Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C1/00—Forme preparation
  • B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
  • B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/04—Negative working, i.e. the non-exposed (non-imaged) areas are removed
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/06—Developable by an alkaline solution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/12—Developable by an organic solution
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
  • B41C2210/264—Polyesters; Polycarbonates
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
  • B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
  • B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
  • B41C2210/266—Polyurethanes; Polyureas
• • 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
  • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
  • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
  • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
  • B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black

Definitions

• the invention relates to a radiation-sensitive (photopolymerizable) mixture with a polymeric binder, a radically photopolymerizable component, a Infrared absorber and a triazine. It continues to apply Recording material with a support and a radiation-sensitive Layer.
• a mixture of the type mentioned is already in EP-A 0 369 645. It comprises a free-radically polymerizable Monomer and a soluble therein photoinitiator system, the trihalomethyl-substituted 1,3,5-triazine, a sensitizer for the triazine and an electron-donor compound with a Oxidation potential of greater than zero and less than that of 1,4-dimethoxy-benzene contains.
• Sensitizers are coumarin, Xanthene, acridine, thiazole, thiazine, oxazine, azine, aminoketone, Methine and polymethine dyes, porphyrins, aminotriarylmethanes, Called merocyanines, squarylium and pyridinium dyes. you are sensitive especially to radiation in the range of 350 to 700 nm. For radiation in the near IR range (700 to 1200 nm) is the Sensitivity, however, only low.
• EP-A 0 315 988 is a photopolymerizable Mixture disclosed for radiation in the range of 600 to 700 nm is sensitive. It comprises a polymerizable, ethylenic unsaturated compound, a radical generator and a substituted one 2-phenyl-2H-naphtho [6,5,4-a, m, n] thioxanthene-1,3-dione or a substituted 3-alkoxy-2-phenyl-naphtho [6,5,4-a, m, n] thioxanthen-1-one as a sensitizer.
• the subject of EP-A-0 441 524 is one upon irradiation crosslinking composition with a polymer to which mono-, di- or trihalomethyl-substituted [1,3,5] triazine residues via a Bridge group are covalently bonded.
• the base polymer may be made a variety of polymers are selected.
• a polyamide a polyester, a polyurethane, a Polysiloxane, a phenolic resin, a polystyrene, a polyacrylate, a Polyacrylic acid, a polyacrylamide, a polyacrylonitrile, a Polyethylene, a polybutadiene, polyvinylpyrrolidone, polycaprolactone, Gelatin, starch or a polysaccharide.
• EP-A 0 563 925 is a photopolymerizable mixture discloses a radically polymerizable monomer substituted 2-phenyl-4-halomethyl (or 4,6-bis-halomethyl) - [1,3,5] triazine and a compound known as Sensitizer for the triazine. The mixture is used for the production of negative-working printing plates.
• a directly imageable recording material for the production of planographic printing plates is described in EP-A 1,106,381. It comprises an electrochemically roughened carrier of a special aluminum alloy and a photosensitive layer, an IR absorber and a water-insoluble, but alkali-soluble contains polymeric binder.
• a photosensitive layer comprises a monomer with one or more polymerisable, substituted acrylate group (s) or derivatives thereof and a Photopolymerization initiator contains.
• a Photopolymerization initiator contains.
• Preferred initiators are aromatic ketones, aromatic onium salts, organic peroxides, Hexaarylbiimidazole, borates, metallocenes and compounds with Carbon-halogen bonds. The latter also count optionally further substituted [1,3,5] triazines with Trihalogenmethyl Reliefn.
