Inkjet printing apparatus and method for making flexographic printing masters

Information

  • Patent Grant
  • 8985019
  • Patent Number
    8,985,019
  • Date Filed
    Tuesday, December 1, 2009
    15 years ago
  • Date Issued
    Tuesday, March 24, 2015
    9 years ago
Abstract
A method for making a flexographic printing master includes the steps of providing a flexographic printing support; applying image-wise on the flexographic printing support subsequent layers of radiation curable liquid by an inkjet printing device whereby one or more applied layers are immobilized using a curing device before one or more subsequent layers are applied, such that a relief with a top hat profile is obtained; and grinding the relief so that the height DT of a top hat segment is reduced. An imaging apparatus includes structure to perform the above method.
Description
BACKGROUND OF THE INVENTION

1. Field of the Invention


The present invention relates to a method for making a flexographic printing master by inkjet printing and an imaging apparatus for performing the method.


2. Description of the Related Art


Flexography is commonly used for high-volume runs of printing on a variety of supports such as paper, paperboard stock, corrugated board, films, foils and laminates. Packaging foils and grocery bags are prominent examples.


Today flexographic printing forms are made by both analogue imaging techniques such as a UV exposure through a film mask, e.g. EP 1594005 (DUPONT), and digital imaging techniques which include:

    • direct laser engraving on flexographic printing form precursors, e.g. US 2004/0259022 (BASF);
    • UV exposure through a LAMS mask, e.g. U.S. Pat. No. 6,521,390 (BASF) and U.S. Pat. No. 7,226,709 (KODAK), wherein LAMS means Laser Ablative Mask System;
    • Mask-less direct UV or violet exposure by laser or LED, e.g. U.S. Pat. No. 6,806,018 (MACDERMID); and
    • Inkjet printing e.g. EP 1428666 A (AGFA), US 2004/0131778 A (AGFA) and US 2006/0055761 (AGFA).


EP 1428666 A (AGFA) discloses a method for making a flexographic printing form by jetting subsequent layers of a UV-curable liquid, having elastomeric properties after being cured. Before jetting the following layer each previous layer is immobilized by a UV curing step. This “layer after layer” recording technique allows the gradual building up of a flexographic printing master wherein the relief can be accurately controlled. Use can be made of different curable liquids or immobilisation steps to obtain different layer characteristics.


Advantages of such a method for preparing a flexographic printing master are the absence of any processing steps and the consumption of no more material as necessary to form a suitable relief image, i.e. the removal of non printing areas is no longer required.


However, several difficulties in controlling the printing surface of the reliefs formed via ink-jet printing can occur. The printing surface of a flexographic printing relief is important because of its role in ink reception from the anilox roller and subsequent transfer to the substrate. Flexography prints with a “kiss impression”, i.e. the least possible squeeze between printing form and substrate.


A flexographic printing form having a very smooth surface often produces printing results having relatively low ink densities in the centre of solid areas while the edges of these solids result in a larger ink density. Such problems can be resolved by incorporating a surface roughness during the flexographic printing master fabrication, e.g. by incorporation matting agents.


It must be clear that the topographic result of different layers of UV-curable liquids subsequently jetted on each other depends upon the drop volume and the spreading properties of the ink used. Especially in solid image areas and in the coarsest printing dots, the surface of the printed relief will be quite rough and uneven. A larger ink drop size in combination with bad spreading properties will intensify this effect. Also the time between jetting and curing has an influence on the surface evenness.


As the surface finish of the printed relief is very important in order to provide excellent printing results, it should be clear that a high surface unevenness can lead to an important loss in Dmax of the printed image and/or a lot of print mottle.


In creating small printing dots on the flexographic printing master, a dot profile will generally have a rounded top, resulting in a smaller printed dot size with the flexographic printing master. Another phenomenon which occurs in creating very small printing dots is the flow down of curable liquid when a next ink drop is deposited on top of such a small printing dot. As a result the smaller printing dots will be less high than larger printing dots or than the solid image areas and the image information of these small printing dots is not printed upon a substrate.


It is at present not clear which adaptations in image processing should be made to obtain an inkjet printing mode capable of resolving all of the above problems. A need exists for making flexographic printing masters by inkjet printing which exhibit high printing quality.


SUMMARY OF THE INVENTION

It was surprisingly found that the above cited problems on the topography of the relief could be solved in a simple manner to deliver excellent printing quality of the flexographic printing master by using a grinding process.


In order to overcome the problems described above, preferred embodiments of the present invention provide a method for making a flexographic printing master as defined below.


A preferred embodiment of the present invention provides an imaging apparatus to perform the above method.


The above and other elements, features, steps, characteristics and advantages of the present invention will become more apparent from the following detailed description of the preferred embodiments with reference to the attached drawings.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 shows a cross-section of a relief dot on a flexographic printing master having a regular profile.



FIG. 2 shows a cross-section of a relief dot on a flexographic printing master having a top hat profile.



FIG. 3 shows a cross-section of an imaging apparatus according to a preferred embodiment of the present invention for making a flexographic printing master.



FIG. 4 shows a cross-section of a relief dot on a flexographic printing master having a top hat profile with a rounded printing surface.



FIG. 5 shows a cross-section of a large relief dot on a flexographic printing master having a top hat profile with an uneven printing surface.



FIG. 6 shows a cross-section of a large relief dot and a small relief dot on a flexographic printing master both having a top hat profile but with different heights of the top hat segment.



FIG. 7 shows a cross-section of a preferred embodiment of the flexographic printing master.



FIG. 8 is a photograph of a flexographic printing result including interrupted lines of 70 μm width.



FIG. 9 is a photograph of a flexographic printing result including uninterrupted lines of 70 μm width.



FIG. 10 is a photograph of a flexographic printing result of dots obtained with a not grinded relief.



FIG. 11 is a photograph of a flexographic printing result of dots obtained with a grinded relief.



FIG. 12 shows a cross-section of an imaging apparatus according to a preferred embodiment of the present invention, wherein the imaging apparatus includes a laser (40) and a profilometer (41).





DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

A method for making a flexographic printing master comprising the steps of:


a) providing a flexographic printing support (1);


b) applying image-wise on the flexographic printing support (1) subsequent layers of radiation curable liquid by an inkjet printing device (32) whereby one or more applied layers are immobilized using a curing device (39) before one or more subsequent layers are applied, such that a relief with a top hat profile is obtained; and


c) grinding the relief so that the height DT of a top hat segment (23) is reduced.


