™ 103, Munzing), from about 0.004 dry parts to about 0.006 dry parts of a sheet color adjusting agent (e.g., CATEREN™ Violet 79732, Clariant), and from about 0.4 dry parts to about 0.6 dry parts of an optical brightening agent (e.g., TINOPAL®, BASF Corp.).
Water is added to the inorganic pigments and other components in order to form the coating composition. The amount of water added may depend, at least in part, on the desirable solids percentage for the final coating composition. In an example, enough water is added to obtain composition including from about 40% solids to about 55% solids.
Referring now to Fig. 1 , at reference numeral 100, the composition is established directly on the base to form the recording medium. The coating composition may be applied to one or both opposing sides of the base. The double-side coated recording medium has a sandwich structure, i.e., both sides of the supporting base are coated with the same coating, and both sides may be printed with images or text. The coat weight of the single ink-receiving and coating layer may be in the range of about 4 gsm (grams per square meter) to 45 gsm per side. In an example, the coat weight of the single ink-receiving and coating layer may be in the range of about 4.5 gsm to about 30 gsm per side. The coating composition of the present disclosure may be applied to the base using any one of a variety of suitable coating methods, such as blade coating, jet blade coating, air knife coating, metering rod coating, curtain coating, or another suitable technique. To obtain a low-cost coated medium for inkjet printing, it may be desirable to have relatively low manufacturing costs in addition to formulation material costs.
Therefore, it may be desirable to use a low-cost coating method, like blade coating or metering rod coating, and run the coating process at high speed. For a double- side coated recording medium, depending on the set-up of production machine in a mill, both sides of the base may be coated during a single manufacture pass, or alternatively, each side may be coated in separate passes.
After the coating composition is deposited, the coated base is then subjected to a drying process to remove water and other volatile components from the ink-receiving and coating layer and the base. The drying means includes, but is not limited to, infrared (IR) dryers, hot surface rolls, and hot air flotation dryers.
After coating and drying, the recording medium is calendered to increase glossiness (reference numeral 102 in Fig. 1 ). Calendering may be accomplished using an on-line or an off-line calender machine, which may be a soft-nip calender or a supercalender. The rolls (e.g., a stainless steel roll positioned against a cotton-filled backing roll) in a calender machine may or may not be heated. The calendering process disclosed herein is performed at a pressure ranging from about 1200 PLI (pressure per linear inch) to about 1500 PLI (i.e., about 3000 psi (pressure per square inch) to about 3500 psi) and at a temperature ranging from about 85°C to about 95°C. The calendering process is performed for a number of passes ranging from 2 to 5 (reference numeral 104 in Fig. 1 ). This calendering process unexpectedly results in desirable sheet gloss (>40), while not sacrificing printability and print quality. In particular, it has been found that the calendering process disclosed herein does not negatively impact the printability because the process does not close up the structure of the coating.
To further illustrate the present disclosure, examples are given herein. It is to be understood that these examples are provided for illustrative purposes and are not to be construed as limiting the scope of the disclosed example(s).
EXAMPLES
Example 1
A composition was generated utilizing the components shown in Table 1 The composition had a total solids amount of 44.5 wt%. Table 1
The composition was coated on a pre-coated offset base via blade coating to form a recording medium having a single ink receiving and coating layer on the pre-coated base. The composition was coated at 7 gsm on 90 gsm of the pre- coated base.
The recording medium was calendered according the examples disclosed herein using a heated 2 roll calender from Independent Machine Co., Fairfield, NJ. In particular, the recording medium was calendered at 3000 psi (~ 1286 PLI) and at about 90°C for 2 passes.
The sheet gloss level of the calendered recording medium was measured at a 75° measurement angle using a Micro gloss 75, which is a gloss meter available from BYK-Gardner. The sheet gloss in this example was 60, which was well above a suitable sheet gloss level of 40. Example 2
A print was generated using the recording medium generated in Example 1 . Standard ink for a T300 webpress printer was utilized, and the ink was printed using a testbed printer that approximates the general webpress print conditions with drying. The print was tested for gamut, black optical density (KOD), image gloss, and black-to-yellow ink bleed. These results are shown in Table 2.
Table 2
Bleed was tested using an Image Analyzer from QEA Inc., and was also visually evaluated after printing. The bleed measurement was 4 mils, which is well below an acceptable level of less than 10 mils of color to color bleed. Color gamut and black optical density (KOD) were measured using an X-Rite 938
transmission/reflection densitometer. KOD was measured using DEN A settings. Gamut was calculated by measuring the L*a*b* values using D65/20 settings. The image gloss level was measured at a 75° measurement angle using the Micro gloss 75. The image gloss in this example was 61 .
These values represent acceptable levels of optical density and image gloss similar to sheet gloss (see Example 1 ). In addition, the ink bleed value as measured by the bleed of black into yellow ink was very low and indicated a very good print.
Example 3
Two compositions (A and B) were generated utilizing the components shown in Table 3. Each of the compositions had a total solids amount of 44.5 wt%. Table 3
Each of composition A and composition B was coated on a respective uncoated base via blade coating to form, respectively, recording medium A and recording medium B, each having a single ink receiving and coating layer on the uncoated base. The respective compositions were coated at 7 gsm on 56 gsm of the respective uncoated bases.
Recording medium A and recording medium B were calendered according the examples disclosed herein using a heated 2 roll calender from Independent Machine Co., Fairfield, NJ. Recording medium A was calendered at 3500 psi
(-1500 PLI) and at about 90°C for 5 passes. Recording medium B was calendered at 3500 psi (-1500 PLI) and at about 90°C for 3 passes.
The sheet gloss level of the calendered recording mediums A and B was measured at a 75° measurement angle using a Micro gloss 75, which is a gloss meter available from BYK-Gardner. The sheet gloss for both recording medium A and recording medium B was 51 , which was well above a suitable sheet gloss level of 40. It is believed that the higher latex amount in recording medium B also improved the sheet gloss, thus requiring less calendering passes.
It is to be understood that the ranges provided herein include the stated range and any value or sub-range within the stated range. For example, a range from about 75 parts to about 85 parts should be interpreted to include not only the explicitly recited limits of about 75 parts to about 85 parts, but also to include individual values, such as 76 parts, 80 parts, 82.5 parts, etc., and sub-ranges, such as from about 77 parts to about 83 parts, from about 80 parts to about 84 parts, etc. Furthermore, when "about" is utilized to describe a value, this is meant to encompass minor variations (up to +/- 10%) from the stated value.
While several examples have been described in detail, it will be apparent to those skilled in the art that the disclosed examples may be modified. Therefore, the foregoing description is to be considered non-limiting.

