EP0839073A1 - Multi-coat painting process - Google Patents
Multi-coat painting processInfo
- Publication number
- EP0839073A1 EP0839073A1 EP96919803A EP96919803A EP0839073A1 EP 0839073 A1 EP0839073 A1 EP 0839073A1 EP 96919803 A EP96919803 A EP 96919803A EP 96919803 A EP96919803 A EP 96919803A EP 0839073 A1 EP0839073 A1 EP 0839073A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- coating
- layer
- coating layer
- coating agent
- layers
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/577—Three layers or more the last layer being a clear coat some layers being coated "wet-on-wet", the others not
Definitions
- the invention relates to a method for producing a multilayer coating of conductive, in particular metallic substrates, which is particularly suitable for automotive coating.
- Today's high-quality automotive OEM coatings generally consist of an electrophoretically applied primer that protects against corrosion and subsequently spray-applied subsequent layers consisting of a filler layer and a subsequently applied decorative coating of coloring and / or effect basecoat and a protective clearcoat layer that seals the surface.
- the total layer thickness of such automotive coatings is in practice between 90 and 130 ⁇ m, which is the sum of 15 to 25 ⁇ m layer thickness for the primer, 30 to 40 ⁇ m for the filler layer, 10 to 25 ⁇ m for the basecoat layer and 30 to 40 ⁇ m for the Clear coat results.
- layer thicknesses are considerably exceeded if paintwork with a particularly good visual appearance, i.e. with outstanding gloss and top coat level, for example, in the painting of motor vehicles of the luxury and luxury class.
- DE-A-42 15070 and DE-A-3839905 describe the application of several layers of clear lacquer to one basecoat. This then results in layer thicknesses of over 110 ⁇ m, e.g. up to 170 ⁇ m, which is undesirable for reasons of material savings and weight savings on the finished vehicle.
- the object of the invention is to provide multi-layer coatings, in particular automotive coatings, which meet the requirements of an outstanding gloss and topcoat level, without the normal measure of the total layer thicknesses of automotive to exceed paintwork and without having to accept disadvantages in the overall property level.
- Multi-layer coating in which a first coating layer of an electrophoretically depositable aqueous coating agent (I) is applied electrophoretically and then baked on an electrically conductive substrate, whereupon further coating layers are applied, which is characterized in that as
- Coating agent (I) uses one which leads to an electrically conductive coating layer in the baked state, whereupon after baking the first coating layer, an electrically insulating second coating layer is electrophoretically deposited and baked from an aqueous coating agent (II) that can be separated from (I) , whereupon a basecoat layer composed of a coloring and / or effect-imparting coating agent is applied as the third coating layer and overpainted and baked with a fourth, transparent coating layer made of a clear lacquer coating agent, whereupon one or more further transparent coating layers are applied, where appropriate, the total dry layer thickness of the lacquer structure is between 90 and 130 ⁇ m, preferably less than 110 ⁇ m, and the dry layer thickness of the transparent coating layer or the total layer thickness of the transparent coating layers is between en is 40 and 80 ⁇ m, preferably between 50 and 60 ⁇ m. If several layers of clear lacquer are applied, they can be created from the same or different clear lacquer coating agents.
- ETL electrophoretically depositable, but different, coating agents (I) and (II), in order to produce the first and second coating layers, it being true that the electrophoretically depositable coating agent (I ) Contains constituents which, in the baked state, of the first coating layer are used for the electrophoretic deposition of a further coating layer from one of (I) give various electrophoretically depositable coating agents (II) sufficiently low resistivity.
- the coating compositions (I) and (II) are aqueous coating compositions with a solids content of, for example, 10 to 20% by weight.
- This consists of conventional binders, at least some of the binders bearing ionic and / or substituents which can be converted into ionic groups, and, if appropriate, groups capable of chemical crosslinking, and any crosslinking agents, electrically conductive constituents, fillers, pigments and additives customary in lacquers.
- the ionic groups or groups of the binders which can be converted into ionic groups can be anionic or groups which can be converted into anionic groups, acidic groups such as -C00H, -S0 3 H and / or -P0 3 H 2 and the corresponding anionic groups neutralized with bases. They can also be cationic or convertible into cationic groups, for example basic groups, preferably nitrogen-containing basic groups; these groups can be present in quaternized form or they are converted into ionic groups using a conventional neutralizing agent, for example an organic monocarboxylic acid, such as, for example, formic acid or acetic acid. Examples are amino, ammonium, for example quaternary ammonium, phosphonium and / or sulfonium groups.
- the usual anionic group-containing anodically depositable electrocoat binders and paints can be used to produce the first and / or second coating layer.