In a preferred embodiment of the method for making a flexographic printing master according to the present invention each applied layer in step b) is immobilized using a curing device (39) before a subsequent layer is applied.


It is necessary that the flexographic printing master has a relief with a top hat profile. Such a top hat profile is well known to the skilled person in flexography. For example, EP 1428666 A (AGFA) discloses in FIG. 5 such a top hat profile made by inkjet printing.


Flexographic printing forms made by an analogue imaging technique such as a UV exposure through a mask results in a relief having a “regular” profile as shown in FIG. 1. It is not possible to make a relief having a “top hat” profile as shown in FIG. 2 by UV exposure through a mask. A relief having a “top hat” profile can only be made by laser engraving or by inkjet printing. The relief having a “regular” profile of FIG. 1 consists of a relief (2) on a flexographic printing support (1). The shoulder (4) of the relief (2) has a slope with a slope angle Θ which is created by light scattering in a photopolymerizable layer when exposing through a mask the flexographic printing precursor to UV light. The unexposed areas of the polymerizable layer are removed, for example, with a suitable solvent. The relief of such a flexographic printing master has the same height D over the whole surface, because the flexographic printing precursor uses a polymerizable layer of uniform thickness. The total height C of the flexographic printing master is called the caliper. The diameter DS of the printing surface (3) determines the dot size of a dot printed with the flexographic printing master.


With inkjet printing it is possible to obtain a relief having a “top hat” profile as shown in FIG. 2. Such a relief includes a sloped segment (21) printed on a flexographic printing support (1). On the plateau (22) of the sloped segment (21) a top hat segment (23) can be printed having a printing surface (3). The top hat segment (23) may have a diameter DS which is smaller than the diameter of the plateau (22), resulting in an area of the plateau having a width WT not covered by the top hat segment (23). Alternatively the diameter DS of the top hat segment (23) may match the diameter of the plateau. In the latter the width WT of the plateau is equal to zero. The top hat segment (23) has a certain height DT, which is preferably between 10 to 500 μm high, more preferably 20 to 200 μm high. The advantage of a top hat profile is that in rubbing off material, e.g. by wear of the flexographic printing master, no physical growth in dot size or broadening of lines is observed, whereas physical growth in dot size or line broadening is observed when using a relief having a “regular” profile as shown by FIG. 1. Preferably the sloped segment (21) made by inkjet printing also has a shoulder (4) with a slope angle Θ. This results in a more robust flexographic printing master. A flexographic printing master can be made wherein the slope angle Θ is equal to 90° C., in which case DT is equal to D and the sloped segment height DB is equal to zero. However, such a profile is not preferred, especially not when the relief includes small dots or thin lines. These small dots and thin lines are very vulnerable and can be easily broken off during flexographic printing.


A relief on a flexographic printing master generally comprises relief dots having different diameters. In inkjet printing a large relief dot (61) and a small relief dot (62) generally a difference in caliper is seen, as shown in FIG. 6. The smaller relief dots are less high than the larger relief dots by a difference in height d(DT), as shown in FIG. 6 between the top hat segments of the large relief dot (61) and the small relief dot (62). Grinding of such a relief leads to a relief wherein all relief dots and lines have the same caliper. Flexographic printing with such a grinded relief results in images wherein also the small image details are present.


In a preferred embodiment, the method according to the present invention delivers in the printing step b) a relief on the flexographic printing support with at least two top hat profiles having a different relief depth D; and the relief is grinded in step c) so that the difference in relief depth D of the two top hat profiles is reduced, preferably to the same caliper.


The method according to a preferred embodiment of the present invention preferably has a relief with a top hat profile wherein the chemical composition of the sloped segment differs from the chemical composition of the top hat segment. In a preferred embodiment the top hat segment has a Shore A hardness which is higher than that of the sloped segment.


In a preferred embodiment of the method for making a flexographic printing master, the relief includes a so-called “mesa relief” as shown by the flexographic printing master (250) in FIG. 7. The layers (212) together define a “mesa relief”. Such a mesa relief is only present in those parts of the flexographic printing master comprising image features such as text, graphics and halftone images. In extended areas where such image features are absent, there is no mesa relief.


The presence of a mesa relief in image areas is optional but preferable. A mesa relief has a height (242) in a range from 50 μm to 1 mm, for example 0.5 mm.


The layers (210), (211) and (212) in FIG. 7, which may differ in chemical composition, define the actual printing relief of the flexographic printing master. The top layer (230) corresponds with a halftone bitmap that defines the image that is to be printed by the printing master. The layers (210), which may differ in chemical composition, are preferably identical in shape and size as the top layer (230), producing a vertical relief slope and defining a “top hat segment”. Such a top hat may have a height (240) between 10 and 500 μm and preferably between 25 and 200 μm. A vertical relief slope for a top hat segment has the advantage that the printing surface (230) remains consistent during printing, even when pressure variations occur between the print master and the anilox roller or between the print master and the printable substrate, or when the printing master wears off.


The intermediate layers (211), together forming a sloped segment, are preferably printed with a slope having an angle (235) that is less than 90 degrees. The angle can be between 25 and 75 degrees, preferably between 40 and 60 degrees, for example 50 degrees. The angle (235) can be controlled by controlling the height (241) of the individual layers, their number and the difference in size between subsequent layers.


Using a lower slope angle (235) has the advantage that small features on the print master will suffer less from buckling. The total height (241) of the intermediate layers (211) is for example between 30 μm and 700 μm, preferably between 50 μm and 250 μm.


In a more preferred embodiment of the current invention, the intermediate layers (210), (211) and (212) are printed in multiple passes with an ink jet printer that jets a radiation curable liquid in combination with a curing device. Each intermediate layer is solidified by a curing device immediately after printing. Especially the upper layer (232) of the mesa relief is preferably only partially cured for ensuring a good adhesion with the lowest intermediate layer (231) of the sloped segment (211). Optionally a final curing step including UV-C is carried out to further harden the layers after all of them have been printed.


The mesa relief is preferably printed on an elastomeric support floor (220) that provides the necessary resilience to the flexographic printing master. Such an elastomeric floor can be obtained by layer-wise spraying or jetting a radiation curable liquid on the support and curing the layers by a UV curing source. The thickness (243) of an elastomeric floor (220) is preferably between 0.3 mm and 2 mm.


