WO2000030870A1 - Method for decorating the surface of a painted substrate - Google Patents
Method for decorating the surface of a painted substrate Download PDFInfo
- Publication number
- WO2000030870A1 WO2000030870A1 PCT/EP1999/008798 EP9908798W WO0030870A1 WO 2000030870 A1 WO2000030870 A1 WO 2000030870A1 EP 9908798 W EP9908798 W EP 9908798W WO 0030870 A1 WO0030870 A1 WO 0030870A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- masks
- irradiation
- coating layer
- energy radiation
- light
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44F—SPECIAL DESIGNS OR PICTURES
- B44F1/00—Designs or pictures characterised by special or unusual light effects
- B44F1/08—Designs or pictures characterised by special or unusual light effects characterised by colour effects
- B44F1/14—Iridescent effects
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/001—Phase modulating patterns, e.g. refractive index patterns
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
Definitions
- the invention relates to a process for the decorative design of a painted substrate surface and to the substrates obtained by the process.
- the method according to the invention can be used in particular in the decorative surface design of vehicle bodies, their components and vehicle parts.
- decorative surface designs are known, in particular from the field of automotive painting.
- this includes individual paintwork, such as effect paintwork, paintwork in special colors or paintwork in the form of pictures, patterns or ornaments, but also the application of appropriately designed adhesive films.
- the object of the invention is to provide a method for the decorative design of a painted substrate surface.
- the process is intended in the field of painting industrially or artisan goods, e.g. Sports articles, device housings and especially in the area of vehicle and vehicle parts painting allow the creation of unique and impressive decorative effects.
- the expression “masks that are permeable to high-energy radiation and that have structures that are less or impermeable to high-energy radiation in the range from 100 to 20,000 nm apart” is of course also intended to include the reverse case, namely the use of masks that are impermeable to high-energy radiation which in the range from 100 to 20,000 nm have structures that are partially or completely transparent to one another for high-energy radiation.
- the masks are held, for example, at a short distance above the coating layer or are brought into direct contact with the coating layer with one or one flat side, without mechanically producing microstructures in the coating layer.
- light preferably with a wavelength of 180 to 1000 nm
- Translucent masks with less translucent or opaque structures are then used.
- place (s) to be decorated also includes the special case of a substrate surface to be decorated over the entire surface.
- the procedure can be such that the areas irradiated through the partially translucent masks contribute to the coating layer the radiation is not fully cured and the complete curing of both the irradiated and the non-irradiated areas then takes place, in particular by irradiation.
- the procedure can be such that the areas of the coating layer which are irradiated through the partially transparent masks are fully cured during the irradiation and the complete curing of the non-irradiated areas subsequently takes place under other conditions, for example thermally or by means of irradiation under other irradiation conditions than in the previous irradiation step, e.g. B. different irradiation duration, wavelength and / or irradiation intensity.
- the inventive method is suitable for the decorative design of a coating layer, for example on industrially produced goods, such as. B.
- the decorative coating layer to be designed can be a single-layer lacquer or a coating layer applied to the viewer in the context of a multi-layer coating.
- the goods themselves provided with the coating layer can, for example, be made of wood, glass, but in particular of metal or plastic, and may already have been precoated with one or more layers of lacquer.
- the coating compositions which are at least partially curable by irradiation with light in the process according to the invention are not subject to any fundamental restriction, they can be aqueous, diluted with solvents or preferably free from solvents and water. They can also be in powder form.
- the coating compositions can be partially or preferably completely curable by irradiation with light. Both Irradiation with light-curable coating agents is in particular the cationically and / or free-radically curing coating agents known to the person skilled in the art. Radically curing coating agents are preferred. When high-energy radiation acts on the coating layers applied from these coating compositions, radicals are formed in the coating layers, which trigger crosslinking of the coating layers by radical polymerization of olefinic double bonds.
- the preferred free-radically curing coating compositions contain prepolymers, such as poly- or oligomers, which have free-radically polymerizable olefinic double bonds, in particular in the form of (meth) acryloyl groups in the molecule.
