Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
  • B41M5/506—Intermediate layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
  • B41M5/508—Supports
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
  • B41M5/52—Macromolecular coatings
  • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core
  • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
  • Y10T428/2942—Plural coatings
  • Y10T428/2949—Glass, ceramic or metal oxide in coating
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31768—Natural source-type polyamide [e.g., casein, gelatin, etc.]
  • Y10T428/31772—Next to cellulosic
  • Y10T428/31775—Paper
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers

Definitions

• the present invention relates to a satin-gloss ink recording material and a method for the production thereof and the use of the ink jet recording material according to the invention for ink jet printing, as well as a printed ink jet recording material.
• Inkjet printing Because of the number of good properties such as the ability to print at high speed, the low noise level during printing, the wide variety of patterns recorded, the simplicity of multi-color printing, the high quality of the printed image, which can even compete with photographic methods and the like Inkjet printing has played an important role in various fields in recent years. Accordingly, great efforts have been made in recent years to provide recording materials for ink jet printing with improved properties. This is reflected in an almost unmanageable amount of publications on inkjet recording material in the specialist and patent literature. Some important properties for ink jet recording materials are summarized below:
• the ink jet on recording material should have certain surface properties, and these should be achieved without adversely affecting the ink jet recording properties specified above.
• the common procedure for surface treatment is e.g. B. calendering, whereby the surface is smoothed and the coating layer is solidified.
• DE-A 3151471 describes a process for producing an inkjet recording material in which a plurality of coating layers composed of an inorganic pigment and an aqueous binder composition are applied to a substrate and the coating color is then dried.
• the recording material is exposed to a relatively high pressure of 200 N / mm and a temperature of approximately 70 ° C, while in the glossy calender the pressure is 90 N / mm and the temperature is approximately 150 ° C.
• DE-A 3151471 does not contain any No details about the gloss or surface smoothness of the ink jet recording material thus produced.
• US-A-4,770,934 relates to an ink jet recording material in which an ink recording layer containing a pigment such as e.g. B. a synthetic silica with a specific surface area of at least 100 m 2 / g and a binder is applied, and this surface layer is then formed in a cast coating process.
• a pigment such as e.g. B. a synthetic silica with a specific surface area of at least 100 m 2 / g and a binder
• Two different cast coating processes can be used here, namely the direct method (wet process), in which the wet paint is dried under pressure immediately after application of the coating color by contact with a heated polished metal cylinder, in particular with a chrome surface.
• the indirect process rewet process
• Both procedures usually lead to a very high surface gloss. Because of the coating color compositions used in US Pat. No. 4,770,934, however, only medium gloss ranges between 20 and 50% are achieved here at a viewing angle of 75 °.
• EP-A 0 732 219 discloses a two-layer ink recording material.
• an ink recording layer containing a pigment and a binder is applied to a substrate and then to a surface layer which has cationic ultrafine particles with a particle diameter in the range from 1 nm to 500 nm.
• the surface layer has a gloss of at least 45% at a viewing angle of 75 °.
• the recording material described in EP-A 0732219 already has these gloss values without any special surface treatment. However, the gloss can still be improved by a cast coating process.
• the direct and indirect methods mentioned above and the gel method are mentioned here.
• the wet coat gelled by passing the coated substrate through a coagulation or gelation bath and then brought into contact with the heated cylinder.
• the ink recording material described in EP-A 0732219 has excellent ink recording properties, but due to the inherent high gloss, even if no cast coating process is used, it is only suitable for applications in which a high gloss is desired.
• EP 0879709 B1 describes another casting process for producing a glossy ink jet on a drawing sheet.
• the coating layer has a very high water content after application to the substrate sheet and before drying on the highly polished surface of the metal cylinder. If the water content of the coating layer falls below a critical value, the highly polished surface of the metal cylinder cannot be transferred to the ink jet recording material. This results in surface defects that are inhomogeneously distributed over the entire paper and that result in inhomogeneous low gloss and smoothness values.
• DE-A 2 310 891 describes a further method for the surface treatment of a paper.
• This document deals with the problem of very smooth, high-gloss coatings that are comparable with those that are known from the casting processes described above.
• an aqueous composition of a binder which is essentially free of pigments, is applied to form a surface layer.
• the moist coating is then passed through a heating zone and brought to a temperature which is above the film-forming temperature of the binder, so that a polymer film is formed.
• the substrate is then brought into contact with a heated, polished roller.
• DE-A 2310891 relates to the application of a protective plastic coating to already printed substrates. This means that the plastic coating should not have any porosity and is therefore completely unsuitable for inkjet printing.
• Another object of the present invention is to provide a method by which an ink recording material having the above-mentioned requirements can be produced.
• This object is accomplished by a method of making an ink jet recording material: a) applying an aqueous coating slip containing a pigment and a binder to at least one surface of a substrate for forming at least one ink-receiving layer, b) applying an aqueous coating slip containing cationic inorganic particles, a binder and a release agent to the
• Ink-receiving layer (s) to form a surface layer c) partially drying the recording material and d) contacting the partially dried recording material with a heated metal cylinder without rewetting the coating