The elastomeric floor (220) may itself be supported by a support (200). A support (200) of a sheet form typically has a thickness (244) from 0.005 to 0.127 cm. A preferred thickness (244) for the sheet form is 0.007 to 0.040 cm. A sleeve form typically has a wall thickness (244) from 0.1 to 1 mm for thin sleeves and from 1 to as much as 100 mm for other sleeves. The selection of the thickness (244) depends upon the application.


Radiation Curable Liquids


The radiation curable liquid is preferably curable by actinic radiation which can be UV light, IR light or visible light. Preferably the radiation curable liquid is a UV curable liquid.


The radiation curable liquid preferably contains at least a photo-initiator and a polymerizable compound. The polymerizable compound can be a monofunctional or polyfunctional monomer, oligomer or pre-polymer or a combination thereof.


The radiation curable liquid may be a cationically curable liquid but is preferably a free radical curable liquid.


The free radical curable liquid preferably contains substantially acrylates rather than methacrylates for obtaining a high flexibility of the applied layer. Also the functionality of the polymerizable compound plays an important role in the flexibility of the applied layer. Preferably a substantial amount of monofunctional monomers and oligomers are used.


In a preferred embodiment of the present invention, the radiation curable liquid includes:


a) a photoinitiator; and


b) a polymerizable compound selected from the group consisting of lauryl acrylate, polyethyleneglycol diacrylate, polyethylene glycol dimethacrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, propoxylated neopentylglycol diacrylate, alkoxylated hexanediol diacrylate, isobornylacrylate, isodecyl acrylate, hexane diol diacrylate, caprolacton acrylate and urethane acrylates.


In a more preferred embodiment of the present invention, the radiation curable liquid includes an aliphatic urethane acrylate. Aromatic type urethane acrylates are less preferred.


In an even more preferred embodiment, the urethane acrylate is a urethane monoacrylate. Commercial examples include GENOMER™ 1122 and EBECRYL™ 1039.


The flexibility of a given urethane acrylate can be enhanced by increasing the linear molecular weight between crosslinks. Polyether type urethane acrylates are for flexibility also more preferred than polyester type urethane acrylates.


Preferably the radiation curable liquid does not include amine modified polyether acrylates which reduce the flexibility of the cured layer.


An elastomer or a plasticizer is preferably present in the radiation curable liquid for improving desired flexographic properties such as flexibility and elongation at break.


The radiation curable liquid may contain a polymerization inhibitor to restrain polymerization by heat or actinic radiation.


The radiation curable liquid may contain at least one surfactant for controlling the spreading of the liquid.


The radiation curable liquid may further contain at least one colorant for increasing contrast of the image on the flexographic printing master.


The radiation curable liquid may further contain at least one acid functionalized monomer or oligomer.


The radiation curable liquid preferably has a viscosity at a shear rate of 100 s−1 and at a temperature between 15 and 70° C. of not more than 100 mPa·s, preferably less than 50 mPa·s, and more preferably less than 15 mPa·s.


Monofunctional Monomers


Any polymerizable monofunctional monomer commonly known in the art may be employed. Particular preferred polymerizable monofunctional monomers are disclosed in paragraphs [0054] to [0058] of EP 1637926 A (AGFA).


Two or more monofunctional monomers can be used in combination.


The monofunctional monomer preferably has a viscosity smaller than 30 mPa·s at a shear rate of 100 s−1 and at a temperature between 15 and 70° C.


Polyfunctional Monomers and Oligomers


Any polymerizable polyfunctional monomer and oligomer commonly known in the art may be employed. Particular preferred polyfunctional monomers and oligomers are disclosed in paragraphs [0059] to [0063] of EP 1637926 A (AGFA).


Two or more polyfunctional monomers and/or oligomers can be used in combination.


The polyfunctional monomer or oligomer preferably has a viscosity larger than 50 mPa·s at a shear rate of 100 s−1 and at a temperature between 15 and 70° C.


Acid Functionalized Monomers and Oligomers


Any polymerizable acid functionalized monomer and oligomer commonly known in the art may be employed. Particular preferred acid functionalized monomers and oligomers are disclosed in paragraphs [0066] to [0070] of EP 1637926 A (AGFA).


Photo-Initiators


The photo-initiator, upon absorption of actinic radiation, preferably UV-radiation, forms free radicals or cations, i.e. high-energy species inducing polymerization and crosslinking of the monomers and oligomers in the radiation curable liquid.


A preferred amount of photo-initiator is 1 to 10% by weight, more preferably 1 to 7% by weight, of the total radiation curable liquid weight.


A combination of two or more photo-initiators may be used. A photo-initiator system, comprising a photo-initiator and a co-initiator, may also be used. A suitable photo-initiator system comprises a photo-initiator, which upon absorption of actinic radiation forms free radicals by hydrogen abstraction or electron extraction from a second compound, the co-initiator. The co-initiator becomes the actual initiating free radical.


Irradiation with actinic radiation may be realized in two steps, each step using actinic radiation having a different wavelength and/or intensity. In such cases it is preferred to use 2 types of photo-initiators, chosen in function of the different actinic radiation used.


Suitable photo-initiators are disclosed in paragraphs [0077] to [0079] of EP 1637926 A (AGFA).


Inhibitors


Suitable polymerization inhibitors include phenol type antioxidants, hindered amine light stabilizers, phosphor type antioxidants, hydroquinone monomethyl ether commonly used in (meth)acrylate monomers, and hydroquinone, methylhydroquinone, t-butylcatechol, pyrogallol may also be used. Of these, a phenol compound having a double bond in molecules derived from acrylic acid is particularly preferred due to its having a polymerization-restraining effect even when heated in a closed, oxygen-free environment. Suitable inhibitors are, for example, SUMILIZER™ GA-80, SUMILIZER™ GM and SUMILIZER™ GS produced by Sumitomo Chemical Co., Ltd.


Since excessive addition of these polymerization inhibitors will lower the sensitivity to curing of the radiation curable liquid, it is preferred that the amount capable of preventing polymerization be determined prior to blending. The amount of a polymerization inhibitor is generally between 200 and 20,000 ppm of the total radiation curable liquid weight.