- Prepolymers can be used in combination with conventional reactive diluents, i.e. reactive liquid monomers.
- prepolymers or oligomers are (meth) acrylic-functional (Mefh) acrylic copolymers, epoxy resin (meth) acrylates, polyester (meth) acrylates,
- Mn number average molecular weights
- reactive diluents are used, they are used in amounts of 1 to 50% by weight, preferably 5 to 30% by weight, based on the total weight of prepolymers and reactive diluents. These are defined low-molecular compounds that can be mono-, di- or polyunsaturated.
- reactive diluents examples include: (meth) acrylic acid and its esters, maleic acid and its half esters, vinyl acetate, vinyl ether, substituted vinyl ureas, ethylene and propylene glycol di (meth) acrylate, 1,3- and 1,4-butanediol di (meth) acrylate, Vinyl (meth) acrylate, allyl (meth) acrylate, glycerol tri, di and mono (mefh) acrylate, trimethylolpropane tri, di and mono (meth) acrylate, styrene, vinyl toluene, divinyl benzene, pentaerythritol tri and
- the preferred free-radically curing coating agents can contain customary photoinitiators, for example in amounts of 0.1 to 5% by weight, preferably 0.5 to 3% by weight, based on the sum of free-radically polymerizable prepolymers, reactive diluents and photoinitiators.
- photoinitiators are benzoin and derivatives, acetophenone and derivatives, for example 2,2-diacetoxyacetophenone, benzophenone and derivatives, thioxanthone and derivatives, anthraquinone, 1-benzoylcyclohexanol, organophosphorus compounds such as acylphosphine oxides.
- the photoinitiators can be used alone or in combination.
- other synergistic components for example tertiary amines, can be used.
- the coating compositions which can be at least partially hardened by irradiation with light can be coating compositions which can be partially hardened by irradiation with light, preferably coating compositions which can be completely hardened by irradiation with light.
- thermolabile radical initiators are: organic peroxides, organic azo compounds or C-C-cleaving initiators. The preferred amounts are between 0.1 and 5% by weight, based on the total of free-radically polymerizable prepolymers, reactive diluents and free-radical initiators.
- the coating compositions which are only partially curable by irradiation with light can also be a mixture of, for example, 50 to 99% by weight of a binder system curable by irradiation with light and 1 to 50% by weight of a and / or physically curable by addition and / or condensation reactions contain drying binder system, wherein the wt .-% each relate to the solid and add up to 100 wt .-%, and / or the binder system, which is curable by irradiation with light, may additionally be capable of crosslinking by addition and / or condensation reactions Have groups.
- lacquer chemical crosslinking reactions known to the person skilled in the art, such as, for example ring opening addition of an epoxy group to a carboxyl group to form an ester and a hydroxyl group, the addition of a hydroxyl group to an isocyanate group to form a urethane group, the reaction of a hydroxyl group with a blocked isocyanate group to form a urethane group and elimination of the blocking agent, the reaction of a hydroxyl group with an N
- Methylol group with elimination of water the reaction of a hydroxyl group with an N-methylol ether group with elimination of the etherification alcohol, the transesterification reaction of a hydroxyl group with an ester group with elimination of the esterification alcohol, the umurethanization reaction of a hydroxyl group with a carbamate group with alcohol elimination, the reaction of a carbamate group with an N-methylol Cleavage of the etherification alcohol.
- the coating compositions which are at least partially curable by irradiation with light can be pigmented or colorless transparent or colored transparent. It is preferably colorless clearcoats or color and / or effect coating agents, for. B. basecoats.
- the coating compositions which are at least partially curable by irradiation with light can be applied to the substrates to be decorated by customary methods, for example by spray application.
- the application can take place on the entire substrate surface or on one or more partial surfaces thereof or only on the areas of the substrate surface to be decorated, for example in a dry layer thickness of 5 to 250 ⁇ m.
- the uncured coating layer at the points to be decorated with one or more per se transparent masks which have less transparent or opaque structures spaced apart in the range from 100 to 20,000 nm, preferably from 800 to 20,000 nm, for example at a short distance of generally not more than 2 cm, preferably not more than 2 mm, or in each case covered in direct contact with the or a flat side of the masks which are transparent per se.