- ATL anionic group-containing anodically depositable electrocoat binders and paints
- Epoxy resin esters (meth) acrylic copolymer resins, maleate oils or polybutadiene oils with a weight average molecular weight (Mw) of, for example, 300-10000 and an acid number of 35-300 mg KOH / g.
- the binders carry -C00H, -S0 3 H and / or -P0 3 H 2 groups. After neutralization of at least some of the acidic groups, the resins can be converted into the water phase.
- the binders can be self-crosslinking or externally crosslinking.
- the paints can therefore also Usual crosslinkers contain, for example triazine resins, crosslinkers which contain groups capable of transesterification or blocked polyisocyanates.
- the usual cathodic electrocoat materials (KTL) based on cationic or basic binders can also be used in the process according to the invention for producing the first and / or second coating layer.
- Such basic resins are, for example, primary, secondary and / or tertiary amino groups-containing resins whose amine numbers are e.g. are 20 to 250 mg KOH / g.
- the weight average molar mass (Mw) of the base resins is preferably 300 to 10,000.
- base resins are amino (meth) acrylate resins, aminoepoxide resins, aminoepoxy resins with terminal double bonds, amino epoxy resins with primary OH groups, aminopolyurethane resins, amino group-containing polybutadiene resins Carbon dioxide-amine reaction products. These base resins can be self-crosslinking or they are used in a mixture with known crosslinking agents. Examples of such crosslinkers are aminoplast resins, blocked polyisocyanates, crosslinkers with terminal double bonds, polyepoxide compounds or crosslinkers which contain groups capable of transesterification.
- Examples of base resins and crosslinking agents which can be used in cathodic immersion baths are in EP-A-0082 291, EP-A-0 234395, EP-A-0227 975, EP-A-0 178531, EP-A-0 333 327, EP-A-0 310 971, EP-A-0 455 270, US 3922 253, EP-A-0261 385, EP-A-0 245 786, DE-A-33 24 211, EP-A- 0414 199, EP-A-0476514. These resins can be used alone or in a mixture.
- non-yellowing CTL systems are preferably used, which prevent yellowing or discoloration of the multi-layer coatings produced by the process according to the invention during stoving.
- KTL systems that crosslink using specially selected blocked polyisocyanates, as described, for example, in EP-A-0 265 363.
- the electrocoat (ETL) coating agent (I) contains components that impart electrical conductivity. They should be one of the first coating layer in the baked state for electrophoretic Deposition of a further coating layer from the electrophoretically depositable coating agent (II) impart a sufficiently low specific resistance, for example between 10 3 and 10 s Ohm.cm.
- Such constituents are particulate inorganic 5 or organic electrical conductors or semiconductors, such as, for example, iron oxide black, graphite, carbon black, metal powder, for example made of aluminum, copper or stainless steel, molybdenum disulfide or polymers with electrical conductivity, such as preferably polyaniline.
- Examples of electrodeposition paints containing such constituents can be found in US 3,674,671, GB 2,129,807, EP-A-0409821 and EP-A-0426 327.
- the constituents imparting electrical conductivity are in the ETL coating agent (I) contained in an amount such that the desired specific resistance of the coating layer deposited therefrom is achieved in the baked state.
- the proportion of the constituent (s) which confer electrical conductivity is, for example, between 1 and 30% by weight.
- the proportion can easily be determined by a specialist; it depends, for example, on the specific weight, the specific electrical conductivity and the particle size of the constituents imparting electrical conductivity.
- One or more of these components can be present in combination.
- Coating layer in the baked state components imparting electrical conductivity can contain the ETL coating compositions (I) and (II) pigments, fillers and / or additives customary in lacquers.
- Suitable pigments are, for example, the customary inorganic and / or organic colored pigments and / or fillers. Examples are titanium dioxide, iron oxide pigments, phthalocyanine pigments, quinacridone pigments, kaolin, talc, silicon dioxide or coarse coal as black pigments, finely divided soot produced by incomplete combustion, coarse soot obtained by catalytic or thermal decomposition of liquid or gaseous hydrocarbons.
- the pigments can be dispersed into pigment pastes, for example using known paste resins. Resins of this type are familiar to the person skilled in the art. Examples of paste resins that can be used in KTL baths are described in EP-A-0 183025 and in EP-A-0469 497.
- additives as are known in particular for ETL coating agents, are possible as additives.
- these are wetting agents, neutralizing agents, leveling agents, catalysts, corrosion inhibitors, antifoams, solvents, but in particular light stabilizers, if appropriate in combination with antioxidants.
- the basecoats which can be used according to the invention for the production of the third coating layer can be physically drying or can be crosslinked to form covalent bonds.