Oxygen Inhibition


Suitable combinations of compounds which decrease oxygen polymerization inhibition with radical polymerization inhibitors are: 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butane-1 and 1-hydroxy-cyclohexyl-phenyl-ketone; 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone; 2-methyl-1[4-(methylthio)phenyl]-2-morpholino-propane-1-on and diethylthioxanthone or isopropylthioxanthone; and benzophenone and acrylate derivatives having a tertiary amino group, and addition of tertiary amines. An amine compound is commonly employed to decrease an oxygen polymerization inhibition or to increase sensitivity. However, when an amine compound is used in combination with a high acid value compound, the storage stability at high temperature tends to be decreased. Therefore, specifically, the use of an amine compound with a high acid value compound in ink-jet printing should be avoided.


Synergist additives may be used to improve the curing quality and to diminish the influence of the oxygen inhibition. Such additives include, but are not limited to ACTILANE™ 800 and ACTILANE™ 725 available from AKZO NOBEL, EBECRYL™ P115 and EBECRYL™ 350 available from UCB CHEMICALS and CD 1012, CRAYNOR™ CN 386 (amine modified acrylate) and CRAYNOR™ CN 501 (amine modified ethoxylated trimethylolpropane triacrylate) available from CRAY VALLEY.


The content of the synergist additive is in the range of 0 to 50% by weight, preferably in the range of 5 to 35% by weight, based on the total weight of the radiation curable liquid.


Plasticizers


Plasticizers are usually used to improve the plasticity or to reduce the hardness of adhesives, sealing compounds and coating compositions. Plasticizers are liquid or solid, generally inert organic substances of low vapour pressure.


Suitable plasticizers are disclosed in paragraphs [0086] to [0089] of EP 1637926 A (AGFA).


The amount of plasticizer is preferably at least 5% by weight, more preferably at least 10% by weight, each based on the total weight of the radiation curable liquid.


The plasticizers may have molecular weights up to 30,000 but are preferably liquids having molecular weights of less than 5,000.


Elastomers


The elastomer may be a single binder or a mixture of various binders. The elastomeric binder is an elastomeric copolymer of a conjugated diene-type monomer and a polyene monomer having at least two non-conjugated double bonds, or an elastomeric copolymer of a conjugated diene-type monomer, a polyene monomer having at least two non-conjugated double bonds and a vinyl monomer copolymerizable with these monomers.


Preferred elastomers are disclosed in paragraphs [0092] and [0093] of EP 1637926 A (AGFA).


Surfactants


The surfactant(s) may be anionic, cationic, non-ionic, or zwitter-ionic and are usually added in a total quantity below 20% by weight, more preferably in a total quantity below 10% by weight, each based on the total radiation curable liquid weight.


A fluorinated or silicone compound may be used as a surfactant, however, a potential drawback is bleed-out after image formation because the surfactant does not cross-link. It is therefore preferred to use a copolymerizable monomer having surface-active effects, for example, silicone-modified acrylates, silicone modified methacrylates, fluorinated acrylates, and fluorinated methacrylates.


Colorants


Colorants may be dyes or pigments or a combination thereof. Organic and/or inorganic pigments may be used.


Suitable dyes and pigments include those disclosed by ZOLLINGER, Heinrich. Color Chemistry: Syntheses, Properties, and Applications of Organic Dyes and Pigments. 3rd edition. WILEY-VCH, 2001. ISBN 3906390233. p. 550.


Suitable pigments are disclosed in paragraphs [0098] to [0100] of EP 1637926 A (AGFA).


The pigment is present in the range of 0.01 to 10% by weight, preferably in the range of 0.1 to 5% by weight, each based on the total weight of radiation curable liquid.


Solvents


The radiation curable liquid preferably does not contain an evaporable component, but sometimes, it can be advantageous to incorporate an extremely small amount of a solvent to improve adhesion to the ink-receiver surface after UV curing. In this case, the added solvent may be any amount in the range of 0.1 to 10.0% by weight, preferably in the range of 0.1 to 5.0% by weight, each based on the total weight of radiation curable liquid.


Humectants


When a solvent is used in the radiation curable liquid, a humectant may be added to prevent the clogging of the nozzle, due to its ability to slow down the evaporation rate of radiation curable liquid.


Suitable humectants are disclosed in paragraph [0105] of EP 1637926 A (AGFA).


A humectant is preferably added to the radiation curable liquid formulation in an amount of 0.01 to 20% by weight of the formulation, more preferably in an amount of 0.1 to 10% by weight of the formulation.


Biocides


Suitable biocides include sodium dehydroacetate, 2-phenoxyethanol, sodium benzoate, sodium pyridinethion-1-oxide, ethyl p-hydroxy-benzoate and 1,2-benzisothiazolin-3-one and salts thereof. A preferred biocide for the radiation curable liquid suitable for the method for manufacturing a flexographic printing master according to a preferred embodiment of the present invention, is PROXEL™ GXL available from ZENECA COLOURS.


A biocide is preferably added in an amount of 0.001 to 3% by weight, more preferably in an amount of 0.01 to 1.00% by weight, each based on radiation curable liquid.


Preparation of Radiation Curable Liquids


The radiation curable liquid may be prepared as known in the art by mixing or dispersing the ingredients together, optionally followed by milling, as described for example in paragraphs [0108] and [0109] of EP 1637926 A (AGFA).


Flexographic Printing Supports


Two forms of flexographic printing supports can be distinguished: a sheet form and a cylindrical form (sleeve). Sleeve forms provide improved registration accuracy and faster change-over-time on press. Furthermore, sleeves may be well-suited for mounting on an inkjet printer having a rotatable drum. Seamless sleeves have applications in the flexographic printing of continuous designs such as in wallpaper, decoration, gift wrapping paper and packaging.


The term “flexographic printing support”, as used in the preferred embodiments of the present invention, encompasses two types of support:


1) a support without elastomeric layers on its surface; and


2) a support with one or more elastomeric layers on its surface.


In a preferred embodiment, the flexographic printing support is a sleeve, which encompasses a basic sleeve and a flexographic printing sleeve. The term “basic sleeve” means a sleeve without elastomeric layers on its outer surface, while the term “flexographic printing sleeve” means a basic sleeve having one or more elastomeric layers on its outer surface.


Although here below the type of materials, the wall thicknesses, etc are written for sleeves, the same type of materials, wall thicknesses, etc can be used for flexographic printing supports having a sheet form.


Basic Sleeves


The basic sleeve can be any material that is conventionally used to prepare flexographic printing masters. For good printing results, a dimensionally stable support is required. Basic sleeves, often also called a sleeve base, ordinarily consist of composites, such as epoxy or polyester resins reinforced with glass fibre or carbon fibre mesh. Metals, such as steel, aluminium, copper and nickel, and hard polyurethane surfaces (e.g. durometer 75 Shore D) can also be used.


