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
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
  • G09F3/04—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps to be fastened or secured by the material of the label itself, e.g. by thermo-adhesion
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
  • B29C49/24—Lining or labelling
  • B29C2049/2414—Linings or labels, e.g. specific geometry, multi-layered or material
  • B29C2049/24302—Label materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/744—Labels, badges, e.g. marker sleeves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M1/00—Inking and printing with a printer's forme
  • B41M1/06—Lithographic printing
• • 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
  • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers

Definitions

• a label is set in a mold in advance so that the surface side on which the label is printed is in contact with the mold wall surface, and a molten thermoplastic resin parison is guided and hollow-molded in the mold, or
• the present invention relates to a label used for in-mold molding in which a molten thermoplastic resin is injection-molded, or a molten thermoplastic resin sheet is vacuum-formed or pressure-formed to produce a label bonding container.
• a blank or label is inserted in the mold in advance, and then the container is molded in the mold by injection molding, hollow molding, differential pressure molding, foam molding, etc. Molding and painting on containers.
• Such an in-mold molding label is, for example, a non-stretched transparent film obtained by extrusion molding or force-rendering of crystalline polypropylene or polyethylene, and the base material is coated with ethylene / butyl acetate. Labels obtained by coating and drying a solution of low melting point resin such as coalescing with a gravure coater, etc., or laminating low melting point resin film to the substrate using an adhesive, or extrusion lamination Labels obtained by direct lamination have been proposed.
• the non-stretched transparent film obtained in this way has insufficient antistatic properties, and when offset printing is performed on a sheet-by-sheet basis, there is a problem in paper feeding and discharging properties in a printing press. Further, when a migration-type antistatic agent is incorporated for the purpose of imparting antistatic performance, there is a problem that not only the long-term antistatic effect is insufficient but also the adhesion of the offset ink is poor. Also, although the transparent in-mold label described in Japanese Patent No. 2790197 has excellent adhesiveness to a container, Tensile modulus 2, 0 0 0-6, the lower the 0 0 0 kg / cm 2, there is a problem in paper feeding and discharging properties of the offset printing with similarly sheet.
• the present invention Since the present invention has excellent antistatic properties and excellent ink adhesion, it is possible to print a table in offset printing by sheet-by-sheet, and as a result, it can respond to orders for small lot labels with short delivery time.
• the purpose of the present invention is to provide a transparent label for in-mold molding which excels in cutting and punching of a label after printing, and has excellent insertability into a mold, and is firmly fused to a container without generation of a plister.
• thermoplastic resin composition forming a surface layer contains a permanent antistatic agent, an inorganic fine powder, and Z or an organic filler.
• a thermoplastic resin composition forming a surface layer contains a permanent antistatic agent, an inorganic fine powder, and Z or an organic filler.
• the present invention is a non-stretched multilayer film comprising at least two layers of a surface layer and a heat transfer resin layer, wherein the surface layer comprises at least one of a permanent antistatic agent, an inorganic fine powder, and an organic boiler.
• the present invention provides a transparent label for in-mold molding, comprising a thermoplastic resin composition containing the same, and a center line average roughness of a surface layer of 0.2 to 3 / m. More preferably, the present invention provides a transparent label for molding, wherein the heat-sealable resin layer contains a permanent antistatic agent in the ethylene resin.
• FIG. 1 is a cross-sectional view of an in-mold molding label of one embodiment of the present invention.
• 4 is a center layer
• 5 is a heat-sealing resin layer
• 6 is an embossed peak
• 7 is an embossed valley.
• Figure 1 is a schematic cross-sectional view of a label for hollow molding.
• 1 is a label for in-mold molding
• 2 is printing
• 3 is a surface layer
• 4 is a center layer
• 5 is a heat-sealing resin.
• the center layer 4 can be provided between the surface layer 3 and the heat-sealing resin layer 5 if necessary.
• the surface of the heat-sealable resin layer is embossed to prevent the occurrence of pre-star during in-mold molding.
• Examples of the material of the surface layer of the present invention include propylene-based resin, high-density polyethylene, medium-density polyethylene, linear-linear low-density polyethylene, ethylene'acetic acid biel copolymer, ethylene polyacrylic acid copolymer, and alkyl ethylene polyacrylate.
• Polyamide resins such as copolymers, polyethylene terephthalate resins, polychlorinated vinyl resins, polyamide resins such as nylon-16, nylon-6,6, nylon-16,10, nylon-6,12, ABS Resins, ionomer resins and the like, and preferably propylene resin, It is a thermoplastic resin having a melting point in the range of 130 to 280 ° C, such as high-density polyethylene and polyethylene terephthalate resin, and these resins can be used as a mixture of two or more kinds.