Claims

What is claimed is:
1 . A method of improving sheet gloss, comprising:
establishing a composition directly on a base to form a recording medium, the composition including modified calcium carbonate and precipitated calcium carbonate;
exposing the recording medium to a calendering process at a pressure ranging from about 1200 pressure per linear inch (PLI) to about 1500 PLI and at a temperature ranging from about 85°C to about 95°C; and
performing the calendering process for a number of passes ranging from 2 to 5.
2. The method as defined in claim 1 wherein the pressure is about 1286 PLI, the temperature is about 90°C, and the number of passes is 2.
3. The method as defined in claim 2 wherein the sheet gloss of the calendered recording medium is about 60 measured at 75° measurement angle.
4. The method as defined in claim 1 wherein the pressure is about 1500 PLI, the temperature is about 90°C, and the number of passes is 3 or 5.
5. The method as defined in claim 4 wherein the sheet gloss of the calendered recording medium is greater than 40 measured at 75° measurement angle. 6. The method as defined in claim 1 , further comprising forming the composition to include:
75 to 85 dry parts of the precipitated calcium carbonate;
15 to 25 dry parts of the modified calcium carbonate;
3 to 10 dry parts latex binder;
2 to 7 dry parts polyvinyl alcohol binder; 3 to 7 dry parts plastic pigments;
8 to 10 dry parts calcium chloride;
0.3 to 0.4 dry parts of a defoaming agent;
0.004 to 0.006 dry parts of a sheet color adjusting agent; and
0.4 to 0.
6 dry parts of an optical brightening agent.
7. The method as defined in claim 6 wherein the forming of the composition includes excluding clay from the composition.
8. A recording medium, comprising:
a base; and
a single ink receiving and coating layer established on the base, the single ink receiving and coating layer including modified calcium carbonate and precipitated calcium carbonate;
the single ink receiving and coating layer being in direct contact with the base and also being an outermost layer of the recording medium;
and the recording medium having been exposed to a calendering process performed at a pressure ranging from about 1200 PLI to about 1500 PLI, at a temperature ranging from about 85°C to about 95°C, and for a number of passes ranging from 2 to 5.
9. The recording medium as defined in 8 wherein the base is a raw base paper or a pre-coated base paper.
10. The recording medium as defined in claim 8 wherein the single ink receiving and coating layer includes:
75 to 85 dry parts of the precipitated calcium carbonate;
15 to 25 dry parts of the modified calcium carbonate;
3 to 10 dry parts latex binder;
2 to 7 dry parts polyvinyl alcohol binder; 3 to 7 dry parts plastic pigments;
8 to 10 dry parts calcium chloride;
0.3 to 0.4 dry parts of a defoaming agent;
0.004 to 0.006 dry parts of a sheet color adjusting agent; and
0.4 to 0.6 dry parts of an optical brightening agent.
1 1 . The recording medium as defined in claim 10 wherein the single ink receiving and coating layer excludes clay.
12. The recording medium as defined in claim 8 wherein the recording medium exhibits a sheet gloss greater than 40 after the calendering process is performed.
13. The recording medium as defined in claim 8 wherein the modified calcium carbonate has a median pore size of about 0.05 nm.
EP11879159.9A 2011-11-29 2011-11-29 Methods of improving sheet gloss Not-in-force EP2785530B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2011/062352 WO2013105912A2 (en) 2011-11-29 2011-11-29 Methods of improving sheet gloss