The sleeve may be formed from a single layer or multiple layers of flexible material, as for example disclosed by US 2002/0046668 (ROSSINI). Flexible sleeves made of polymeric films can be transparent to ultraviolet radiation and thereby accommodate backflash exposure for building a floor in the cylindrical printing element. Multiple layered sleeves may include an adhesive layer or tape between the layers of flexible material. Preferred is a multiple layered sleeve as disclosed in U.S. Pat. No. 5,301,610 (DU PONT). The sleeve may also be made of non-transparent, actinic radiation blocking materials, such as nickel or glass epoxy.


Depending upon the type of tubing and the number of layers of mesh applied, the wall thickness of these sleeve bases varies. The sleeve typically has a wall thickness from 0.1 to 1.5 mm for thin sleeves and from 2 mm to as high as 100 mm for other sleeves.


For thick sleeves often combinations of a hard polyurethane surface with a low-density polyurethane foam as an intermediate layer combined with a fibreglass reinforced composite core are used as well as sleeves with a highly compressible surface present on a sleeve base.


Depending upon the specific application, sleeve bases may be conical or cylindrical. Cylindrical sleeve bases are used primarily in flexographic printing.


As press speeds have increased, press bounce has become a more frequent problem. Various approaches can be taken to reduce press bounce, including the use of cushioned sleeves. Sleeves come in different constructions, e.g. with a hard or a compressible core or surface, with varying wall thicknesses.


The basic sleeve or flexographic printing sleeve is stabilized by fitting it over a steel roll core known as an air mandrel or air cylinder. Air mandrels are hollow steel cores which can be pressurized with compressed air through a threaded inlet in the end plate wall. Small holes drilled in the cylindrical wall serve as air outlets. The introduction of air under high pressure permits it to float into position over an air cushion. Certain thin sleeves are also expanded slightly by the compressed air application, thereby facilitating the gliding movement of the sleeve over the roll core.


Foamed adapter or bridge sleeves are used to “bridge” the difference in diameter between the air-cylinder and a flexographic printing sleeve containing the printing relief. The diameter of a sleeve depends upon the required repeat length of the printing job.


Flexographic Printing Sleeves


A flexographic printing sleeve is a basic sleeve provided with one or more elastomeric layers. The elastomeric layers may be any material that is conventionally used to prepare flexographic printing masters. The elastomeric layers are preferably partially or fully cured photopolymer layers, but can also be rubber or polyurethane layers. It is also possible to use a partially or fully cured conventional UV exposure flexographic printing form precursor as flexographic printing sleeve. A wide variety of such conventional flexographic printing form precursors are commercially available.


A printing relief can be formed in several ways on the flexographic printing sleeve. In a preferred embodiment the relief is formed by inkjet printing on the one or more elastomeric layers already present as an “elastomeric floor”. In the latter, the one or more elastomeric layers are preferably partially cured layers to enhance the adhesion of the relief jetted onto the elastomeric layers. Alternatively the elastomeric floor may also be applied to the surface of the basic sleeve by inkjet printing.


In another preferred embodiment, the elastomeric layers are fully cured and the relief is formed by laser engraving. In laser engraving, the elastomeric layers of a different hardness can be used to obtain the desired hardness.


In another preferred embodiment the flexographic printing sleeve is prepared by a coating method as disclosed in WO 2008/034810 (AGFA GRAPHICS).


Different types of printing applications require flexographic printing forms with differing degrees of hardness. Softer flexographic printing forms are more suited for rough substrates because they can better cover the highs and lows. The harder flexographic printing forms are used for even and smooth substrates. The optimum hardness of a flexographic printing form also depends on whether the image is solid or halftone. Softer flexographic printing forms will transfer the ink better in solid areas, though harder flexographic printing forms have less dot gain. The hardness is a measure of the printing form's mechanical properties which is measured in degree of Shore A. For example, printing on corrugated board requires usually a hardness of 35° Shore A, whereas for reel presses 65° to 75° Shore A is a standard.


Depending on the substrate to be printed upon, the hardness and thickness of the flexographic printing form have to be adjusted. Depending on the application, the relief depth varies from 0.2 to 4 mm, preferably from 0.4 to 2 mm.


Imaging Apparatuses


The imaging apparatus for making a flexographic printing master according to a preferred embodiment of the present invention comprises:


a) a rotatable drum (31) for holding a flexographic printing support;


b) an inkjet printing device (32) and a curing device (39) for printing respectively curing a relief with a top hat profile (38) on the flexographic printing support (1); and


c) a grinding device (35) having a grinding surface for grinding the printing surface of the relief with the top hat profile


In one preferred embodiment, the rotatable drum of the imaging apparatus is a drum of a flexographic printing press.


A preferred embodiment of the imaging apparatus is schematically shown in FIG. 3 where a flexographic printing support (1) is mounted upon a rotatable drum (31) having a rotation direction (34). An inkjet print head (32) jets image-wise droplets (33) towards the rotatable drum (31) to form a layer on the flexographic support (1) which is then immobilized by the curing device (39) before a subsequent layer is applied by the inkjet print head (32). Through rotation of the rotatable drum (31) and applying subsequent layers, a relief with a top hat profile (38) can be formed. After the relief is formed a grinding device (35) is moved in a direction (37) preferably perpendicular on the surface of the rotatable drum (31). The grinding device includes a grinding surface (36) of which the distance the printing surface of the relief can be accurately controlled, preferably on a micrometer scale. The grinding surface (36) is brought into a position where it grinds part of the top hat segment away, such that the whole relief obtains the same caliper and a printing surface having the desired flatness and evenness.


Ink flow down after drop deposition results in an oblated spheroidal shaped top surface of printed relief dots. In FIG. 4, such a relief dot is shown having a sloped segment (21) with a shoulder (4) and a top hat segment (23) with a rounded printing surface (3). This can lead to a significant dot loss in printed screens. A rounded printing surface (3) only results in a low amount of ink transfer during flexographic printing. By grinding the printing surface (3) to a flattened surface having the diameter of the base surface of the top hat segment (23), the exact amount of ink is transferred during flexographic printing. The fact that a top hat profile is used has the advantage that grinding does not result in any dot gain as long as the grinding occurs in the top hat segment.


