Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
  • C09D11/104—Polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/0045—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or film forming compositions cured by mechanical wave energy, e.g. ultrasonics, cured by electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams, or cured by magnetic or electric fields, e.g. electric discharge, plasma
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
  • B41M7/02—Dusting, e.g. with an anti-offset powder for obtaining raised printing such as by thermogravure ; Varnishing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent

Definitions

• This invention relates to a new coating for substrates such as board packages which is obtainable by the use of a specific offset ink in an in-line varnishing process, and to a process of varnishing substrates in line.
• Packaging materials such as board packages are commonly printed by means of the offset printing process. This process is particularly suitable for such type of substrates since due to the indirect transfer of the ink from the printing plates to the substrate the rather sensitive plates do not come into direct contact with the rough surface of the substrate, resulting in a longer serviceability of the printing machines.
• the present invention is only related to traditional offset inks and not to UV curable inks.
• UV curable inks are used for in line varnishing processes since they can be cured with radiation before varnishing.
• the use of UV curable inks is not advisable due to the higher costs involved with the use of UV curable inks. Therefore, in the context of the present invention, the term "traditional offset ink” comprises any offset inks which are not UV curable offset inks.
• traditional offset Inks to be used in an offset-printing process have to meet certain criteria. In order to allow good printing, those inks should be viscous and adhesive, i.e. providing a certain tack, without solidifying within the printing machine.
• traditional offset inks are composed of a pigment which is not soluble in the wetting medium used in the offset-printing process, a binder which is soluble in the solvent used in the ink and is preferably a hard resin such as a rosin resin, a film forming agent such as linseed oil or alkyd resins providing mechanical resistance to the final print, a solvent such as a mineral oil which should readily evaporate from the final print or penetrate into the substrate, as well as certain other additives.
• lacquer layer is designed to protect the underlying print against environmental influences.
• said overlying lacquer layer the visual effects of the print are enforced by providing a glossy or matt effect.
• lacquer layer there can be used various compositions. Preferred are lacquers which can be cured by means of ultraviolet (UV) radiation, such as lacquers being composed of acrylated species.
• UV radiation ultraviolet
• lacquers being composed of acrylated species.
• the varnish In order to achieve the increase of the gloss of the print the varnish must not be too viscous. However, when applied to a porous material, with low viscosity varnishes a problem of soak-in can arise. Also, the glueability and scuff and rub resistance of the varnish have to be chosen in dependence of the properties the final coating consisting of the print and the lacquer layer should exhibit.
• a common formulation for a UV-curable varnish comprises, for example, one or a mixture of several acrylate resins such as bisphenol A epoxy acrylate resin and benzophenone as a photoinitiator.
• the varnish can be applied to the printed substrate.
• the majority of varnishing is carried out through a varnishing unit with an anilox roller.
• varnishing via a dry-offset method is used.
• the lacquer layer is applied to the printed substrate several hours after the traditional offset ink has been printed onto the substrate. This means that the ink is given a sufficient amount of time to dry, for example by evaporation of the solvent or by absorption of the solvent. Therefore, the lacquer layer is applied on a dry layer of ink, i.e. on a hard surface. This usually leads to good results with respect to the visual characteristics of the printed substrate, i.e. the final gloss is high and independent on the ink density variation across several areas of the print. Most of the time, the lacquer layer is applied on presses only dedicated to such varnishing operations. This process is called "off-line process".
• EP-A-1 333 073 a process for in-line varnishing was described.
• a combination of a specific offset ink comprising a particular solvent and of a lacquer comprising a photoinitiator which is poorly soluble in said solvent was used.
• said process did not fulfil all the requirements imposed on an in-line varnishing process.
• the above object has been surprisingly solved by the use of a traditional offset ink in an in-line varnishing process, said ink having a setting speed ratio of lower than 40%, and a contact angle of lower than 25°.