- a translucent release film be placed between the mask and the uncured coating layer to make it easier to remove the mask later.
- the partially translucent masks which are spaced apart from one another in the range from 100 to 20,000 nm, preferably from 800 to 20,000 nm, and are less translucent or highly opaque, can be made of glass or preferably of transparent plastics, for example polyester, polycarbonate, polystyrene, poly (meth) acrylate or Made of silicone plastic.
- the masks are preferably made of flexible, possibly elastic, plastic.
- the masks on the corresponding flat side can expediently be specially equipped.
- This equipment can consist, for example, in that the mask material as such has non-stick properties, for example due to appropriate additives, or the mask surface is provided with a non-stick coating.
- the masks have areas of different light transmission.
- the masks which are translucent per se have less translucent or opaque structures spaced apart from one another in the range from 100 to 20,000 nm, preferably from 800 to 20,000 nm.
- the less translucent or opaque structures can be a relief characterized by amplitude maxima spaced from one another in the range from 100 to 20,000 nm, preferably from 800 to 20,000 nm, or they can be structures inherently located within the masks, for example comparable to a photographic microfilm negative or positive.
- the reliefs can have depressions, elevations and / or holes.
- the reliefs can be produced, for example, by standard methods of microstructure technology, for example photolithographic methods associated with etching techniques or vapor deposition methods and laser techniques. When spaced apart in the range from 100 to 20,000 nm, preferably from 800 to 20,000 nm
- Amplitude maxima characterized, preferably on one side of the masks, are reliefs with an amplitude height in the range, for example, between 100 and 5000 nm.
- the amplitude maxima can be in the form of points, lines or Plateaus are present.
- the distance specification from 100 to 20,000 nm, preferably from 800 to 20,000 nm between the amplitude maxima relates to the distance between adjacent plateau edges or between a plateau edge and adjacent amplitude maxima which are present as points or lines.
- the relief may have irregular structures or it may be regular structures, such as optical diffraction gratings, for example cross gratings or, in the simplest case, optical grating gratings.
- the grid lines cannot be arranged equidistantly or equidistantly.
- the distance relates to the distance resulting from supervision.
- the structures inherently located within the masks can be produced, for example, by means of microphotographic or photolithographic processes.
- the structures inherent within the masks can be in the form of dots, lines or areas. In the case of structures present as surfaces, the distance from 100 to 20,000 nm, preferably from 800 to 20,000 nm between the structures relates to the distance between neighboring ones
- Area boundary lines or between an area boundary line and neighboring structures present as points or lines.
- the structures can be irregular or they are regular structures, such as optical diffraction gratings, for example cross gratings or, in the simplest case, optical grating gratings.
- the grid lines cannot be arranged equidistantly or equidistantly.
- the masks can take on any surface area, for example from a few square centimeters to a few square meters.
- the less translucent or opaque structures can extend over the entire surface of the masks.
- the less translucent or opaque structures can, however, also only extend over a partial surface of the masks, the outer contour line of the structured areas being able to match the outer contour line of the masks.
- the masks can have a structured frame and, if appropriate, further structured or unstructured areas, likewise delimited by contour lines, within the structured frame. Unstructured areas can be translucent or opaque, for example. Due to the many possible variations in the design of the masks, a wide variety of decorative elements can be created at the locations to be decorated, for example pictures, ornaments, patterns, logos, symbols, initials, type designations, etc.
- the uncured coating layer is, according to the invention, as already described above, in the areas to be decorated with one or more per se transparent masks which have less transparent or opaque structures spaced apart in the range from 100 to 20,000 nm, preferably from 800 to 20,000 nm a short distance, for example generally not more than 2 cm, preferably not more than 2 mm, or in each case covered in direct contact with the or a flat side of the masks which are transparent per se.
- the uncured coating layer is then preferably irradiated through the masks with light having a length of 180 to 1000 nm. This can be mono- or polychromatic light. It is preferably ultraviolet light.