For flexographic printing a large solid image area, a very broad relief dot is shown in FIG. 5 having a sloped segment (21) with a shoulder (4) and a top hat segment (23) which is created by jetting and curing, layer by layer, several droplets next to each other on the sloped segment (21). As a result, an undesired surface unevenness of the printing surface (3) is obtained. This surface unevenness can be removed by grinding until the printing surface (3) has the desired flat, even topography.


A relief on a flexographic printing master generally comprises relief dots having different diameters. In inkjet printing a large relief dot (61) and a small relief dot (62) generally a difference in caliper is seen, as shown in FIG. 6. The smaller relief dots are less high than the larger relief dots by a difference in height d(DT), as shown in FIG. 6 between the top hat segments of the large relief dot (61) and the small relief dot (62). Grinding of such a relief leads to a relief wherein all relief dots and lines have the same caliper. Flexographic printing with such a grinded relief results in images wherein also the small image details are present.


It should be clear that the inkjet printing device and the grinding device are positioned in such a manner that grinded material from the grinding process does not interfere with the inkjet printing device for making subsequently other flexographic printing masters, e.g. through clogging of an inkjet nozzle by dust particles generated by the grinding process. The skilled person is well aware of methods and devices to physically separate the inkjet printing device and the grinding device, such as for example:

    • positioning the inkjet print head (32) in a closed maintenance station;
    • positioning a separation wall (not shown in FIG. 3) between the inkjet print head (32) and the grinding device (35);
    • selecting around the rotatable drum (31) a suitable angle between the inkjet print head (32) and the grinding device (35) of e.g. 90° or even up to a preferred 180°; and
    • providing a dust removing device for removing dust particles generated by the grinding process e.g. by air suction and/or brushes.


In one preferred embodiment, the grinding process can also be performed off-line, i.e. not on the apparatus containing the inkjet printing device but on a second apparatus containing a grinding device. Although no clogging of inkjet nozzles can then occur, the off-line grinding is less preferred because it requires extra manutention for de-mounting and re-mounting of the flexographic printing form, which is not desirable from an economical point of view.


Device for Inkjet Printing


The device for inkjet printing includes any device capable of coating a surface by breaking up a radiation curable liquid into small droplets which are then directed onto the surface. In the most preferred embodiment the radiation curable liquids are jetted by one or more printing heads ejecting small droplets in a controlled manner through nozzles onto a flexographic printing support, which is moving relative to the printing head(s).


A preferred printing head for the inkjet printing system is a piezoelectric head. Piezoelectric inkjet printing is based on the movement of a piezoelectric ceramic transducer when a voltage is applied thereto. The application of a voltage changes the shape of the piezoelectric ceramic transducer in the printing head creating a void, which is then filled with radiation curable liquid. When the voltage is again removed, the ceramic expands to its original shape, ejecting a drop of liquid from the print head. However the inkjet printing method is not restricted to piezoelectric inkjet printing. Other inkjet printing heads can be used and include various types, such as a continuous type and thermal, electrostatic and acoustic drop on demand type.


At high printing speeds, the radiation curable liquids must be ejected readily from the printing heads, which puts a number of constraints on the physical properties of the liquid, e.g. a low viscosity at the jetting temperature, which may vary from 25° C. to 110° C., a surface energy such that the printing head nozzle can form the necessary small droplets, a homogenous radiation curable liquid capable of rapid conversion to a dry printed area, . . . .


The inkjet printing head normally scans back and forth in a transversal direction across the moving flexographic printing support. The inkjet print head does not need to print on the way back, but bi-directional printing is preferred for reasons of productivity. Another preferred printing method is by a “single pass printing process”, which can be performed by using page wide inkjet printing heads or multiple staggered inkjet printing heads which cover the entire width of the flexographic printing support. In a single pass printing process, the inkjet printing heads usually remain stationary and the flexographic printing support is transported under the inkjet printing heads, e.g. by the rotatable drum (31) described above in FIG. 3.


Device for Curing Radiation Curable Liquids


The imaging apparatus contains a device for curing (39) a radiation curable liquid. Radiation curable liquids are cured by exposing them to actinic radiation, e.g. by UV curing, by thermal curing and/or by electron beam curing. Preferably the curing is performed by UV radiation.


The curing device (39) may be arranged in combination with the inkjet print head, travelling therewith so that the curable liquid is exposed to curing radiation very shortly after been jetted.


In such an arrangement it can be difficult to provide a small enough radiation source connected to and travelling with the print head. Therefore, a static fixed radiation source may be employed, e.g. a source of curing UV-light, connected to the radiation source by a flexible radiation conductive device such as a fibre optic bundle or an internally reflective flexible tube.


Alternatively, the actinic radiation may be supplied from a fixed source to the radiation head by an arrangement of mirrors including a mirror upon the radiation head.


The source of radiation arranged not to move with the print head, may also be an elongated radiation source extending transversely across the flexographic printing support surface to be cured and adjacent the transverse path of the print head so that the subsequent rows of images formed by the print head are passed, stepwise or continually, beneath that radiation source.


Any ultraviolet light source, as long as part of the emitted light can be absorbed by the photo-initiator or photo-initiator system, may be employed as a radiation source, such as, a high or low pressure mercury lamp, a cold cathode tube, a black light, an ultraviolet LED, an ultraviolet laser, and a flash light.


For curing the inkjet printed radiation curable liquid, the imaging apparatus preferably has a plurality of UV light emitting diodes. The advantage of using UV LEDs is that it allows a more compact design of the imaging apparatus.


Specifically, a UV-A light source is preferred due to the higher penetration depth therewith resulting in more efficient interior curing. UV radiation is generally classed as UV-A, UV-B, and UV-C as follows:

    • UV-A: 400 nm to 320 nm
    • UV-B: 320 nm to 290 nm
    • UV-C: 290 nm to 100 nm.


In a preferred embodiment, the subsequent layers forming the relief are cured with UV-A radiation and on completing the relief, it is cured with UV-C radiation before commencing the grinding step c).


For facilitating curing, the imaging apparatus preferably includes one or more oxygen depletion units. The oxygen depletion units place a blanket of nitrogen or other relatively inert gas (e.g. CO2), with adjustable position and adjustable inert gas concentration, in order to reduce the oxygen concentration in the curing environment. Residual oxygen levels are usually maintained as low as 200 ppm, but are generally in the range of 200 ppm to 1200 ppm.