• polyolefin-based resin it is preferable to use a polyolefin-based resin. Further, among the polyolefin-based resins, it is more preferable to use a propylene-based resin or high-density polyethylene in view of cost, water resistance, and chemical resistance.
• Such a propylene-based resin includes isotactic or syndiotactic, propylene homopolymer (polypropylene) having various degrees of stereoregularity, propylene as a main component, ethylene, 1-butene, Copolymers with ⁇ -olefins such as hexene, 11-heptene and 4-methyl-1-pentene can be preferably used.
• These copolymers may be binary, ternary, or quaternary, and may be random or block copolymers. Further, the content of 4 0-9 4 wt 0/0, it is preferred that preferably 3 0-9 0% by weight.
• the type of the inorganic fine powder and the inorganic or organic filler contained in the surface layer is not particularly limited.
• Examples of the inorganic fine powder include heavy calcium carbonate, light calcium carbonate, calcined sauce, tanolek, barium sulfate, diatomaceous earth, magnesium oxide, zinc oxide, titanium oxide, silicon oxide, and the like. It may be. Above all, heavy calcium carbonate, calcined clay, and talc are inexpensive and have good moldability.
• Organic fillers include polyethylene terephthalate, polybutylene terephthalate, polyamide, polycarbonate, polyethylene naphthalate, polystyrene, melamine resin, polyethylene sulphite, polyimide, polyether ether ketone, polyether ether ketone, and polyphenylene.
• Select one of the above inorganic fine powder and / or organic filler and use it alone Or two or more of them may be used in combination. Further, its content is preferably 1 to 20% by weight, more preferably 2 to 15% by weight.
• Examples of the permanent antistatic agent constituting the surface layer include polyether ester amides described in JP-A-58-18838, JP-A-11-163324 and the like. be able to.
• Lactams such as caprylactam and laurolactam and salts of diaminedicarboxylic acids such as hexamethylenediamine-sebacate and hexamethylenediamine-isophthalate. , Especially force prolatatam, 12-amino dodecanoic acid, hexamethylene Diamine monoadipate is preferably used.
• Poly (alkylene oxide) glycols which are constituents of polyether ester amides, include polyethylene glycol, poly (1,2-propylenoxide) glycolone, poly (1,3-propylene oxide) glycol, and poly (1,3-propylene oxide) glycol.
• poly (Tetramethylene oxide) glycol poly (hexamethylene oxide) glycol, block or random copolymer of ethylene oxide and polypyrene oxide, or block or random copolymer of ethylene oxide and tetrahydrofuran Used.
• polyethylene glycol is particularly preferably used because of its excellent antistatic properties.
• the number average molecular weight of poly (alkylene oxide) glycol is used in the range of 200 to 6,000, especially 250 to 4,000, and if the number average molecular weight is less than 200, If the obtained polyetheresteramide has poor mechanical properties, and the number average molecular weight exceeds 6,000, the antistatic properties are insufficient, which is not preferable.
• dicarboxylic acids 4 to 20 carbon atoms which are constituents of polyetheresteramide
• dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-1,2,6-dicarboxylic acid, naphthalene-1,2,7-dicarboxylic acid, diphenyl-1,4,4, dicarboxylic acid, and diphenoxyethanedicarboxylic acid.
• Aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and alicyclic dicarboxylic acids such as dicyclohexyl 4,4, dicarboxylic acid
• Aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, sebacic acid and dodecandioic acid (decanedicarboxylic acid), and the like
• the (ii) poly (alkylene oxide) glycol and the (iiii) dicarponic acid react in a molar ratio of 1: 1 in the reaction, but are usually supplied in different charge ratios depending on the type of dicarboxylic acid used.
• polyetheresteramide constituent units of polyetheresteramide and are used in the range of 90 to 10% by weight / 0. If it exceeds 0% by weight, the mechanical properties of the polyetheresteramide are inferior. If it is less than 10% by weight, the resulting resin has poor antistatic properties, which is not preferable.
• the method for polymerizing the polyetheresteramide is not particularly limited.
• (C) a method in which the compounds (i), (ii) and (iii) are simultaneously charged into a reaction vessel, melt-mixed, and then polymerized at once under a high vacuum;
• antimony-based catalysts such as antimony trioxide
• tin-based catalysts such as monobutyl sulphoxide
• titanium-based catalysts such as tetrabutyl titanate, tetrabutyl zirconate, etc.
• zirconate-based catalysts may be used.
• the content of the polyetheresteramide (b) in the surface layer component is usually 5 to 40% by weight, preferably 6 to 30% by weight. / 0 .
• the amount of the component (b) is less than the above range, the antistatic property is insufficient, and when the amount exceeds the above range, the strength of the label surface is insufficient.
• Sodium chlorate, sodium perchlorate, calcium hydroxide, magnesium hydroxide, zirconium hydroxide, calcium oxide are used for the purpose of more reliably expressing the antistatic properties of the above polyether ester amide.