• a load of 1.8 to 2 g/m 2 ink is printed onto a Invercoat G coated paper (240 g/m 2 , from INAPA group lggesund paperboard).
• the load of the ink is calculated by subtracting the weight of the inking roller after printing from the weight of the inking roller before printing and dividing it by the area of the surface of the printed layer.
• Optical density values are measured with a common densiometer (a well-known device). Further details of the determination of the setting speed ratio are given in the example section.
• the term "contact angle” is defined as the value obtained by depositing a liquid droplet of TPGDA (tripropyleneglycol diacrylate) having a weight between 0.0065 and 0.0085 g onto the surface of a just printed ink layer having a thickness of between 35 and 40 ⁇ m, and measuring the contact angle, i.e. the angle between the surface of the ink layer and the liquid droplet with a standard contact angle goniometer 20 s after printing. Further details of the determination of the contact angle value are given in the example section.
• TPGDA tripropyleneglycol diacrylate
• said ink comprises a phenolic-modified rosin ester, a vegetable ester as a solvent, an organic pigment, a drier and optionally additives such as wax.
• a varnish or lacquer
• said ink provides a very fast setting speed as well as a good compatibility with a varnish (or lacquer), preferably an UV varnish to be applied in-line.
• the inks of the present invention provide for high gloss of the UV varnish applied on top of said ink. This is due to the fact that the inks of the present invention exhibit, at the same time, a very fast setting speed and a very good compatibility with the UV varnish. It was found for the first time that the drawbacks hitherto observed in in-line varnishing applications as described above can be overcome if an ink is used which simultaneously satisfy the criteria of fast setting speed and low contact angle value. It was moreover surprisingly found that the inks of the present invention provide also for the desired high gloss if a water-based varnish is applied in-line on top of said inks.
• the terms diluent and solvent shall have the same meaning.
• the applied ink layer will exhibit a stabilized surface. Thereby, heterogeneities at the interface of ink and varnish are avoided which would result from applying the varnish layer onto a not set ink layer which still has a moving surface. These heterogeneities would result in a lower and worse gloss.
• a setting speed ratio as defined above of lower than 40%, preferably lower than 30% and even more preferably lower than 20% is necessary in order to render an ink suitable for the in-line varnishing process of the present invention.
• the varnish preferably UV varnish
• This compatibility is defined according to the present invention by the contact angle value, which indicates the spreading of a droplet of the monomer TPGDA (tripropyleneglycol diacrylate) on the surface of a printed ink layer.
• TPGDA is a monomer which is commonly used in UV varnishes.
• the contact angle value is the angle between the surface of the just printed ink layer and the liquid droplet of TPGDA applied thereto, as measured after 20s as described above.
• a contact angle value as defined above of lower than 25°, preferably lower than 23° is necessary in order to render an ink suitable for the in-line varnishing process of the present invention.
• the ink has to possess a setting speed ratio as defined above of lower than 40% and simultaneously a contact angle value as defined above of lower than 25°.
• a preferred embodiment involves an ink comprising a phenolic-modified rosin ester as a binder and a vegetable ester as a solvent.
• Phenolic-modified rosin esters in their different grades and their manufacture are well- known in the art. While in principle any phenolic-modified rosin ester may be used, according to the present invention it is preferred to use phenolic-modified rosin esters with a very high polarity.
• Vegetable esters are well-known to the skilled man. According to the present invention, any vegetable ester may be used. According to a preferred embodiment, an ester of rapeseed oil (9-octadecenoic acid) is used in the offset printing ink.
• a combination of a phenolic-modified rosin ester and a vegetable ester results in a particularly preferred printing ink which provides both a very fast setting speed and a good compatibility with UV-varnishes conventionally used in said field.
• an offset ink comprising a mineral oil distillate as solvent component, similar to the ones described in EP-A-1 333 073, showed much less compatibility with conventional UV varnishes.