Thermal curing can be performed image-wise e.g. by use of a thermal head or a laser beam. If a laser beam is used, then preferably an infrared laser is used in combination with an infrared dye in the curable liquid.


When electron beams are employed, the exposure amount of the electron beam is preferably controlled to be in the range of 0.1-20 Mrad. An exposure amount of less than 0.1 Mrad does not result in sufficient curing of the curable liquids. Accepted as electron beam exposure systems are, for example, a scanning system, a curtain beam system, and a broad beam system. An appropriate acceleration voltage during electron beam exposure is preferably 100-300 kV.


Grinding Device


The apparatus according to a preferred embodiment of the present invention comprises a grinding device. The grinding device includes any device having a grinding surface which can be positioned accurately at a certain distance from the flexographic printing support and capable of grinding or polishing the printing surface of a flexographic printing master.


The grinding device can have any form suitable for grinding a top hat profile, such as a grinding wheel, a grinding stone, abrasive grinding paper, an abrasive cloth roll and a sanding pad.


Even commonly used sandpaper mounted in a suitable manner for grinding a flexographic printing form on a rotatable drum can be used as a grinding device. The material used for grinding usually includes abrading particles from aluminium oxide, silicon carbide, alumina-zirconium (an aluminium oxide-zirconium oxide alloy) and chromium oxide. Both coated abrasives, as well as bonded abrasives can be used.


Sandpaper may be “stearated” where a dry lubricant is loaded to the abrasive. Stearated papers are useful because this increases the useful life of the sandpaper. Aluminium Oxide with stearate is also known as PS33.


The grit size of a sand paper refers to the size of the particles of abrading materials embedded in the sandpaper. A number of different standards have been established for grit size. These standards establish not only the average grit size, but also the allowable variation from the average. The most common is the European FEPA (Federation of European Producers of Abrasives) “P” grade. The FEPA system is the same as the ISO 6344 standard. Preferred sandpapers in the present method for making a flexographic printing master have an ISO/FEPA grit designation of P240 to P2500, more preferably P320 to P1000.


The roughness of the applied sanding paper or grinding device can be advantageously used to determine the printing surface structure of the flexographic printing form.


Suitable abrasive type materials include aluminum oxide, silicon carbide, zirconium, cork, boron carbide, ceramic, garnet, diamond, CBN, tungsten carbide and copper or nickel coated abrasives.


The grinding can be performed by dry or wet grinding. Wet grinding has the advantage that dust particles generated by the grinding process are largely removed together with the applied liquid, thereby preventing clogging of the inkjet print head. For grinding top hat segments with a high Shore A hardness, the grinding liquid is preferably a cooling liquid to maintain efficient grinding.


Grinding is preferably performed bidirectionally, i.e. by rotating the rotatable drum (31) alternatively in both directions during grinding. The advantage of bidirectional grinding is that the grinding occurs uniformly and a sloped printing surface (3) is avoided.


In a more complex imaging apparatus, the grinding device is no longer some kind of physical contact grinding device but a laser. In such a case it becomes necessary to include a profilometer into the imaging apparatus; A profilometer is capable of measuring the height DT of the top hat segment, the height D or even the caliper C (see FIG. 2 for these heights). Such measuring techniques include contact less measurement, e.g. interferometry, and contact measurement, e.g. perthometry. Preferably the height measurement is contact less in order to avoid damages of the relief.


Suitable lasers include those normally used in manufacturing flexographic printing forms by direct laser engraving. Examples of such lasers are disclosed in EP 1700691 A (DAINIPPON SCREEN) incorporated herein as reference.


A preferred example of the laser is a laser having an emitting wavelength in an infrared region or near infrared region, for example, a carbon dioxide gas laser, a YAG laser, a semiconductor laser or a fibre laser. Also, an ultraviolet laser having an emitting wavelength in an ultraviolet region, for example, an excimer laser, a YAG laser wavelength-converted to the third harmonic or the fourth harmonic or a copper vapour laser is also able to conduct ablation processing which cleaves a bond between molecules of organic compound and thus is suitable for microfabrication. A laser having an extremely high peak power, for example, a femtosecond laser can also be employed. The laser irradiation may be performed continuously or pulse wise.


Preferred lasers for laser engraving include CO2-lasers and Nd-YAG lasers. For example, a Stork Agrios triple beam CO2-laser can be used. Fibre lasers can also be used if, for example, a carbon black pigment is present in the radiation curable liquid.


Device for Removal of Grinded Material


In a preferred embodiment of the imaging apparatus according to the present invention a device is present to actively remove grinded top hat segment material.


The grinded top hat segment material can be removed by any appropriate method, for example:

    • a method of washing out, for example, with a solvent or water optionally containing a surfactant;
    • a method of spraying an aqueous cleaning agent, for example, by a high-pressure sprayer;
    • a method of spraying high-pressure steam or air;
    • a method employing an ultrasonic device; and
    • a method of wiping off with a cloth, a brush or the like.


In one preferred embodiment the grinded top hat segment material is sucked away by an air stream, e.g. into a collector for the grinded material.


In another preferred embodiment the grinded top hat segment material is removed by a liquid, and is preferably collected on a filter system.


EXAMPLES
Materials

All materials used in the following examples were readily available from standard sources such as ALDRICH CHEMICAL Co. (Belgium) and ACROS (Belgium) unless otherwise specified. The water used was deionized water.


SR506D is isobornylacrylate available as SARTOMER™ SR506D from SARTOMER. It has a viscosity of 10 mPa·s at 25° C. SR610 is polyethyleneglycol 60 diacrylate available as SARTOMER™ SR610 from SARTOMER. It has a viscosity of 90 mPa·s at 25° C.


GENOMER™ 1122 is 2-acrylic acid 2-(((acryl-amino)carbonyl)oxy)ethylester available from RAHN AG (Switzerland). It has a viscosity of 30 mPa·s at 25° C.


GENOCURE™ EPD is the co-initiator ethyl 4-dimethylaminobenzoate available from RAHN AG (Switzerland).


DAROCUR™ ITX is the photo-initiator isopropylthioxanthone available from CIBA.


DAROCUR™ TPO is the photo-initiator 2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide available from CIBA.


EBECRYL™ 1360 is a polysiloxane hexa acrylate from UCB S.A. (Belgium).


Measurements


1. Viscosity


The viscosity was measured with a MCR500 Rheometer (manufacturer Anton Paar), equipped with a CC27 spindle and a coaxial cylinder geometry (shear rate 10 s−1).