• an ink recording material comprising a substrate which has at least on one side of the substrate an ink-receiving layer which contains a pigment and a binder and thereon a surface layer, the surface layer containing cationic inorganic particles, a binder and a release agent and the surface layer one Gloss value in the range from 5 to 35 measured according to DIN 54502 R '(75 °) (measuring angle 75 °) and a surface smoothness according to the Parker Print Surf process (PPS) according to DIN ISO 8791-4 of less than 2, 5 ⁇ m.
• PPS Parker Print Surf process
• the method of the present invention achieves significantly lower gloss values compared to the classic cast coating method, without the smoothness of the recording material being significantly reduced thereby.
• Another procedural advantage of the present invention lies in the fact that the process can be carried out on existing casting lines and the reduced gloss is produced by the process according to the invention, without, for example, B. the polished metal cylinder by a surface-modified metal cylinder, as taught in DE-A 19755724, can be replaced uss.
• the decisive advantage of the method according to the invention is that it provides a satin-matt ink recording material with excellent ink absorption properties.
• the partial drying of the recording material in step c) of the method according to the invention is carried out in such a way that the recording material al has a residual moisture content of 14 to less than 20% by weight, preferably 16 to less than 20% by weight and particularly preferably 16 to 18% by weight of water, based on the total weight of the recording material, is dried.
• This can e.g. B. by hot air drying at 30 ° C to 80 ° C, preferably at 40 ° C to 60 ° C for 3 to 60 seconds, preferably 10 to 30 seconds.
• infrared drying with comparable drying performance can also be used.
• the recording material is pressed onto the heated cylinder with a pressure roller with a line pressure of 400 to 800 N / cm, preferably 500 to 750 N / cm.
• the surface temperature of the cylinder is preferably 90 ° C to 120 ° C, particularly preferably 100 ° C to 115 ° C.
• the metal cylinder can be any cylinder normally used in the cast coating process, in particular a cylinder with a polished chrome surface.
• an aqueous coating slip for forming the ink-receiving layer is applied to at least one side of a flat substrate.
• the aqueous coating slip for forming the ink receiving layer and thus the ink receiving layer itself contains a pigment and a binder.
• pigments suitable for the ink recording layer include inorganic pigments such as. As silica, aluminum oxide, aluminum oxide hydrate, aluminum silicate, magnesium silicate, magnesium carbonate, talc, clay, hydrotalcide, calcium carbonate, titanium dioxide and zinc oxide as well as plastic pigments such as polyethylene, polystyrene and polyacrylate. These pigments can be used either individually or in combination. Pigments are particularly preferred, selected from silica, aluminum oxide, aluminum oxide hydrate and magnesium carbonate. The particle size of these pigments can range between 0.1 to 20 microns.
• Water-soluble resins such as. B. polyvinyl alcohol, starch, cationized starch, casein, gelatin, acrylic resins, urethane resins, Natriu alginate, polyvinylpyrrilidone, carboxymethyl cellulose and hydroxyethyl cellulose suitable.
• latices can be acrylic polymers such.
• B. ethylene vinyl acetate copolymers can be used.
• These binders can be used either individually or in combination.
• the ratio of binder to pigment in the ink recording layer is preferably 2: 1 to 1:10, particularly preferably 1: 1 to 1: 5.
• the aqueous coating slip for forming the ink-receiving layer and thus the ink-receiving layer itself can also contain additional components such as e.g. B.
• Crosslinking agents such as melamine resins, glyoxal and isocyanates, surfactants, antifoams, antioxidants, optical brighteners, UV absorbers, viscosity modifiers for pH adjustment, etc. include.
• the ink-receiving layer can be applied either as a single layer or as a multiple layer, it being possible for the individual layers to be both identical and different.
• the ink absorption layer preferably has a weight per unit area of 5-20 g / m 2 based on the dry weight.
• the recording material it is preferred to dry the recording material after applying the ink-receiving layer and before applying the surface layer.
• wet-on-wet application of the surface layer to an ink receiving layer that has not or only partially dried is also possible.
• a commercially available substrate that has a primer that meets the criteria defined above for the ink-receiving layer can also be used as a starting material for the application of the surface layer.
• the surface layer is also applied with an aqueous coating slip to the already applied ink-receiving layer.
• aqueous coating slip to form the surface layer has cationic inorganic particles, a binder and a release agent.
• the cationic particles for the surface layer are selected from aluminum oxide, aluminum oxide hydrate or silica, the surface of which has been cationized.
• ⁇ -, ⁇ -, ⁇ - and ⁇ -aluminum oxide can be used as a suitable aluminum oxide.
• Suitable aluminum oxide hydrates are gibbsite, bayerite, northeast randite, crystalline boehmite, diaspore and pseudoboehmite.
• cationic silicas examples include silicas that are subjected to surface treatment with a compound that contains cationic metal oxides or metal atoms, or silicas that are subjected to surface treatment with an organic compound that have both amino groups or quaternary ammonium groups and functional groups that have silanol groups on the surface with the silica react like B.
• Ainoethoxysilan or Aminoalkylglycidi1ether contain.
• the cationic particles have an average particle diameter in the range from 1 to 1,000 nm, preferably 10 to 500 nm.
• the ink jet recording material has an at least two-layer coating, the surface layer being intended to provide the desired surface properties and the combination of surface layer and ink receiving layer being intended to provide the desired ink receiving properties. It is particularly important that the ink recording material has a high ink absorption capacity as well as a high recording speed. Furthermore, it is essential that the color pigments of the inks are preferably fixed in the surface or near the surface in order to provide a high color density and color brilliance. It is also important that the liquid and volatile carrier fluid of the ink is absorbed as quickly as possible by the ink recording material and separated from the ink dyes so that there is no bleeding and that sharp contours are always generated in the printed image. To achieve this, the cationic particles in the surface layer are particularly important.
