WO2005033218A1 - Pigment destine a des peintures pouvant etre gravees au laser - Google Patents

Pigment destine a des peintures pouvant etre gravees au laser Download PDF

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Publication number
WO2005033218A1
WO2005033218A1 PCT/EP2004/010139 EP2004010139W WO2005033218A1 WO 2005033218 A1 WO2005033218 A1 WO 2005033218A1 EP 2004010139 W EP2004010139 W EP 2004010139W WO 2005033218 A1 WO2005033218 A1 WO 2005033218A1
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WO
WIPO (PCT)
Prior art keywords
pigment
lacquer
laser
composition according
pigments
Prior art date
Application number
PCT/EP2004/010139
Other languages
German (de)
English (en)
Inventor
Philip Betten
Original Assignee
Mankiewicz Gebr. & Co. (Gmbh & Co.Kg)
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mankiewicz Gebr. & Co. (Gmbh & Co.Kg) filed Critical Mankiewicz Gebr. & Co. (Gmbh & Co.Kg)
Publication of WO2005033218A1 publication Critical patent/WO2005033218A1/fr

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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • B41M5/24—Ablative recording, e.g. by burning marks; Spark recording
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds

Definitions

  • Pigment for lacquer that can be engraved by laser
  • the present invention relates to a paint composition containing iron blue pigment, which is used for producing a laser-engravable paint layer.
  • the invention also relates to the use of iron blue pigment in a lacquer composition which is suitable for producing a lacquer layer capable of laser engraving, a laser engraving method and a coated substrate which has coated and laser engraved areas.
  • the invention further relates to the use of the coating composition in laser engraving.
  • a lacquer is usually referred to as laser-engravable if the coatings produced with it can be removed from the substrate without leaving residues, with sharp contours and without traces of smoke.
  • the substrates are thermoplastic materials for "day-night design" applications in the automotive industry.
  • the production of blue or bluish black shades of the lacquers, which are suitable for laser engraving, is problematic.
  • the phthalocyanine pigments contained in the paints in these shades cannot be removed from the substrate without residues by the laser engraving carried out under the usual and suitable conditions. Rather, parts of the lacquer layer remain in an uncontrollable manner, which too lead to an undesirable and uncontrolled blue coloring of the substrate.
  • Residue-free removal is only possible when high laser energy is applied, but then the substrate will be damaged. The realization of blue tones is therefore currently taking place.
  • the first layer being phth.alocyanine-free (sacrificial primer) and the second layer containing phthalocyanine. With laser engraving, both layers can be removed without residue. It is obvious that this two-layer structure has technical and economic disadvantages compared to a single-layer lacquer.
  • DE-Al-199 01 609 discloses a multilayer pearlescent pigment based on a platelet-shaped substrate.
  • the substrate can contain organic pigments such as Berlin blue.
  • the pigments are also intended for laser marking of plastics.
  • the document also describes varnishes, printing inks, plastics, polymer films, etc. that are pigmented with the pigment. On a. Laser engraving is not accepted.
  • the object of the invention is now to find a pigment which on the one hand allows in an extremely thin layer of lacquer, a residue-free removal of the layer by means of laser and • on the other hand has a low transparency and good color properties.
  • iron blue pigment can be used in the laser-engravable lacquers to solve the above-mentioned problems and to overcome the problems in the prior art.
  • the invention relates to a lacquer composition for laser engraving, which comprises a) binder polymer, b) solvent and / or dispersion medium and c) iron blue pigment u,
  • a lacquer layer produced therefrom can be laser-engraved with a trace of smoke and residue and meets at least one of the following parameters:
  • the lacquer layer has a reflectometer value (determined according to DIN EN ISO 2813 at a measuring angle of 60 °) of ⁇ 20,