- UV radiation sources Preference is given to UV radiation sources with emissions in the wavelength range from 180 to 420 nm, particularly preferably from 200 to 400 nm.
- Preferred examples of UV radiation sources are optionally doped high-pressure, medium-pressure and low-pressure mercury lamps, gas discharge tubes, e.g. Xenon low pressure lamps, black light tubes, UV flash lamps.
- Electron radiation for example, can also be used as high-energy radiation.
- Conventional electron emitters can be used under the usual conditions of use familiar to those skilled in the art.
- the radiation duration is in the range of the duration of a UV flash, for example from 1 millisecond to 5 minutes, depending on the radiation method used and the type of UV radiation sources.
- a radiation duration ie an actual exposure time of the UV radiation of less than 5 minutes, is preferred.
- the areas not yet cured in the coating layer are cured thermally and / or by irradiation with high-energy radiation after the partially transparent masks have been removed.
- the expression "as yet unhardened areas in the coating layer” denotes those areas which the radiation has not reached through the partially transparent masks. Furthermore, the term “as yet unhardened areas in the coating layer” also includes outside of the Masks lying
- a clear coat of any clear coat or any transparent plastic film can be applied to the decorated areas or to the entire painted substrate surface.
- the method according to the invention can be used as a separate method step in a method for producing a multi-layer lacquer.
- the lacquer layers comprising decorative elements are applied by the process according to the invention to unpainted substrates or substrates which have been precoated with a single- or multi-layer lacquer and provided with a final clear lacquer layer.
- the process according to the invention can preferably be carried out in such a way that as a coating agent at least partially curable by irradiation with light, a clear lacquer coating agent is applied to dark, e.g. black, or dark, e.g. black painted substrates is applied.
- a coating agent at least partially curable by irradiation with light a clear lacquer coating agent is applied to dark, e.g. black, or dark, e.g. black painted substrates is applied.
- dark e.g. black
- dark e.g. black painted substrates
- the effect that can be achieved according to the invention can be perceived particularly intensively on dark substrates.
- a curable coating agent, a coloring and / or effect coating agent, e.g. B. to use a basecoat, which is preferably dark, particularly preferably black pigmented.
- painted substrate surfaces can be provided with decorative elements which have an effect which is dependent on the viewing angle.
- decorative elements Deviating from the viewing angle-dependent light / dark and / or color flop known from the field of effect painting, for example metallic painting, decorative elements can be produced with the method according to the invention which have a novel viewing angle-dependent flop effect, a so-called
- the decorative elements can be described as e.g. holographic image appearing in all spectral colors. If in the simplest case the decorative elements have been produced by means of a mask having an optical grating, the decorative elements are in the form of a continuous, e.g. all spectral colors have a perceptible spectrum, i.e. for the viewer there is a rainbow-like effect.
- the method according to the invention can also be used for partial and thus decorative, more or less strong weakening of the reflection behavior (anti-reflective coating) of outer, glossy lacquer coating layers on substrates.
- the masks then have structures which are less permeable or impermeable to high-energy radiation and are suitable for generating destructive interference in the coating layer.
- painted substrate surfaces can be designed in an impressively decorative manner.
- the method according to the invention can be used particularly advantageously, for example in the motor vehicle sector, which includes the design of motor vehicles and parts in the craft sector as well as in the industrial field of original equipment, in particular also, for example, as an integrated process step in the context of automotive painting.
- the original equipment can be, for example, a decorative design of the entire visible outer surface of a motor vehicle, parts in the interior of a motor vehicle or an individual decorative design based on customer requirements, for example the attachment of the customer's initials, etc., or it can be a standard decorative design, for example the application of a company logo, a type designation or the decorative emphasis of edges or transitions between different areas of a body, for example also between adjacent vehicle parts, etc..
- the craft sector for example, it can also be a decorative design of the entire visible outer surface of a motor vehicle, parts in the interior of a motor vehicle or an individual decorative design of a motor vehicle (part) s which is carried out according to customer requirements, or a repair of a motor vehicle (part) s which has already been designed in a corresponding manner.