• the inks of the present invention provide for the same good compatibility with water-based varnishes.
• the traditional offset inks according to the present invention furthermore comprise an organic pigment. It has been found that organic pigments do not adversely influence the good compatibility of the ink provided by the above combination of resin and solvent.
• the offset inks which are preferred according the present invention are mainly composed of an ink vehicle which comprises said phenolic-modified rosin resin and said vegetable ester, and said organic pigment.
• said ink comprises 65 to 90 wt.-% of a combination of said resin and said vegetable ester and 10 to 35 wt.-% of said pigment.
• one or more driers are present in the offset ink used according to the present invention. Those driers aid in the oxidative drying of the ink film.
• any conventional drier for offset inks may be used, according to the present invention acrylates and more preferred octoates are chosen.
• said drier is a metal octoate selected from the group consisting of cobalt octoate and manganese octoate, or a mixture thereof.
• the offset inks used according to the present invention typically comprise 0.2 to 1.5 wt.-% of said one or more drier components.
• additives which are conventionally used in offset inks may be included.
• rheology modifiers such as gelling agents, antioxidants or waxes.
• Those additives are used in the typical amounts in which they are used in conventional offset inks.
• the traditional offset inks of the invention may further contain a wax component in the grinding medium.
• a wax component in the grinding medium.
• Any commonly used wax can also be incorporated into the traditional offset inks of the invention.
• Examples are polyethylene, polytetrafluoroethylene or synthetic paraffine waxes.
• An especially preferred wax according to the present invention is a micronised polyethylene/Fischer-Tropsch wax, i.e. a synthetic wax, which is sold under the trade name Polysperse by Eastman.
• the traditional offset inks of the invention preferably contain in the grinding medium a little amount of an anti-oxidant. Since an anti-oxidant adversely influences the drying properties of the traditional offset ink, only a very little amount thereof should be included.
• the amount of anti-oxidant in the final traditional offset ink should not exceed 2 %, more preferably lie in a range of from 0,1 to 1 ,5 % by weight, based on the weight of the entire final traditional offset ink. Any commonly used anti-oxidant may be included into the traditional offset inks of the invention.
• Oximes such as methyl ethyl ketoxime, substituted phenols such as butylated hydroxy toluene, or Quinones such as hydroquinone. From those compounds, Quinones and especially hydroquinone derivatives are the most preferred ones according to the present invention.
• the offset inks to be used according to the present invention may be obtained by mixing the individual components under conventional conditions.
• Offset inks as they are useful for the present invention are known in the art. For example, in US-5, 178,672, similar offset inks are described. However, up to now it has not been known that such offset inks may be used in an in-line varnishing process for the manufacture of printed articles.
• the in-line varnishing process of the present invention is carried out as known in the art on equipment commonly used for that process.
• the desired substrate is printed on at least one of its surfaces by means of an offset-printing process, frequently also called lithographic printing process.
• an offset-printing process frequently also called lithographic printing process.
• Any of the commonly used offset-printing processes such as the web or sheet-fed process can be used for the process according to the present invention. Reference is made in this respect to The Printing ink manual, R. H. Leach (ed.), 5 th ed., Blueprint, London 1993, p. 15-33, the content of which is incorporated herewith by reference.
• the substrate may be printed with one single traditional offset ink or with various different traditional offset inks, as known in the art. In the process according to the present invention, printing with up to six different colours is preferred.
• board package i.e. carton board
• any other substrate commonly printed by means of an offset-printing process such as paper or metal, can be used in the process according to the present invention.
• either one or any of the surfaces of the substrate may be printed.
• substrates having a smoothness of more than 200 are particularly preferred with respect to the desired high gloss. It is especially preferred if the substrate satisfies both criteria in parallel.
• An example for such an especially preferred substrate is a gloss coated paper sold under the name Magno star (from Sappi).