  • the lacquer layer has a characteristic value of the cross-cut test (according to DIN EN ISO 2409) of 2 or less, III) the lacquer layer has a dry layer thickness of 120 ⁇ m or less.
  • lacquer layers produced with preferred lacquer compositions have an adhesive peel strength (according to DIN EN ISO 4624, 2 cm stamp diameter) of> 2 MPa.
  • Coatings can be produced with iron-blue pigment-containing lacquers capable of being engraved, which on the one hand completely cover an underlying substrate and on the other hand can be removed without residue, the removal not requiring any laser radiation which could damage the underlying substrate.
  • the paint composition containing iron blue pigment means that color shades (DIN 6174) can be set in a wide range in laser-engravable paint coats.
  • the brightness on the L axis can be set between 0 and 100.
  • the hue on the a-axis is arbitrary and on the b-axis preferably in the negative range as desired.
  • the use of iron blue pigment also offers residue-free, smudge-free laser engraving in single-layer paints.
  • Lacquer compositions according to the invention result in a comparatively matt lacquer layer and thus differ from the high-gloss lacquers, such as those e.g. be used outdoors in automotive engineering.
  • the reflectometer value (determined in accordance with DIN EN ISO 2813 at a measurement angle of 60 °) is ⁇ 15, preferably ⁇ 10, in particular ⁇ 8.
  • a preferred characteristic value of the cross-hatch test according to DIN EN ISO 2409 is 1, in particular 0, whereby at ⁇ 80 ⁇ m dry layer thickness measurements are preferably made with a cutting distance of 2 mm and, in deviation from the norm, the procedure is carried out at a cutting distance of ⁇ 2 mm, such as 1.5 mm or 1 mm is feasible and evaluable.
  • the dry layer thickness of the lacquer layer (e.g. determined in accordance with DIN EN ISO 2808) is at most 120 ⁇ m, preferably ⁇ 80 ⁇ m, more preferably ⁇ 50 ⁇ m, and most preferably ⁇ 40 ⁇ m, in particular 3 to 35 ⁇ m.
  • the term iron blue pigment is defined by ISO 2495. By varying the cation and the production conditions, green to violet tones and red tones can be produced. Because of their fine particle size, iron blue pigments are very strong in color.
  • ammonium (sodium) iron lukewarm pigment (which sometimes is also referred to as soluble blue) and in particular ammonium iron blue pigment is used.
  • the iron blue pigment can be surface-treated in a conventional manner (e.g. surface-coated).
  • a typical average primary particle size of the iron blue pigment is approximately 33 nm (arithmetic mean DN), particle sizes of 10 jois 100 nm being preferred, in particular 20 to 90 nm, according to the invention.
  • DN average primary particle size
  • the polymer of the coating composition serving as a binder is preferably selected from polyurethane, acrylate, polyurethane-acrylate hybrid, polyol, polyalcohol, urethane acrylate, polyester, unsaturated polyester, dendritic polymer, epoxy resin, polycarbonate, melamine resin, phenolic resin, acrylic-polyurethane Hybrid and mixtures thereof.
  • the polymers mentioned can contain functional groups (for example OH groups, amine functionalities or blocked isocyanate groups) as well as non-functional polymers.
  • the polymers mentioned can be contained in the lacl composition according to the invention both in the form of a solution and of a dispersion.
  • the amount of binder is preferably 15 to 60% by weight, more preferably 20 to 45% by weight, in particular 25 to 40% by weight (based on the coating composition).
  • the coating system can be both aqueous and solvent-based or solvent-based or a high-solid system.
  • the solvent and / or dispersion medium is selected from water, ketones, esters, aliphatic hydrocarbons, aromatic hydrocarbons, glycols and glycol derivatives, N-methylpyrrolidone, alcohols, ethers and glycol ethers and mixtures thereof.
  • the amount of solvent and / or dispersion medium is preferably 10 to 75% by weight, more preferably 15 to 65% by weight, in particular 20 to 60% by weight, based on the coating composition.
  • the coating composition can further comprise one or more inorganic pigments, organic pigments, effect pigments and / or fillers.