Publications (3)

Publication Number Publication Date
EP2785530A2 true EP2785530A2 (en) 2014-10-08
EP2785530A4 EP2785530A4 (en) 2015-07-08
EP2785530B1 EP2785530B1 (en) 2017-08-23

Family

ID=48782041

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11879159.9A Not-in-force EP2785530B1 (en) 2011-11-29 2011-11-29 Methods of improving sheet gloss

Country Status (2)

Country Link
EP (1) EP2785530B1 (en)
WO (1) WO2013105912A2 (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3995745B2 (en) * 1996-12-27 2007-10-24 奥多摩工業株式会社 Method for producing light calcium carbonate / heavy calcium carbonate mixed aqueous slurry
US6287424B1 (en) * 1998-09-22 2001-09-11 International Paper Company Method for finishing paperboard to achieve improved smoothness
WO2001053893A1 (en) 2000-01-19 2001-07-26 S. D. Warren Services Company Multifunctional coated printing sheets for use in electrophotographic and offset printers
US6777075B2 (en) 2002-03-15 2004-08-17 S.D. Warren Services Company Burnish resistant printing sheets
FR2852600B1 (en) * 2003-03-18 2005-06-10 NEW MINERAL PIGMENT CONTAINING CALCIUM CARBONATE, AQUEOUS SUSPENSION CONTAINING SAME AND USES THEREOF
US7051883B2 (en) * 2003-07-07 2006-05-30 Reemay, Inc. Wetlaid-spunbond laminate membrane support
US8361572B2 (en) * 2009-10-30 2013-01-29 Hewlett-Packard Development Company, L.P. Coated medium for inkjet printing

Also Published As

Publication number Publication date
WO2013105912A2 (en) 2013-07-18
EP2785530A4 (en) 2015-07-08
EP2785530B1 (en) 2017-08-23
WO2013105912A3 (en) 2013-10-10

Similar Documents

Publication Publication Date Title
US8236393B2 (en) Inkjet recording material
US8361572B2 (en) Coated medium for inkjet printing
EP2142701B1 (en) Paper and method for making paper
CA2825968C (en) Glossy recording medium for inkjet printing
EP3126151B1 (en) Printable recording media
JP5778366B1 (en) Sublimation type inkjet printing transfer paper
US8821998B2 (en) Recording medium for inkjet printing
CA2868520C (en) Recording medium for inkjet printing
US8080292B2 (en) Coated paper for pigment-based inkjet printers
WO2016122485A1 (en) Printable recording media
US8900678B2 (en) Coated medium for inkjet printing and method of fabricating the same
EP2988948B1 (en) Printable recording media
WO2016122487A1 (en) Printable recording media
EP2785530B1 (en) Methods of improving sheet gloss
WO2016017313A1 (en) Coated paper for printing with industrial inkjet printers and printed-matter manufacturing method
JP2006281606A (en) Inkjet recording medium
EP2780170B1 (en) Inkjet recording material
US10875344B2 (en) Recording media
JP3965687B2 (en) Inkjet recording medium for pigment ink

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

17P Request for examination filed

Effective date: 20140520

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20150608

RIC1 Information provided on ipc code assigned before grant

Ipc: B41M 5/10 20060101AFI20150601BHEP

Ipc: B41M 5/124 20060101ALI20150601BHEP

Ipc: B41M 5/52 20060101ALI20150601BHEP

Ipc: B41M 5/00 20060101ALI20150601BHEP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011040998

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: B41M0005100000

Ipc: B41M0005520000

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RIC1 Information provided on ipc code assigned before grant

Ipc: B41M 5/52 20060101AFI20170217BHEP

Ipc: B41M 5/00 20060101ALI20170217BHEP

INTG Intention to grant announced

Effective date: 20170321

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): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602011040998

Country of ref document: DE

Representative=s name: SCHOPPE, ZIMMERMANN, STOECKELER, ZINKLER, SCHE, DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 920902

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170915

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011040998

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20170823

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 920902

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171123

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171223

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171124

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011040998

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

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

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

26N No opposition filed

Effective date: 20180524

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171129

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20171130

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171129

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20181023

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20181024

Year of fee payment: 8

Ref country code: FR

Payment date: 20181024

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20111129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602011040998

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170823

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20191129

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: 20191130

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20191129

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20200603