• the photosensitive layer may be next to it Sensitizer dyes included.
• On the photosensitive Layer may additionally be a polyvinyl alcohol layer.
• a major disadvantage of this recording material is in that the monomers are synthetically difficult to access and thus are correspondingly expensive. Furthermore, the reactivity and so that the photosensitivity of the layer is reduced.
• EP-A-1 176 007 and EP-A-1 162 078 describe a radiation-sensitive A mixture comprising a free-radically polymerizable (meth) acrylate monomer having at least two (Meth) acrylate groups and at least one photooxidizable group, a Radical initiator, an IR-absorbing heptamethine cyanine dye, and an organic contains polymeric binder.
• the radical initiator absorbs near infrared radiation.
• Heptamethine cyanine dye contains and acrylate and / or Methacrylate monomers having at least one photooxidizable group.
• the subject of the present invention is accordingly a radiation-sensitive mixture containing a radical polymerizable acrylate or methacrylate monomer and / or oligomer with at least two acrylate and / or meth-acrylate groups and at least one photooxidizable group, a photoinitiator, an IR absorbing dye and an organic polymer Contains binder, and characterized in that the IR-absorbing Dye is a heptamethine cyanine dye, that the mixture is sensitive to the near infrared region, and the photoinitiator does not absorb this radiation.
• heptamethine cyanine dyes in which 3 Methine carbon atoms part of a 5- to 7-membered isocyclic or heterocyclic ring.
• the name "Heptamethine cyanine dyes” includes amphoteric as well as ionic Connections.
• the aromatic end groups in the dyes are preferably indole or indolium groups, to which, if appropriate still more rings, especially carbocyclic rings, fused could be.
• the binder can be made from a whole range of organic Be selected polymers. Also mixtures of different binders can be used. Suitable examples are chlorinated Polyalkylenes (especially chlorinated polyethylene and chlorinated Polypropylene), poly (meth) acrylic acid alkyl ester or alkenyl ester (in particular polymethyl (meth) acrylate, polyethyl (meth) acrylate, Polybutyl (meth) acrylate, polyisobutyl (meth) acrylate, Polyhexyl (meth) acrylate, poly [(2-ethyl-hexyl) - (meth) acrylate] and Poly [allyl (meth) acrylate]), copolymers of (meth) acrylic acid alkyl esters or alkenyl esters with other copolymerisable Monomers (in particular with (meth) acrylonitrile, vinyl chloride, Vinylidene chloride, styrene and / or butadiene), poly
• binders which Contain carboxy groups, particularly suitable. That's in particular Copolymers containing units of ⁇ , ⁇ -unsaturated carboxylic acids or Dicarboxylic acids (preferably acrylic acid, methacrylic acid, crotonic acid, Vinylacetic acid, maleic acid or itaconic acid).
• copolymers with units of (meth) acrylic acid and Units of alkyl (meth) acrylates, allyl methacrylates and / or (Meth) acrylonitrile, as well as copolymers with units of Crotonic acid and units of alkyl (meth) acrylates and / or (Meth) acrylonitrile, and finally vinylacetic acid / alkyl (meth) acrylate copolymers.
• copolymers with Units of maleic anhydride or maleic acid monoalkyl esters are also suitable.
• copolymers with units Maleic anhydride and styrene, substituted styrenes, unsaturated ethers or esters or unsaturated aliphatic ones Hydrocarbons, as well as those obtainable from such copolymers Esterification.
• products from the Reaction of hydroxyl-containing polymers with intramolecular Dicarboxylic anhydrides arise.
• copolymers here are polymers with units of at least 2 different Monomers are understood, including terpolymers and higher Copolymers. Also useful are polymers in which groups with acidic hydrogen atoms occur, part or all of them with activated isocyanates is reacted.
• (meth) acrylic acid is related to the present invention for "acrylic acid and / or methacrylic acid”. The same applies to (meth) acrylonitrile, - (meth) acrylate, (meth) acrylamide, etc.