  • Preferred inorganic pigments are titanium dioxide, carbon black, chromium oxide, ultramarine, molybdate red, chrome yellow, cobalt blue, mixed oxide pigment, iron oxides (such as iron oxide red, iron oxide yellow, iron oxide black), bismuth vanadate, chromium titanium yellow and nickel titanium yellow, with carbon black being used particularly frequently.
  • Preferred organic pigments are, for example, azo pigments, diazo pigments, polycyclic pigments, quinacridone pigments, dioxazine pigments, perylene pigments, diketo-pyrrolo pigments and isoindoline pigments.
  • aluminum flake pigments and pearlescent pigments are preferred as effect pigments.
  • the amount of pigmentation in the paint composition must be less than or equal to the critical pigment volume concentration (KPVK).
  • Preferred total amounts of pigment (including iron blue pigment), based on the coating composition are less than 20% by weight, more preferably less than 15% by weight, in particular less than 10% by weight.
  • the amount of iron blue pigment is drew on the paint composition. preferably 0.1 to 10% by weight, more preferably 1 to 5% by weight, in particular 2 to 4% by weight.
  • the amount of additional pigment (especially carbon black), based on the coating composition is generally 0.1-10%, preferably 2 to 10%, in particular 3 to 8%.
  • the pigments are in their powdered form in the agglomerated state.
  • the agglomerated pigments are broken up and dispersed, for example, by stirrers, dissolvers, agitator ball mills, ball mills, colloid mills, three-roll mills or high-pressure homogenizers, so that a granularity, measured using the grinder according to DIN EN ISO 1524, generally less than 120 ⁇ m, preferably less than 50 ⁇ m, in particular less than 30 ⁇ m, is achieved.
  • the paint composition according to the invention can include one or more customary additives selected from defoamers, deaerators, wetting dispersants, surface additives (such as leveling and slip additives), wax dispersions, waxes, matting agents (silicates or polyamide powder, polymer powder), theological additives (thickeners , Associative thickener or thixotropic agent), aerosils, layered silicates, adhesion promoters, substrate wetting agents, catalysts, accelerators, photoiniators, dyes, biocides and mixtures thereof.
  • Preferred amounts of matting agent, based on the coating composition are generally less than 30% by weight, preferably less than 20% by weight, in particular less than 15% by weight.
  • the invention further relates to a laser engraving method in which
  • a coating composition according to the invention is applied to a substrate
  • the substrate may be, for example, from thermoplastic material (such as polycarbonate, Polymethacrylmethacrylat, polyamide, acrylonitrile / butadiene / styrene, polybutylene terephthalate, Po ⁇ lystyrol, polyethylene, polypropylene, or thermoplastic elastomers).
  • thermoplastic material such as polycarbonate, Polymethacrylmethacrylat, polyamide, acrylonitrile / butadiene / styrene, polybutylene terephthalate, Po ⁇ lystyrol, polyethylene, polypropylene, or thermoplastic elastomers).
  • thermoplastic can be transparent, opaque or colored, for example white.
  • thermosets or polyurethanes are examples of substrates made of thermosets or polyurethanes, such as hard or soft foams or integral foams.
  • metals come e.g. Steels or metal sheets, iron sheets or aluminum sheets in question.
  • plastics and metals mentioned are generally not colored black and are preferably too black in one contrasting color, or are uncolored, opaque or transparent substrates.
  • All manual or automatic application methods that are customary for paints are suitable as application methods. Exemplary methods are in A. Goldschmidt, H-J. Streitberger, BASF Handbook of Painting Technology, Vincentz Verlag Hannover, 2002. These include e.g. Spray applications such as pneumatic atomization or electrostatically assisted pneumatic atomization, mist-reduced pneumatic atomization (HVLP), high-speed atomization, hydraulic atomization (airless), pneumatically assisted hydraulic atomization, whereby all atomization methods can also be used electrostatically assisted, or other application methods such as e.g. Rolling, casting, painting, dipping, drumming, winding or printing.
  • HVLP mist-reduced pneumatic atomization
  • airless hydraulic atomization