• Metal salts such as magnesium, magnesium oxide, and sodium phosphate; and ionomers having a counter ion of Zn or Na (a copolymer of ethylene or propylene with an ⁇ ,] 3-unsaturated carponic acid derivative has a valence of 1).
• An ionic polymer to which 3 to 3 metal ions have been added can be added preferably in the range of 0.01 to 5% by weight.
• maleic acid-modified polypropylene preferably modified polyolefin and maleic acid-modified polyethylene from 0.5 to 5 weight 0 / 0 may be added.
• a center layer may be provided between the surface layer and the heat-sealing resin layer.
• a thermoplastic resin used for the surface layer can be used.
• polyolefin resins propylene resins and / or ethylene resins (high-density polyethylene, medium-density polyethylene, linear linear low-density polyethylene, etc.) may be contained in terms of cost, water resistance, and chemical resistance. More preferred.
• isotactic propylene having high stereoregularity of a propylene homopolymer is preferable because of its high rigidity. It is more preferable to add a nucleating agent to these thermoplastic resins for the purpose of improving rigidity and transparency.
• nucleating agents include 1,3,2,4-dibenzylidenesol bitonore, 1,3,2,4-zy (p-methinolebenzylidene) sonolebitonele, 1,3-o-methylbenzylidene 2,4- ⁇ -methinole Benzylidene, -t-butylinole aluminum benzoate, bis (4-t-butylphenyl) sodium phosphate, 2,2,1-ethylidene-bis (4,6-di-t-butylphenyl) sodium phosphate, sodium oxide
• Any of benzylidene sorbitol-based, carboxylic acid-based, inorganic phosphate-based, and inorganic substances, such as aluminum, force olin clay, and talc, can be suitably used, and the added amount thereof is preferably 0.001-1. % By weight.
• ethylene-based resin constituting the heat sealable resin layer
• 9 70 g / cm 3 density polyethylene density of from 0.900 to 0.9 3 5 g / cm 3
• Low high-pressure polyethylene of a density or medium density density 0. 880 ⁇ 0.
• a high pressure method polyethylene having a crystallinity (X-ray method) force S of 10 to 60% and a number average molecular weight of 10,000 to 40,000, or a linear linear polyethylene is preferable.
• a high pressure method polyethylene having a crystallinity (X-ray method) force S of 10 to 60% and a number average molecular weight of 10,000 to 40,000, or a linear linear polyethylene is preferable.
• ethylene from the adhesive surface to the container and carry one Orefin 60-2 wt 0/0 of carbon atoms 3 to 30, meta spout catalyst, especially meta spout 'Al Mokisan catalyst Or, for example, a catalyst comprising a meta-mouth compound as disclosed in International Publication W092 / 01 1723 pamphlet and the like and a compound which reacts with the meta-mouth compound to form a stable aion.
• the most suitable is a linear polyethylene obtained by copolymerization.
• weight 0/0 is preferably preferably from 7 0-9 0% by weight.
• the permanent antistatic agent constituting the heat-sealing resin layer examples include a resin composition having the same components as the polyetheresteramide contained in the surface layer. Further, its content is preferably 5 to 40% by weight, more preferably 10 to 30% by weight.
• additives include slip agents such as fatty acid amides, anti-blocking agents, dyes, plasticizers, release agents, antioxidants, flame retardants, ultraviolet absorbers and the like. Thickness
• the thickness of the surface layer of the present invention is in the range of 1 to 40 / xm, preferably 2 to 20 / im. If it is less than 1 Aim, the antistatic property and ink adhesion are poor, and if it exceeds 30 m, the opacity is reduced.
• the thickness of the central layer is in the range of 0 to 20 ° ⁇ m, preferably 0 to 100 ⁇ m.
• the thickness of the heat sealable resin layer is in the range of 1 to 30 m, preferably 2 to 20 / xm.
• the surface layer of the present invention is preferably roughened so that the center line average roughness is in the range of 0.2 to 3 ⁇ .
• the surface roughening may be performed by extruding the resin composition from a die and cooling the cast sheet by transferring the satin pattern applied to the surface of the cast roll.
• the surface may be roughened by pressing a matte roll having a center line average roughness of 0.5 to 5 ⁇ while reheating.
• the heat-sealable resin layer of the label is formed on the heat-sealing resin layer in order to prevent the occurrence of prestar during the hollow molding.
• Embossing can be performed as described in the gazette.
• the embossed pattern is preferably embossed with 5 to 300 lines per 2.54 cm, and any pattern such as a gravure type, a pyramid type, a diagonal line type and the reverse type can be transferred.