• the organic polymers used as binders have in general, a mean molecular weight Mw of 600 to 200,000, preferably 1,000 to 100,000. Preference is furthermore given to polymers which an acid number between 10 and 250, preferably from 20 to 200, or a hydroxyl number of 50 to 750, preferably 100 to 500, exhibit.
• the proportion of binder (s) is generally 10 to 90 wt .-%, preferably 20 to 80 wt .-%, each based on the total weight the non-volatile components of the radiation-sensitive Mixture.
• the radically polymerizable acrylate or methacrylate compound with at least one photooxidizable group For example, a connection with a primary, secondary and in particular tertiary amino group.
• urea group is meant in context with the present invention, a group of the formula> N-CO-N ⁇ be understood, in which the valencies on the nitrogen atoms with Hydrogen atoms or hydrocarbon radicals are saturated (It should not have more than one valence on each of them Nitrogen atoms are saturated with a hydrogen atom). It is but also possible that a valence on a nitrogen atom the Binding to a carbamoyl group (i.e., a -CO-NH group) producing a biuret structure.
• Aryl radicals R are generally mono- or binuclear, but preferably mononuclear. They may be substituted by (C 1 -C 5 ) alkyl or (C 1 -C 5 ) alkoxy groups. When R 1 and R 2 are alkyl or alkoxy groups, they preferably contain 1 to 5 carbon atoms. R 3 is preferably a hydrogen atom or a methyl group.
• X 1 is preferably a straight-chain or branched aliphatic and / or cycloaliphatic radical having preferably 4 to 10 carbon atoms.
• X 2 comprises in a preferred embodiment 2 to 15 carbon atoms.
• X 2 is a saturated, straight-chain or branched aliphatic and / or cycloaliphatic radical having this number of carbon atoms. Up to 5 methylene groups in these radicals may be replaced by oxygen atoms.
• X 2 consists of pure hydrocarbon chains, the radical generally comprises 2 to 12, preferably 2 to 6 carbon atoms. X 2 may also be a cycloaliphatic group having 5 to 10 carbon atoms, in particular a cyclohexanediyl group.
• the saturated heterocyclic ring formed by D 1 , D 2 and the two nitrogen atoms generally comprises 5 to 10 ring members, in particular 6 ring members.
• the heterocyclic ring is preferably a piperazine and the radical derived therefrom is a piperazine-1,4-diyl radical.
• the moiety E in a preferred embodiment is an alkanediyl group, usually comprising about 2 to 6 carbon atoms.
• the bivalent 5- to 7-membered, saturated, isocyclic group E is preferably a cyclohexanediyl, in particular a cyclohexane-1,4-diyl group.
• the divalent isocyclic aromatic group E is preferably an ortho, meta or para-phenylene group.
• the divalent 5- or 6-membered aromatic heterocyclic group E preferably contains nitrogen and / or sulfur atoms in the heterocyclic ring.
• c is preferably 1, ie each of the radicals in the square bracket generally contains only one polymerisable group, in particular only one (meth) acryloyloxy group.
• Hydroxyalkylamines are diethanolamine, triethanolamine, tris- (2-hydroxy-propyl) -amine, Tris (2-hydroxybutyl) amine and alkyl bishydroxyalkyl amines.
• Hydroxy-containing esters are preferably hydroxyethyl (meth) acrylate, Hydroxypropyl (meth) acrylate and hydroxyisopropyl (meth) acrylate used.
• the compounds of formula II are analogous to those of Formula I prepared, instead of from reaction products Hydroxyalkyl acrylates or alkacrylates and diisocyanates the corresponding acrylic acid or alkacrylic acid glycidester used become. Such compounds and processes for their preparation are otherwise disclosed in EP-A 0 316 706.
• X 1 , R 3 , a and b in the formula IV have the abovementioned meaning;
• X 2 represents a divalent hydrocarbon group in which up to 5 methylene groups may be replaced by oxygen atoms.
• the running number a in this formula is preferably 0 or 1;
• i is preferably a number from 2 to 10.
• polymerizable compounds with photooxidizable groups are also reaction products of mono- or diisocyanates with polyhydric alcohols in which all or part of the Hydroxy groups are esterified with (meth) acrylic acid suitable. Preference is given to products as they result from the implementation of Hydroxyalkyl (meth) acrylates with diisocyanates arise.