  • pneumatically assisted hydraulic atomization whereby all atomization methods can also be used electrostatically assisted, or other application methods such as e.g. Rolling, casting, painting, dipping, drumming, winding or printing.
  • the paint composition according to the invention is first applied by pneumatic spray application.
  • a preferred spray application method is characterized, for example, by the following parameters:
  • spray application is possible with a nozzle diameter of 0.8 mm, an atomizing air pressure of 4 bar, a material pressure of 0.5 bar at 22 ° C ambient temperature and 60% relative air humidity.
  • the paint composition is then allowed to flash off at 22 ° C. ambient temperature and 60% relative atmospheric humidity for 10 minutes, dried at 80 ° C. for 30 minutes and then aged at 60 ° C. for 48 hours.
  • the coating composition according to the invention When carrying out the method according to the invention, it is possible to apply the coating composition according to the invention as a single layer to the substrate. This means that un ⁇ indirectly applied no other lasergraviercopye lacquer layer on the substrate (s) than the resist layer of the inventive coating composition comprising the iron-blue pigment. Alternatively, it is possible to put on a body (for example made of plastic or metal)
  • the substrate is not changed by the laser engraving and accordingly forms the visible surface in the laser-engraved areas.
  • the substrate Before the coating composition is applied, the substrate can be surface-treated in a conventional manner.
  • the curing processes include oxidative curing, curing at room temperature, forced curing at higher temperatures, UV curing, amine curing and reactive crosslinking, for example with isocyanates (for example tolylene diisocyanate, TDI, hexamethylene diisocyanate, HDI, isophorone diisocyanate, IPDI, methylene phenylene diisocyanate, MD or Polyisocyanate) possible.
  • isocyanates for example tolylene diisocyanate, TDI, hexamethylene diisocyanate, HDI, isophorone diisocyanate, IPDI, methylene phenylene diisocyanate, MD or Polyisocyanate
  • One-component systems for example based on blocked isocyanates, can also be used.
  • Laser engraving processes which remove a layer of lacquer, which has been produced by applying and curing a lacquer composition according to the invention, without smoke and residues are known to those skilled in the art.
  • the amount of energy that is applied to a certain area of the lacquer layer in a certain period of time and that removes the lacquer layer without damaging the substrate is usually determined in a preliminary test. It has been found according to the invention that removal of a blue pigment-coated lacquer layer without smoke and residues is possible if the lacquer composition used to produce the lacquer layer comprises iron blue pigment.
  • customary lasers are used with which the lacquer is removed without damaging the substrate.
  • phthalocyanine e.g. copper phthalocyanine blue
  • varnishes containing blue if the substrate is not to be damaged, blue residues remain visibly.
  • the opacity of the coated areas is assessed visually by holding a lamp under the substrate.
  • the transparency of the laser-engraved areas and the edge sharpness between the coated area and the laser-engraved area are also assessed visually.
  • a typical laser engraving process uses a neodymium YAG laser with a wavelength of 1064 nm. Such lasers with an output of 50 watts in continuous operation are suitable, for example. In practice, predominantly one Combination of continuous and pulsed operation applied, with higher performance occurring in the short term.
  • the invention further relates to a coated substrate, with
  • the laser-engravable lacquer layer is produced on a component in the interior of the automobile that is backlit ("day-night design").
  • a special application of the invention is the production of consoles for car radios and control and switching buttons in the automotive interior.
  • the invention further relates to the use of the above-mentioned lacquer composition in a laser engraving process.
  • the invention is also suitable for the decorative field such as Lampshades.