- Formation of covalent crosslinking basecoats can be self- or externally crosslinking systems.
- the color and / or effect basecoats which can be used in the process according to the invention are liquid coating compositions. It can be a one- or multi-component coating agent, single-component are preferred. It can be systems based on organic solvents or it is preferably water-based paints, the binder systems of which are suitable, e.g. anionic, cationic or non-ionic, are stabilized.
- the basecoat coating compositions which can be used are conventional lacquer systems which contain one or more conventional base resins as film-forming binders. If the base resins are not self-crosslinking or self-drying, they can optionally also contain crosslinking agents. Both the base resin component and the crosslinker component are not subject to any limitation. Polyester, polyurethane and / or (meth) acrylic copolymer resins, for example, can be used as film-forming binders (base resins). In the case of the preferred waterborne basecoats, polyurethane resins are preferably present, particularly preferably at least in a proportion of 15% by weight, based on the solid resin content of the waterborne basecoat.
- crosslinking agents which may be present is not critical, it depends on the functionality of the base resins, ie the crosslinking agents are selected such that they have a reactive functionality which is complementary to the functionality of the base resins.
- Examples of such complementary functionalities between base resin and crosslinker are: hydroxyl / methylol ether, hydroxyl / free isocyanate, hydroxyl / blocked isocyanate, carboxyl / epoxide. If compatible with one another, several such complementary functionalities can also be present side by side in a basecoat.
- the crosslinking agents optionally used in the basecoats can be present individually or in a mixture.
- the basecoats used in the process according to the invention contain inorganic and / or organic colored pigments and / or effect pigments, such as, for example, titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone pigments, and metal pigments, for example from aluminum pigments or copper, interference pigments, such as, for example, titanium dioxide-coated aluminum, coated mica, graphite effect pigments, platelet-shaped / iron oxide, platelet-shaped copper pthalocyanine pigments and effect pigments which develop a strong color flop, in particular on dark substrates.
- inorganic and / or organic colored pigments and / or effect pigments such as, for example, titanium dioxide, iron oxide pigments, carbon black, azo pigments, phthalocyanine pigments, quinacridone pigments, and metal pigments, for example from aluminum pigments or copper, interference pigments, such as, for example, titanium dioxide-coated aluminum, coated mica, graphite effect pigments, platelet-shaped
- effect pigments are described in EP-A-0358 208, EP-A-0 383 376, EP-A-0 601 483, EP-A-0 686 674, EP-A-0688833, US 4,434,010, WO 95 17 480, WO 95 32 247, WO 95 32 248.
- Basecoat materials containing such effect pigments are preferably applied to dark, particularly preferably to black, two-layered coatings multi-layer coatings produced by electrocoating.
- the basecoats may also contain customary paint additives, e.g. Fillers, catalysts, leveling agents, anti-cratering agents or, in particular, light stabilizers, optionally in combination with antioxidants.
- customary paint additives e.g. Fillers, catalysts, leveling agents, anti-cratering agents or, in particular, light stabilizers, optionally in combination with antioxidants.
- solvent-based basecoat systems which can be used in the process according to the invention can be found in DE-A-37 15254, DE-A-39 13001, DE-A-41 15948, DE-A-42 18 106, EP-A- 0289 997 and W0-91 00895.
- waterborne basecoat systems which can preferably be used in the process according to the invention can be found in DE-A-29 26 584, DE-A-36 28 124,
- the electrocoating lacquer used to produce the second coating layer has a color tone which is close to or identical to that of the basecoat used to produce the third coating layer.
- the closest color tones are to be understood to mean that the difference in color, comprising the difference in brightness, hue and difference in color, between the hues of the second and third coating layers determined in each case with opaque coating and a measurement geometry of (45/0 °) n-fold ⁇ E * (CIELAB) value does not exceed, the ⁇ E * (CIELAB) reference value being that which is shown in the CIE x, y diagram (chromaticity diagram) familiar to the person skilled in the art based on DIN 6175 for the The color of the third coating layer results and the following relationship applies:
- all customary clear lacquers or transparent colored or colorless pigmented coating compositions are suitable as clear coating compositions for the production of the fourth and possibly further coating layers.
- These can be single-component or multi-component clear lacquer coating compositions. They can be solvent-free (liquid or as a powder clearcoat), or they can be systems based on solvents, or they can be water-dilutable clearcoats, the binder systems of which are suitable, e.g. anionic, cationic or non-ionic, are stabilized.
- the water-dilutable clear lacquer systems can be water-soluble or water-dispersed systems, for example emulsion systems or powder slurry systems.