• the smoothness of a substrate is determined according to the Bekk measurement test: The substrate is put on a glass ring with a differential pressure (vacuum). Then, the time is measured until a defined air volume has flown out between glass and paper. This is a normalized test well-known to the skilled man. Usually, the respective value is given in the Technical Data Sheet of the substrate. A high value in said test (i.e. if it takes a long time for the air to flow out of the device) indicates that the air has difficulties to flow through the space between glass and substrate, because said space is very small. In other words, the substrate has a very smooth surface. On the other hand, a low value in said test (i.e.
• the substrate has a rough surface, resulting in a large gap between glass and substrate.
• the penetration speed is determined with a porometric ink test: A small quantity of porometric ink is put on a glass surface. The ink to be tested is put in a metallic plug. Said plug is placed onto the substrate for a period of 7 seconds, and the excess of ink is wiped off. The optical density on the imprint (D7sec) and on the comet trail (Dosec) is measured, respectively.
• a high value in said test indicates that much ink is absorbed within 7 s, i.e. a quick penetration has taken place.
• _A lowh value in said test indicates that little ink is absorbed within 7 s, i.e. a slow penetration has taken place.
• the printed substrates are overprinted with a lacquer layer in order to achieve several effects.
• that lacquer layer is designed to protect the underlying print against environmental influences.
• by means of said overlying lacquer layer the visual effects of the print are enforced by providing a glossy or matt effect.
• the present invention preferably deals with UV curable lacquer layers.
• lacquer layers are described in the art, for example in The Printing ink manual, R. H. Leach (ed.), 5 th ed., Blueprint, London 1993, p. 636-677, the content of which is incorporated herewith by reference.
• water-based lacquer layers may be used for the in-line varnishing process of the present invention.
• the lacquer layer is applied in-line directly after the substrate has been printed via an offset-printing process.
• the traditional offset ink is not given a sufficient amount of time to dry after being applied to the substrate, so that the lacquer layer is applied onto the printed substrate while the traditional offset ink is still wet. Therefore, the process according to the present invention may be described as a wet-on-wet coating process. If more than one surface of the substrate have been printed in the first step, then any of the printed surfaces is coated with the lacquer layer.
• any UV-curable varnish composition commonly used in this field may be used for generating the lacquer layer of the products of the invention.
• the composition can be readily chosen by the man skilled in the art in view of the end-user requirements imposed on the product to be made.
• a UV-curable varnish composition useful in the present invention comprises a prepolymer, a diluent, a photoinitiator, a co-initiator, and optionally additives such as surfactants, waxes or perfumes.
• the prepolymer component will polymerise upon radiation with UV light.
• cati- onic polymerising species are known, commonly free radical polymerising prepolymers are the most frequently used components in this field and also preferred according to the present invention. Any of the known prepolymers can be considered for the purposes of this invention.
• the most preferred species are acrylated species such as ep- oxy acrylates, polyurethane acrylates or polyester acrylates.
• diluents are added thereto.
• diluents which either penetrate into the substrate after the application of the lacquer layer or remain in said layer serving as plasticisers.
• examples for such diluents are high boiling esters, highly branched alcohols or alkyl phosphates.
• diluents which have functional groups giving them the ability to participate in the polymerisation process by serving as co-polymers.
• monofunctional monomers such as isodecyl acrylate (IDA) or phenoxy ethyl acrylate (PEE), difunctional monomers such as 1 -4-butane diol diacrylate (BDDA), poylethylene gylcol diacrylate (PEGDA) or thpropylene glycol diacrylate (TPGDA), trifunctional monomers such as pentaerythritol thacrylate (PETA) or trimethy- lol propane triacrylate (TMPTA) or monomers on the basis of glycerol, or higher functional monomers on the basis of acrylate moieties.
• trifunctional monomers such as TMPTA are particularly preferred.