  • the invention can be used in the tampon print area and in the heat seal area (in each case without backlighting).
  • iron blue pigments in laser lacquers according to the invention enables laser-engraved removal of the residue-free, sharp-contoured and smear-free traces of the resultant provided coatings. Due to the replacement of the phthalocyanine pigments by iron blue pigments, laser coatings that can be used in one layer can be formulated.
  • the advantage of the iron blue pigments is that the color tones of the laser lacquers on the b-axis in the CIELAB color space can be set as desired, especially in the negative range, regardless of the intrinsic color tone of the binders.
  • the laser lacquers according to the invention can be applied in one layer and can also be laser-engraved without residue without sacrificial primer.
  • the standards mentioned in the description of the invention are the currently applicable standards.
  • the cross-cut test was carried out in accordance with DIN EN ISO 2409.
  • the dry layer thickness was determined in accordance with DIN EN ISO 2808.
  • the reflectometer value was determined in accordance with DIN EN ISO 2813.
  • a 75% solution of a commercially available polyisocyanate (e.g. based on a hydrophilized HDI and an isocyanate content of approx. 17%) in methoxypropyl acetate was used as the hardener.
  • the mixture obtained in this way was ground in a bead mill to a granularity of 5 ⁇ m (measurement by grinder meter elevator).
  • 50 g of commercially available silicate matting agent, 50 g of butyl glycol and a further 100 g of the above-mentioned polyurethane dispersion were then added, and the mixture was dispersed for 20 minutes using a dissolver.
  • the mixture was finished by adding about 175 g of deionized water so that the finished mixture had a non-volatile content of 35%.
  • a 75% solution of a commercially available polyisocyanate (e.g. based on a hydrophilized HDI and an isocyanate content of approx. 17%) in methoxypropyl acetate was used as the hardener.
  • the mixture was finished by adding about 175 g of deionized water so that the finished mixture had a non-volatile content of 35%.
  • a 75% solution of a commercially available polyisocyanate (e.g. based on a hydrophilized HDI and an isocyanate content of approx. 17%) in methoxypropyl acetate was used as the hardener.
  • the laser lacquers previously described in Examples 1-3 were applied to a plastic plate made of polycarbonate (PC) with the dimensions 200 ⁇ 100 mm ⁇ 3 mm, so that a dry layer thickness of 35 ⁇ m was obtained. After a flash off time of The coating was dried at 80 ° C for 10 minutes at 22 ° C for 30 minutes and aged at 60 ° C for 48 hours.
  • PC polycarbonate
  • the lacquers of Examples 1-3 cannot be completely removed if the laser's energy input is too low.
  • Paints 1 and 2 can be completely removed from the substrate with optimal energy input without the substrate being charred or damaged. A sharply contoured laser engraving is obtained. If the energy input is too high, the plastic substrate becomes charred or damaged.
  • Lacquer 3 cannot be laser engraved in such a way that the lacquer is completely removed and the substrate is not damaged. There are always clearly visible blue or colored residues of the paint in the engraved area or the plastic substrate is charred.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne une composition de peinture contenant un pigment au bleu de Prusse, servant à la fabrication d'une couche de peinture pouvant être gravée au laser. Ladite peinture peut être gravée au laser sans traces d'enfumage ni de résidus et permet donc d'éviter les problèmes survenant notamment dans le cas de peintures présentant des tons noirs bleutés ou bleuâtres. On fait de préférence intervenir un pigment au bleu de Prusse d'ammonium présentant une granulométrie moyenne de 10 à 100 nm. L'invention trouve de préférence son application dans des substrats en plastiques thermoplastiques destinés à être employés dans le 'design jour/nuit' dans l'industrie automobile.
PCT/EP2004/010139 2003-09-18 2004-09-10 Pigment destine a des peintures pouvant etre gravees au laser WO2005033218A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10343704A DE10343704A1 (de) 2003-09-18 2003-09-18 Pigment für lasergravierfähige Lacke
DE10343704.5 2003-09-18