• the cationic particles in the surface layer produce sufficient porosity of the surface layer, which enables the ink to be absorbed quickly. Due to the cationic nature of the particles, the ink dyes, which are often anionic, are at least partially immediately fixed in the surface layer, while the carrier fluid of the ink is quickly transported into the ink-receiving layer located below the surface layer. This ensures that a significant proportion of the ink dyes in the top layer of the recording material is fixed even if a part of the ink dyes is held in the underlying ink receiving layer. In any case, it is ensured that the ink dyes are fixed close to the surface. Furthermore, the structure of the ink recording material according to the invention enables the fluid carrier of the ink to be removed very quickly, as a result of which very high ink absorption speeds and short drying times are achieved.
• the cationic particles have an average particle diameter in the range from 1 to 1,000 nm, preferably 10 to 500 nm.
• optimal ink recording properties and surface properties can be achieved.
• a particular advantage of these preferred particle sizes is that the transparency of the surface layer can be increased, so that the inkjet printed image has excellent color brilliance.
• binders that were described above in connection with the ink-receiving layer can be used as binders for the surface layer.
• Polyurethanes are a particularly preferred binder.
• the ratio of cationic inorganic particles to binder in the surface layer is preferably within a range from 50: 1 to 1: 2.
• finely divided organic resins can also be present in the surface layer. This increases the porosity of the surface layer.
• the particles of the organic resins preferably have a diameter in the range of 0.05 ⁇ m to 2 ⁇ m.
• Examples of fine particles of organic resins include latices of acrylic polymers such as. B. Polymers of acrylic esters or methacrylic esters and copolymers of these monomers with other monomers, latices of carboxyl-modified conjugated diene polymers, latices of vinyl copolymers such as e.g. B.
• ethylene-vinyl acetate copolymers fine-particle polyvinyl chloride, fine-particle pol ethylene, fine-particle copolymers of vinylpyrrolidone and styrene and fine-particle copolymers of vinyl alcohol and styrene.
• Another essential component of the surface layer is a release agent to ensure that when the method according to the invention is carried out while the partially dried recording material is brought into contact with the heated metal cylinder, the line is formed uniformly and completely without the line coming off and / or adheres to the metal cylinder.
• Suitable release agents are oleic acid, rapeseed oil, metal stearates, ammonium stearates, polyethylenes, ethoxylated polyethylenes, waxes, metal and ammonium salts of aliphatic acids, ketene dimers, surface-active agents based on fatty acids, sulfonated and sulfated oils, fatty acid triglycerides and fatty acid ide, where Oleic acid and rapeseed oil are particularly preferred.
• the release agents can be used alone or in combination.
• the total amount of release agent in the aqueous coating slip to form the surface layer is preferably 1-10% by weight, based on the total mass of the solids in the coating slip.
• either the aqueous coating slip to form the ink-receiving layer or the aqueous coating slip to form the surface layer or both coating slips contains a cationic compound which is not a pigment. It is particularly advantageous if at least the surface layer contains such a cationic compound in order to improve the fixation of the usually anionic color pigments of the ink in the surface layer and thus to improve the wet strength of the inkjet print.
• Possible cationic compounds are: polyallylamine and its quaternary ammonium salts, polyamine sulfone and its quaternary ammonium salts, polyvinylamine and its quaternary ammonium salts, chitosan and its acetates, polymers of monomers selected from the group consisting of dimethylaminoethyl (eth) acrylate, diethylaminoethyl (meth) - acrylate, methylethyl aminoethyl (meth) acrylate, dimethylaminostyrene, diethylaminostyrene, copolymers of vinyl pyrrolidone with a quaternary salt of an aminoalkyl (meth) acrylate and a copolymer of (meth) acrylamide with a quaternary salt of aminoethyl (meth) acrylamide.
• the pH of the coating slip in the acidic range.
• the pH is preferably in the range from 2.5 to 5.0.
• Paper can be used as the substrate. It is preferred if the substrate itself is porous, that is to say it has a liquid absorption capacity, the desired dimensional stability for the recording material is provided, and it exhibits sufficiently good adhesion to the recording layer. Therefore, paper is particularly preferred as the substrate.
• the weight per unit area of the paper substrate is preferably 40 to 300 g / m 2 .
• the ink recording material according to the invention which can be produced using the method according to the invention, has a surface which has a gloss value in the range from 5% to 35%, measured according to DIN 54502 R '(75 °) (measuring angle 75 °) and a surface smoothness according to the Parker Print Surf process (PPS) according to DIN ISO 8791-4 of less than 2.5 ⁇ m.
• the gloss value is 5 to less than 30 X, in particular 10 X to less than 30 X, very particularly preferably 12% to 25 X and the surface smoothness is less than 2.2 ⁇ m. Consequently provides a satin ink recording material with excellent ink absorption properties and high smoothness.
• a particular advantage of the ink recording material according to the invention lies in the extremely short drying time close to zero of the applied ink jet print image.
• a coating color in accordance with the composition given in Table 1 with a solids content of 27% by weight was applied by means of an inking roller to the pre-coated paper web at a web speed of 30 m / min. So much excess coating color was removed with an air brush that a coating amount of 11 g / m 2 (in the dried state) remains on the paper web.
• the coated paper web When passing through hot air drying at 50 ° C for 20 seconds, the coated paper web is dried to a residual moisture content of 16% by weight of water, based on the total weight of the paper web, and then immediately into the nip, which consists of an elastic pressure roller and a highly polished Chrome cylinder is formed without rewetting performed.
• the line pressure of the roller / chrome cylinder pair was 625 N / cm and the temperature of the chrome cylinder surface was 110 ° C.
• the inkjet recording material showed excellent printability in inkjet printing and had a surface gloss of 19 X at a viewing angle of 75 °, measured in accordance with DIN 54502.