• the photoinitiator commonly species which readily undergo a Norrish I or Norrish Il defragmentation upon being irradiated with UV light are used in the field. For species undergoing primarily a Norrish Il defragmentation, it is necessary to add a co-initiator in order to ascertain the efficiency of the photoinitiator. Hydrogen donors are frequently used for that purpose, and any compound having sufficiently acidic H atoms will be considered by the man skilled in the art. Examples are amines such as tertiary or secondary amines, for example N-methyl diethanolamine (MDEA).
• MDEA N-methyl diethanolamine
• the UV-curable varnish composition of the invention may further comprise additives such as surfactants, waxes or perfumes, which are commonly known to the man skilled in the art.
• the UV-curable varnish composition comprises between 15 to 30 % by weight, preferably 18 to 25 % by weight, based on the weight of the entire UV-curable varnish composition, of the prepolymer; between 40 to 70 % by weight, preferably between 50 and 70 % by weight, based on the weight of the entire UV-curable varnish composition, of the diluent; between 1 to 10 % by weight, preferably between 2 and 7 % by weight, based on the weight of the entire UV-curable varnish composition, of the photoinitiator(s); between 1 to 10 % by weight, preferably between 5 to 10 % by weight, based on the weight of the entire UV-curable varnish composition, of the co-initiator; and the balance of additives such as surfactants or perfumes.
• the ingredients of the UV-curable varnish composition are mixed together at room temperature until a complete dissolution of the photoinitiators in the medium has taken place.
• the thus prepared UV-curable varnish composition can be applied as described above onto the desired substrate.
• UV-curable varnish composition After the UV-curable varnish composition has been applied as described above onto the substrate, curing is carried out according to any conventional method known to the man skilled in the art.
• a source for UV radiation may be used a mercury vapour lamp, either of the high pressure, medium pressure or low pressure type, the me- dium pressure type being the most preferred one.
• the lamp is fitted in a short distance above the target to be irradiated at some convenient position.
• water-based varnishes may be used in the inline varnishing process of the present invention.
• These water-based varnishes are generally known in the art.
• a useful example is a water-based varnish comprising a mixture of an acrylic resin and of an emulsion resin such as a styrene-acrylic copolymer emulsion as a binder component, in water as a solvent.
• Additives such as wax, tensides of antifoaming agents may be present.
• Water-based varnishes may be cured by evaporation of the solvent water (drying). Said evaporation may be supported by using e.g. an infrared dryer or a flow of hot air. Both water-based varnishes and methods of drying them are known in the art.
• the products obtained by the in-line printing and varnishing process according to the present invention exhibit a significantly reduced variation of gloss between printed and not printed parts of the surface in comparison to products obtained in an-line process by not using the specific traditional offset inks and UV-curable varnish compositions.
• the above offset-ink and the above UV varnish used for the above described in-line varnishing process can also be used for other applications, for example for a double- coating application.
• the ink layer is first applied to a substrate, thereafter another layer such as a layer of waterborne varnish is applied to the ink layer, followed by the application of a UV varnish on said another layer.
• 59.50 wt.-% of said varnish were mixed at ambient temperature with additional 8.40 wt.- % of the above vegetable ester (9-octadecenoic acid methyl ester, sold by Novance under the trade name Estorob 926.65), 0.50 wt.-% of the drier cobalt octoate (10%, sold by lngfer FiIt & Minerals), 0.90 wt.-% of the drier manganese octoate (10%, sold by lngfer FiIt & Minerals), and 1.00 wt.-% of the anti-oxidant mono-t-butylhydroquinone (MTBHQ, sold by PEP under the trade name Ennelox TP50V) .
• MTBHQ mono-t-butylhydroquinone
• Comparative example 1 was a yellow ink of the TEMPO MAX series.
• Com- parative example 2 was a magenta ink of the TEMPO MAX series.
• Comparative example 3 was a cyan ink of the TEMPO MAX series.
• Comparative example 4 was a black ink of the TEMPO MAX series.