Publications (1)

Publication Number Publication Date
WO2005033218A1 true WO2005033218A1 (fr) 2005-04-14

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Application Number Title Priority Date Filing Date
PCT/EP2004/010139 WO2005033218A1 (fr) 2003-09-18 2004-09-10 Pigment destine a des peintures pouvant etre gravees au laser

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DE (1) DE10343704A1 (fr)
WO (1) WO2005033218A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008046461A1 (de) 2008-09-09 2010-03-11 Tesa Se Verfahren zur Herstellung einer mehrfarbig laserbeschriftbaren Folie
US20140255608A1 (en) * 2013-03-11 2014-09-11 Ppg Industries Ohio, Inc. Coatings that exhibit a tri-coat appearance, related coating methods and substrates
WO2017167651A1 (fr) 2016-03-29 2017-10-05 Covestro Deutschland Ag Procédé de coloration partielle de pièces en matière plastique
WO2019002118A1 (fr) 2017-06-28 2019-01-03 Covestro Deutschland Ag Procédé amélioré de coloration partielle de pièces en matière plastique

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Publication number Priority date Publication date Assignee Title
US7906214B2 (en) * 2007-01-26 2011-03-15 Transitions Optical, Inc. Optical elements comprising compatiblizing coatings and methods of making the same
CN103827231B (zh) 2011-09-16 2018-04-10 巴斯夫欧洲公司 涂层体系
GB201222955D0 (en) 2012-12-19 2013-01-30 Innovia Films Ltd Film
EP3532866A1 (fr) 2016-10-28 2019-09-04 PPG Industries Ohio, Inc. Revêtements d'augmentation des distances de détection proche infrarouge
KR20210087991A (ko) 2018-11-13 2021-07-13 피피지 인더스트리즈 오하이오 인코포레이티드 은닉 패턴을 검출하는 방법

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US4309480A (en) * 1980-02-28 1982-01-05 The Mearl Corporation Iron blue nacreous pigments
EP0290359A2 (fr) * 1987-05-06 1988-11-09 Eastman Chemical Company Dispersions aqueuses de mélanges de polyesters et polyuréthanes et encres d'imprimerie à base de celle-ci
EP0716135A1 (fr) * 1994-06-24 1996-06-12 Nippon Kayaku Kabushiki Kaisha Composition pour marquage et procede de marquage par laser
EP0750012A1 (fr) * 1995-06-23 1996-12-27 MERCK PATENT GmbH Plastics pour marquage par laser
US6019831A (en) * 1993-11-25 2000-02-01 Merck Patent Gesellschaft Mit Beschrankter Haftung Non-lustrous pigments
DE19901609A1 (de) * 1999-01-18 2000-07-20 Merck Patent Gmbh Mehrschichtiges Perlglanzpigment
EP1099565A2 (fr) * 1999-11-11 2001-05-16 Basf Aktiengesellschaft Procédé d'écriture sur surfaces en plastique

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JPS63227657A (ja) * 1987-03-16 1988-09-21 Nippon Soda Co Ltd アルキツド樹脂組成物
JPH04120178A (ja) * 1990-09-07 1992-04-21 Kajima Corp 飛散しにくい塗料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4309480A (en) * 1980-02-28 1982-01-05 The Mearl Corporation Iron blue nacreous pigments
EP0290359A2 (fr) * 1987-05-06 1988-11-09 Eastman Chemical Company Dispersions aqueuses de mélanges de polyesters et polyuréthanes et encres d'imprimerie à base de celle-ci
US6019831A (en) * 1993-11-25 2000-02-01 Merck Patent Gesellschaft Mit Beschrankter Haftung Non-lustrous pigments
EP0716135A1 (fr) * 1994-06-24 1996-06-12 Nippon Kayaku Kabushiki Kaisha Composition pour marquage et procede de marquage par laser
EP0750012A1 (fr) * 1995-06-23 1996-12-27 MERCK PATENT GmbH Plastics pour marquage par laser
DE19901609A1 (de) * 1999-01-18 2000-07-20 Merck Patent Gmbh Mehrschichtiges Perlglanzpigment
EP1099565A2 (fr) * 1999-11-11 2001-05-16 Basf Aktiengesellschaft Procédé d'écriture sur surfaces en plastique

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102008046461A1 (de) 2008-09-09 2010-03-11 Tesa Se Verfahren zur Herstellung einer mehrfarbig laserbeschriftbaren Folie
WO2010028962A1 (fr) 2008-09-09 2010-03-18 Tesa Se Procédé de fabrication d'une feuille pouvant être marquée au laser en plusieurs couleurs
US20140255608A1 (en) * 2013-03-11 2014-09-11 Ppg Industries Ohio, Inc. Coatings that exhibit a tri-coat appearance, related coating methods and substrates
WO2017167651A1 (fr) 2016-03-29 2017-10-05 Covestro Deutschland Ag Procédé de coloration partielle de pièces en matière plastique
CN108778766A (zh) * 2016-03-29 2018-11-09 科思创德国股份有限公司 用于对塑料件进行部分染色的方法
US10662581B2 (en) 2016-03-29 2020-05-26 Covestro Deutschland Ag Method for the partial coloring of plastic parts
WO2019002118A1 (fr) 2017-06-28 2019-01-03 Covestro Deutschland Ag Procédé amélioré de coloration partielle de pièces en matière plastique
US11242464B2 (en) 2017-06-28 2022-02-08 Covestro Deutschland Ag Method for the partial colouring of plastic parts

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