- the method according to the invention can be carried out in the craft sector, for example in a painting workshop as a separate method step or as an integrated method step as part of a full or partial coating.
- a test sheet (5 cm by 10 cm) coated with a commercially available black basecoat is coated with a solvent-free, 100% solids content, UN-curable clearcoat in 100 ⁇ m wet layer thickness.
- a 3 mm thick glass plate which has on one side a line grating produced by chrome vapor deposition, which has a mask area of 2 cm by 2 cm (width of the grating lines designed as plateau: 8 ⁇ m, amplitude height of the grating lines: 120 nm, equidistant spacing of the outer plateau edges: 8 ⁇ m), is placed with its flat side on the uncured clear coat.
- the entire clear lacquer layer, partially covered by the glass plate, is then irradiated with a UN flash lamp (3500 watt seconds) with 5 UN flashes at intervals of 4 seconds.
- the glass plate is then removed and the partly still uncured clear lacquer layer is irradiated analogously with 5 UN flashes.
- a 2 cm by 2 cm area is perceived in the clear lacquer surface as a spectrum with rainbow colors.
- the sample sheet is tilted, the rainbow-colored area is suddenly no longer perceived from a certain viewing angle.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU12717/00A AU1271700A (en) | 1998-11-19 | 1999-11-16 | Method for decorating the surface of a painted substrate |
EP99955997A EP1135266A1 (en) | 1998-11-19 | 1999-11-16 | Method for decorating the surface of a painted substrate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19853385.3 | 1998-11-19 | ||
DE19853385 | 1998-11-19 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000030870A1 true WO2000030870A1 (en) | 2000-06-02 |
Family
ID=7888348
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1999/008798 WO2000030870A1 (en) | 1998-11-19 | 1999-11-16 | Method for decorating the surface of a painted substrate |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1135266A1 (en) |
AU (1) | AU1271700A (en) |
WO (1) | WO2000030870A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60161772A (en) * | 1984-01-28 | 1985-08-23 | Toyota Motor Corp | Mark forming method |
DE3737455A1 (en) * | 1986-11-06 | 1988-05-19 | Westinghouse Electric Corp | DEVICE AND METHOD FOR PRODUCING COLOR PATTERNS |
US4959283A (en) * | 1988-01-15 | 1990-09-25 | E. I. Du Pont De Nemours And Company | Dry film process for altering wavelength response of holograms |
US5182180A (en) * | 1991-08-27 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Dry film process for altering the wavelength of response of holograms |
US5500311A (en) * | 1993-11-08 | 1996-03-19 | E. I. Du Pont De Nemours And Company | Holographic flake pigment |
-
1999
- 1999-11-16 WO PCT/EP1999/008798 patent/WO2000030870A1/en not_active Application Discontinuation
- 1999-11-16 AU AU12717/00A patent/AU1271700A/en not_active Abandoned
- 1999-11-16 EP EP99955997A patent/EP1135266A1/en not_active Withdrawn
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60161772A (en) * | 1984-01-28 | 1985-08-23 | Toyota Motor Corp | Mark forming method |
DE3737455A1 (en) * | 1986-11-06 | 1988-05-19 | Westinghouse Electric Corp | DEVICE AND METHOD FOR PRODUCING COLOR PATTERNS |
US4959283A (en) * | 1988-01-15 | 1990-09-25 | E. I. Du Pont De Nemours And Company | Dry film process for altering wavelength response of holograms |
US5182180A (en) * | 1991-08-27 | 1993-01-26 | E. I. Du Pont De Nemours And Company | Dry film process for altering the wavelength of response of holograms |
US5500311A (en) * | 1993-11-08 | 1996-03-19 | E. I. Du Pont De Nemours And Company | Holographic flake pigment |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 009, no. 331 (C - 321) 25 December 1985 (1985-12-25) * |
Also Published As
Publication number | Publication date |
---|---|
EP1135266A1 (en) | 2001-09-26 |
AU1271700A (en) | 2000-06-13 |
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