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• Ink Jet (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
• Glass Compositions (AREA)
• Particle Formation And Scattering Control In Inkjet Printers (AREA)
• Soft Magnetic Materials (AREA)

Applications Claiming Priority (3)

Publications (2)

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• 2001
  • 2001-03-13 DE DE2001112327 patent/DE10112327A1/de not_active Ceased
• 2002
  • 2002-03-09 CA CA 2440326 patent/CA2440326A1/fr not_active Abandoned
  • 2002-03-09 JP JP2002571303A patent/JP2004522630A/ja active Pending
  • 2002-03-09 US US10/471,689 patent/US20040146726A1/en not_active Abandoned
  • 2002-03-09 AT AT02727392T patent/ATE316472T1/de not_active IP Right Cessation
  • 2002-03-09 EP EP02727392A patent/EP1370421B1/fr not_active Expired - Lifetime
  • 2002-03-09 CN CNB028064828A patent/CN1228505C/zh not_active Expired - Fee Related
  • 2002-03-09 DE DE50205703T patent/DE50205703D1/de not_active Expired - Lifetime
  • 2002-03-09 WO PCT/EP2002/002633 patent/WO2002072359A1/fr active IP Right Grant
• 2004
  • 2004-11-11 HK HK04108889A patent/HK1065983A1/xx not_active IP Right Cessation

Non-Patent Citations (1)

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