• Such Monomers are known and, for example, in DE-A 28 22 190 or DE-A 20 64 079 described.
• the mixture according to the invention can moreover photopolymerizable acrylate and / or alkacrylate compounds with 2 or more, preferably 3 to 6, acrylate and / or alkacrylate, especially methacrylate groups.
• This multifunctional Compounds act as crosslinkers.
• Preferred crosslinkers are (Meth) acrylates of saturated aliphatic or alicyclic, trihydric or polyhydric alcohols, such as alkanediols (especially Ethylene glycol and propylene glycol), bis-phenol-A, trimethylolethane, Trimethylolpropane, pentamethylolpropane, pentaerythritol or Dipentaerythritol.
• ethoxylated and propoxylated trimethylolpropane tri (meth) acrylate ditrimethylolpropane tetra (meth) acrylate, Tris (2-hydroxyethyl) -isocyanurattri (meth) acrylate or glycerol tri (meth) acrylate.
• Proportion of crosslinking acrylate and / or Alkacrylate compounds are generally up to 20% by weight, preferably 5 to 15 wt .-%, each based on the total weight of non-volatile constituents of the radiation-sensitive mixture.
• the proportion of all photopolymerizable monomers or oligomers is generally from 10 to 85% by weight, preferably from 20 to 75% by weight, in each case based on the total weight of the non-volatile Components of the radiation-sensitive mixture. There are generally at least 40% by weight of the photopolymerizable monomers and / or oligomers such with photooxidizable groups.
• the proportion of heptamethine cyanine dye is general 0.01 to 10.0 wt .-%, preferably 0.5 to 8.0 wt .-%, each based on the total weight of the nonvolatile constituents of the photopolymerizable mixture.
• Photoinitiators are known per se.
• Well suited are triazine compounds with at least one photocleavable Trihalogenmethyl devis, in particular a trichloro or Tribromomethyl.
• the trihalomethyl groups can thereby directly, via a conjugated double bond or via a chain of conjugated double bonds to an aromatic carbocyclic or heterocyclic ring.
• Such compounds are for example in DE 2 718 259, EP-A 0 137 452 and in EP-A 0 563,925. Basically absorb the used Triazines do not use the radiation used for imaging.
• Trihalogenmethyltriazine can be used, whose Own absorption is below 300 nm. Such materials are particularly preferred, because thereby the photoreactivity towards the usual interior lighting is reduced.
• usable Trihalomethyltriazines are, for example, those which are (saturated) aliphatic substituents or unsaturated substituents with only a few extended mesomeric ⁇ -electron systems contain.
• Proportion of photoinitiator (s) is generally from 0.1 to 20 wt .-%, preferably 1.0 to 10 wt .-%, each based on the total weight the non-volatile constituents of the photopolymerizable Mixture.
• predispersed phthalocyanine pigments serve primarily for coloring the mixture and the layers produced with it. Their share is generally about 1 to 20 wt .-%, preferably about 2 to 14 wt .-%.
• Particularly suitable Pre-dispersed phthalocyanine pigments are described in DE-A 199 15 717 and DE-A 199 33 139 discloses. Preferred are in particular metal-free phthalocyanine pigments.
• additives that inhibit thermally induced polymerization, hydrogen donors, Dyes, colored and colorless pigments, color formers, Filter dyes, indicator dyes, plasticizers and / or Chain transfer agent.
• additives are suitably selected those that do not absorb the imagewise acting radiation.
• the radiation-sensitive mixture is useful in a dissolved or dispersed organic solvent and the solution or Dispersion applied as a thin film on the support.
• the Can be applied by pouring, spraying, dipping, by applying with the help of rollers or similar, known in the art Procedure done. After drying in this way Receive recording material from which, for example Printing forms for high-pressure, planographic, gravure or screen printing let produce. It can also be a material that makes up Relief copies (for example for the production of texts in Braille), single copies, Gerbordinate, Pigmentmul or similar to produce image-structured products.