• the processing may be performed at the time of casting cooling as described above, or may be performed after cooling and reheating. printing
• Printing includes gravure printing, offset printing (oil-based, UV), flexographic printing, letter press (UV), screen printing, inkjet printing, electrophotographic printing, etc. Enter the barcode, manufacturer, sales company name, character, product name, usage, etc.
• the printed label (1) is separated into labels of required dimensions by punching.
• This label for in-mold molding is usually manufactured as a blank surrounding the side surface of a cup-shaped container, and is manufactured as a label attached to the front side and / or the back side of a bottle-shaped container in blow molding. Ink adhesion
• UV ink “Best Cure 1 16 1 S” (trade name, manufactured by T & KTOKA Corporation) "Cellotape” (trade name, manufactured by Chiban Co., Ltd.) is adhered to the surface on which the seal has been applied, and the ink is peeled off using an internal bond tester (manufactured by Kumagaya Riki Kogyo Co., Ltd.).
• the adhesion strength was measured (kg ⁇ cm).
• the ink adhesion strength is 1 kg ⁇ cm or more, preferably 2 kg ⁇ cm or more. If it is less than 1 kg ⁇ cm, there is resistance when peeling off, but most of the ink is peeled off, causing a practical problem.
• the surface layer In order to improve the ink adhesion, in addition to roughening the surface layer, the surface layer should have an ethylene-butyl acetate copolymer, an ethylene-acrylic acid copolymer, and an ethylene-atalinoleic acid alkyl ester copolymer. It is preferable to include a thermoplastic resin having a polar group such as an ethylene / methacrylic acid alkyl ester copolymer (the alkyl group has 1 to 8 carbon atoms) or a metal salt of the ethylene / methacrylic acid copolymer. ,
• the label After the label is placed such that the printed surface of the label is in contact with the inner surface of the lower female mold of the differential pressure molding mold, the label is fixed to the mold inner wall by suction, and then the container molding material resin sheet The molten material is guided above the lower female mold, subjected to differential pressure molding by a conventional method, and a label bonding container in which the label is integrally fused to the outer wall of the container is formed.
• the differential pressure molding either vacuum molding or compressed air molding can be adopted, but in general, both are used in combination, and the differential pressure molding using plug assist is preferable.
• This label can be particularly preferably used as an in-mold label for hollow molding in which the molten resin parison is pressed against the inner wall of the mold by compressed air.
• the label (1) is fixed in the mold, and then the label and the resin container are integrally molded. Therefore, the label (1) is not deformed.
• the tight adhesion between the container body and the label (1) is strong, there is no prister, and the container decorated with the label has a good appearance.
• the label attached to the container was cut to a width of 15 mm by blow molding, and the adhesive strength between the label and the container was measured using a Shimadzu tensile tester “Autograph, AGS-D type” for 30 OmmZ. It was determined by T-peeling at the tensile speed.
• Propylene homopolymer 70 weight 0/0 (Nippon Polychem Co., Ltd., "Novatec PP, MA- 4" trade name, mp 1 64 ° C), calcium carbonate having an average particle size of 1. 5 / m powder 5 wt%, of the polyether ester amide obtained in preparation example (b 1) 1 9 wt%, maleic acid-modified polypropylene 1 wt 0/0 (Mitsubishi Chemical Co., Ltd., "MOD IC, P- 3 0 OM ”brand name) and 5% by weight of ethylene'butyl acetate copolymer (Novatech EVA, LV440, manufactured by Nippon Polychem Co., Ltd.) at 230 ° C. Was melt-kneaded using the extruder.
• the sheet (A) was extruded into a sheet shape so as to be in contact with the sheet, and the sheet was cooled until the temperature reached 60 ° C.
• the rotation speed of the extruder was adjusted so that the wall thickness of (A) / (B) / (C) was 15 ⁇ m / 70 ⁇ / 15 m, respectively.
• High-density polyethylene “HY540” manufactured by Nippon Polychem Co., Ltd.
• the present invention it is possible to perform front printing in sheet-based offset printing. As a result, it is possible to respond to the order of small lot labels with a short delivery time, and it is possible to cut, punch, and mold the labels after printing. It was possible to provide a transparent mold-forming label that has excellent insertability, does not generate a prestar, and can be firmly fused to a container.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Engineering & Computer Science (AREA)
• Theoretical Computer Science (AREA)
• Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
• Laminated Bodies (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2002
  • 2002-02-12 CN CNA028053532A patent/CN1492800A/zh active Pending
  • 2002-02-12 EP EP02712301A patent/EP1369220A4/en not_active Withdrawn
  • 2002-02-12 WO PCT/JP2002/001146 patent/WO2002066230A1/ja not_active Ceased
  • 2002-02-21 JP JP2002044143A patent/JP3727598B2/ja not_active Expired - Lifetime
• 2003
  • 2003-08-22 US US10/645,591 patent/US20050100751A1/en not_active Abandoned

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