• the Tempo Max series is sold by Siegwerk (versatile series for packaging application).
• the binder of said ink is composed of approx. 43% modified phenolic rosin ester, approx 39% mineral distillate, approx 18% linseed oil.
• the composition of the ink is composed of the binder described above, 5-15% alkyde resin, pigments, mineral distillates for viscosity adjustment, driers, antioxidant, and wax.
• the ink films were printed with the loads indicated below in table 1 on a substrate (In- vercoat G-coated paper, 240 g/m2, from INAPA group (Iggesund paperboard)) such that a load between 1.8 and 2.0 g/m 2 was obtained. Slight deviations from said load were accepted.
• the load of the ink layer was calculated as follows:
• the printing conditions were as follows: Printing pressure at unit 1 (metal form): 400 N Printing pressure at unit 2 (metal form): 400 N Printing speed: 0.5 m/s Thermostat setting: 30 0 C Distributing time: 30 s
• the inks were printed on a prufbau machine (lab printing device).
• the parameters described before were the parameters of the prufbau equipment to conduct the test.
• the chronometer was started and the initial optical density was measured with a densitometer.
• the printed substrate was put in front of the counter print pressure, and a second substrate of the same kind was put onto the printed layer. After 20 s, pressure was applied. Simultaneously, after 20 s, 30 s, and 40 s, the optical density of the printed layer was measured with a densitometer
• the inks of the present invention show a significantly lower setting speed ratio than the inks of the prior art.
• a small droplet of TPGDA was deposited onto the surface immediately after printing the ink layer.
• Said droplet had a weight between 0.0065 and 0.0085 g (which in consideration of the density of TPGDA of 1.11 g/cm 3 corresponds to a volume between 0.0058 and 0.0077 cm 3 ).
• the chronometer was started immediately after the droplet was deposited onto the surface of the ink layer.
• the contact angle was read directly on the graduated goniometer scale after 20 s.
• the test was performed 4 times for each ink in order to verify results. An average of 4 measurements differing at most 2° from each other was taken into consideration. Results are shown below in table 2.
• Table 2 shows that the inks of the present invention exhibited a significantly lower contact angle value 20 s after printing than the conventional inks.
• the conventional inks failed to satisfy the contact angle requirements of below 25° according to the present invention.
• a yellow ink according to the present invention having a setting speed ratio (determined according to the above description in the results section) of below 17%, as well as a contact angle (determined according to the above description in the results section) of lower than 23° was used.
• Gloss measurements were carried out as described above with the exception that one time the same conventional UV varnish as described above was used, whereas the other time a water-based varnish consisting of 30 wt.-% of an acrylic resins solubilized in a mixture of water and an amine, of 55 wt.-% of an emulsion resin (a styrene-acrylic copolymer emulsion), of 10 wt.-% water, and of 5 wt.-% conventional additives (was, surface-active agents, and antifoaming agents) was used.
• the above prepared yellow ink was printed onto a substrate (LumiArt, 135 g/m 2 , from Stora Enso). Directly after printing, the UV-varnish or the above described water-based varnish were applied in-line as described above in the results section. Curing of the UV varnish was carried out as described above in the results section, whereas the water- based varnish was cured by evaporation of the solvent water. Gloss measurements at point T24 were carried out as described above in the results section. In the case of the UV-varnish, gloss at T24 was 74-78, whereas with the water-based varnish, gloss at T24 was 65-79. thus, the water-based varnish showed also a high gloss, comparable with the gloss obtained by using the UV-varnish.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Physics & Mathematics (AREA)
• Electromagnetism (AREA)
• Mechanical Engineering (AREA)
• Plasma & Fusion (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Printing Methods (AREA)

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• 2006
  • 2006-12-18 EP EP06126311A patent/EP1935662A1/de not_active Withdrawn
• 2007
  • 2007-12-17 EP EP07857703A patent/EP2094501A1/de not_active Withdrawn
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