• the mixture according to the invention is also suitable for the production of ⁇ tmreservagen, for example, in the production of Printed circuit boards or name tags can be used, as well as for molding. However, it is preferably used for Production of photoresist layers and printing plates.
• the present invention is accordingly also a Recording material for the production of printing plates with a Carrier and a layer of the invention photopolymerizable mixture.
• carrier material for printing plates are films, tapes or plates made of metal (in particular made of aluminum or an aluminum alloy, steel, zinc or Copper) or plastic (especially polyester - specifically Polyethylene terephthalate or cellulose acetate), for screen printing media also perlon gauze.
• metal in particular made of aluminum or an aluminum alloy, steel, zinc or Copper
• plastic especially polyester - specifically Polyethylene terephthalate or cellulose acetate
• screen printing media also perlon gauze.
• the preferred one Support for offset printing plates is made of aluminum or an Al alloy and is electrochemically roughened on its surface, then anodized, optionally also with a hydrophilicizing agent (for example Polyvinylphosphonic acid).
• the IR laser sources familiar to the person skilled in the art between 700 and 1200 nm are used for imagewise radiation. Preference is given to laser diodes which emit in the NIR range.
• the novel recording material has a particularly high imaging performance and is therefore particularly suitable for digital imaging with NIR laser beams. In the subsequent development process is then differentiated exactly between non-image areas and image locations, so that the dot gain is surprisingly significantly reduced. Even small negative fonts are therefore still clearly reproduced. At the same time, the material has a very high sensitivity in the NIR wavelength range.
• the radiation-sensitive layer It is practically essential to protect the radiation-sensitive layer from atmospheric oxygen during NIR-induced polymerization. This is most easily achieved by a covering layer which is impermeable to oxygen or only slightly permeable ("poorly permeable” means a permeability of not more than 100 cm 3 O 2 / m 2 * d * bar, determined in accordance with DIN 53 380 at 23 ° C. ) applied to the radiation-sensitive layer.
• the cover layer may be self-supporting and be stripped before the subsequent development step. It then consists for example of a laminated polyester film. Also, overcoats of a material that is soluble or dispersible (at least in the uncured areas) in the developer liquid may be used.
• Suitable materials for a cover layer which is completely soluble in aqueous alkaline developers are, for example, polyvinyl alcohol, polyvinylpyrrolidone, polyphosphates, sugars, etc.
• the thickness of the cover layer is generally 0.1 to 10 .mu.m, preferably 1 to 5 .mu.m.
• the printing plate thus obtained was imaged with a CREO Trendsetter 3244T (2400 dpi), heated for 1 min at 100 ° C and then with an aqueous-alkaline developer (Agfa EN 231C) at 28 ° C at a flow rate of 1 m / min. (Agfa VSP85).
• the indicated sensitivity corresponded to that laser energy in the image plane which was required to make a 50% field formed of 1x1 and 8x8 pixels appear bright. The value determined in this way was 18 mJ / cm 2 .

Landscapes

• Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Thermal Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Photosensitive Polymer And Photoresist Processing (AREA)
• Materials For Photolithography (AREA)

Priority Applications (4)

Applications Claiming Priority (1)

Publications (2)

Family

ID=28799725

Family Applications (1)

Country Status (3)

Families Citing this family (119)

Family Cites Families (13)

• 2002
  • 2002-04-29 DE DE50204080T patent/DE50204080D1/de not_active Expired - Lifetime
  • 2002-04-29 EP EP20020100424 patent/EP1359008B1/de not_active Expired - Lifetime
• 2003
  • 2003-04-30 JP JP2003125528A patent/JP2003344997A/ja active Pending

Also Published As

Similar Documents

Legal Events