2. Surface Tension


The surface tension of the inkjet inks was measured with a KRÜSS tensiometer K9 at 25° C. after 60 seconds.


3. Dmax


The maximum optical density Dmax was measured using a MacBeth RD918SB densitometer with a filter complementary to the colour of the printing ink used.


Preparation of the Radiation Curable Liquid LIQ-1


A jettable radiation curable liquid LIQ-1 was made by mixing the components according to Table 1 for 30 minutes. The resulting liquid had a surface tension of 28.7 mN/m.












TABLE 1







Component
wt %



















SR506D
45.90



SR610
19.10



GENOMER ™ 1122
14.40



SANTICIZER ™ 278
5.60



GENOCURE ™ EPD
5.00



DAROCUR ™ ITX
5.00



DAROCUR ™ TPO
4.96



EBECRYL ™ 1360
0.04











Preparation of the Flexographic Print Masters FPM-1 and FPM-2


Two flexographic print masters FPM-1 and FPM-2 were made using a custom-build 3D-inkjet printer having a rotatable drum using an UPH-print head (available from AGFA) for jetting the jettable radiation curable liquid LIQ-1 at 1 dpd on a raw sleeve. The inkjet printing conditions were head temperature of 45° C., voltage=17V, sample clock=250 ns, 720 dpi and drum rotation speed=300 mm/s.


The raw sleeve was a durable fibreglass base ROTEC™ Basic Sleeve available from ROTEC having an internal diameter of 130.623 mm and whereupon a fully cured DuPont CYREL™ NOW flexographic plate was mounted with a double sided mounting tape (Lohmann DUPLOMONT™ 9052 compressible tape). The curing device was made up of UV-LED's emitting at 365 nm from NICHIA.


A mesa relief having a height of 0.54 mm was built up by jetting consecutive layers having a thickness of approximately 5 μm each on the 1.67 mm thick DuPont CYREL™ NOW. On the mesa relief an image relief having a top hat profile with a height of 120 μm was jetted. The image relief included a solid area (100%), lines of different width (70, 105, 140 and 175 μm) and areas with dots, including 2% and 24% dots (@ 103 lpi).


After the relief image has been gradually built up by inkjet, whereby each jetted layer was contiguously cured with UV-A light, a final UV-C post curing step is carried out to remove surface tackiness. This curing step with UV-C was carried out under a N2-atmosphere with 254 nm TL-lamps.


Then grinding was carried out on the top surface of the image relief of the flexographic printing master FPM-2 manually by kiss-contacting a straight plastic support provided with a mounted sheet of ultra fine sand paper 800 grit against the printing surface on top of the relief image.


The flexographic printing master FPM-1 did not receive a grinding step.


Flexographic Printing Test


A flexographic printing test was carried out with the flexographic printing masters FPM-1 and FPM-2 on a laboratory flexographic printing press RK Koater available from RK PRINT-COAT INSTRUMENTS Ltd. (UK), provided with a type 360 anilox roller (cell volume 7.8 cm3/m2 @ 60° screen angle) and a steel doctor blade. Printing speed was aimed to be 32.5 m/min (position 7).


The printing ink was Aqua Base Plus Blue ET-51405, a water based pigment flexographic ink for self-adhesive labels from ROYAL DUTCH PRINTING INK FACTORIES VAN SON.


Printing was performed on Arctic Gloss Paper 150 g/m2, a substrate available from ARCTIC PAPER;


EVALUATION AND RESULTS

The flexographic printing results obtained with the flexographic printing masters FPM-1 and FPM-2 are shown in Table 2.













TABLE 2








FPM-1




Flexographic
(not
FPM-2



printing results
grinded)
(grinded)









Original dot area %
41%
53%



(24% @ 103 1pi)



Dot gain (*)
17%
29%



Dmax
1.37
1.70



Reproducible
105 μm
70 μm



uninterrupted line



width







(*) The dot gain obtained with a DuPont CYREL HIQ printing plate is 29% (orig. dot area % = 25% @ 110 lpi).



Measurements were performed using the Murray-Davies formula.






The larger Dmax of FPM-2 is a direct result of grinding a surface as schematically shown in FIG. 5.



FIG. 8 is a photograph of the flexographic printing result obtained using the flexographic printing master FPM-1 which shows interrupted lines of 70 μm width and uninterrupted lines of 105 μm.



FIG. 9 is a photograph of the flexographic printing result obtained using the flexographic printing master FPM-2 which shows uninterrupted lines of 70 μm and 105 μm width.



FIG. 10 is a photograph of the flexographic printing result of dots with an original dot area % of 2% obtained with the flexographic printing master FPM-1 having a not grinded top hat profile relief.



FIG. 11 is a photograph of the flexographic printing result of dots with an original dot area % of 2% obtained with the flexographic printing master FPM-2 having a grinded top hat profile relief.


It should be clear from Table 2 and the photographs in FIG. 8 to FIG. 11, that an improved printing result was obtained by grinding the top hat profile.


While preferred embodiments of the present invention have been described above, it is to be understood that variations and modifications will be apparent to those skilled in the art without departing the scope and spirit of the present invention. The scope of the present invention, therefore, is to be determined solely by the following claims.

Claims
  • 1. An imaging apparatus for making a flexographic printing master, the imaging apparatus comprising: a rotatable drum arranged to hold a flexographic printing support;an inkjet printing device and a curing device arranged to print and cure, respectively, a relief with a top hat profile on the flexographic printing support; andan engraving device configured to engrave a printing surface of the relief with the top hat profile; whereinthe engraving device includes a laser and a profilometer.
Priority Claims (1)
Number Date Country Kind
08172282 Dec 2008 EP regional
CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage Application of PCT/EP2009/066097, filed Dec. 1, 2009. This application claims the benefit of U.S. Provisional Application No. 61/139,636, filed Dec. 22, 2008, which is incorporated by reference herein in its entirety. In addition, this application claims the benefit of European Application No. 08172282.9, filed Dec. 19, 2008, which is also incorporated by reference herein in its entirety.

PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/EP2009/066097 12/1/2009 WO 00 5/19/2011
Publishing Document Publishing Date Country Kind
WO2010/069749 6/24/2010 WO A
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Entry
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Related Publications (1)
Number Date Country
20110219972 A1 Sep 2011 US
Provisional Applications (1)
Number Date Country
61139636 Dec 2008 US