- the clear lacquer coating agents harden when stoved to form covalent bonds as a result of chemical crosslinking.
- the clearcoats which can be used in the process according to the invention are customary clearcoat coating compositions which contain one or more customary base resins as film-forming binders. If the base resins are not self-crosslinking, they may also contain crosslinking agents. Both the base resin component and the crosslinker component are not subject to any limitation. Polyester, polyurethane and / or (meth) acrylic copolymer resins, for example, can be used as film-forming binders (base resins).
- base resins polyester, polyurethane and / or (meth) acrylic copolymer resins, for example, can be used as film-forming binders (base resins).
- the selection of the crosslinking agents that may be present is not critical; it depends on the functionality of the base resins, i.e. the crosslinkers are selected so that they have a reactive functionality which is complementary to the functionality of the base resins. Examples of such complementary functionalities between base resin and crosslinker are: carboxyl / epoxy, something directly bound to carbon or
- hydroxyl groups bonded directly to silicon also include latent silanol groups, such as, for example Alkoxysilane groups to understand. If compatible with one another, several such complementary functionalities can also be present side by side in a clear lacquer.
- the crosslinking agents optionally used in the clear lacquers can be present individually or in a mixture. 5
- Examples of one (1K) and two-component (2K) non-aqueous clearcoat systems which can be used as clearcoat in the process according to the invention can be found in DE-A-38 26 693, DE-A-40 17 075, DE-A -41 24 167, DE-A-41 33704, DE-A-42 04 518, DE-A-42 04 611, EP-A-0 257 513, EP-A-0408858, EP-A-0 523 267, EP-A-0 557 822, W0-92 11 327.
- Water clearcoat systems which can be used as clearcoat in the process according to the invention can be found in DE-A-39 10829, DE-A-4009 931, DE-A-4009932, DE-A-41 01 696, DE-A-41 32 430 , DE-A-41 34 290, DE-A-42 03510, EP-A-0365098, EP-A-0365775, EP-A-0496079, EP-A-0546640.
- Examples of the powder clearcoat systems preferably used in the process according to the invention for producing the transparent coating layer can be found in EP-A-0 509 392, EP-A-0 509 393, EP-A-0 522648, EP-A-0 544 206, EP- A-0 555 705, DE-A-42 22 194, DE-A-42 27 0 580.
- the transparent coating can be applied in a single layer or in the form of several layers from the same or from several different transparent coating agents.
- the 5 transparent coating layer is expediently applied as a fourth layer comprising only one clear lacquer coating agent.
- Clear coating compositions which are as low as possible are preferably used Have a tendency to run off, for example, high-solids clear lacquers with a correspondingly adjusted rheological behavior. Powder clearcoats are particularly preferred.
- Electrically conductive materials such as metals are suitable as the substrate for the method according to the invention.
- automobile bodies or parts thereof are particularly suitable; they can be made of pretreated or untreated metal or electrically conductive or provided with an electrically conductive layer.
- the first coating layer of the aqueous coating agent (I) is deposited electrophoretically on these substrates in a customary manner in a dry layer thickness of, for example, 5 to 15 ⁇ m and, for example, baked at temperatures between 130 and 180 ° C.
- the second coating layer made of a second coating agent (II) different from (I) different from (I) and having a dry layer thickness of, for example, from 5 to 10 ⁇ m is coated on the substrate thus obtained, which has a specific resistance of 10 3 to 10 s ohm.cm. 35 ⁇ m, preferably between 10 to 25 ⁇ m, applied and likewise baked, for example, at temperatures between 130 and 180 ° C.
- the second coating layer generally has practically no electrical conductivity, ie it has a specific resistance of more than 10 9 ohm.cm in the baked state.
- the coating obtained by electrodeposition from the coating agent (I) serves in particular to protect against chemical and corrosive attack, so that it is advantageous to coat the entire surface of a three-dimensional substrate, for example a body, if possible.
- the coating obtained by electrodeposition from the coating agent (II) and electrically insulating in the baked state can, but does not have to cover the entire three-dimensional area
- a possible double coating is, for example, a full-surface first coating
- the third coating layer is then sprayed from the color and / or effect basecoat in a dry layer thickness of 10 to 25 ⁇ m, depending on the color, for example by 10 compressed air sprayers, airless sprayers or ESTA high-speed rotary sprayers.
- the fourth coating layer is applied from a customary liquid or powder clearcoat (in this case it is a dry-in-wet application) and baked together with the third coating layer, for example at temperatures from 80 to 160 ° C. If necessary, further layers of clear lacquer from the
- the layer thickness of the transparent coating layer or the total layer thickness of the transparent coating layers is between 40 and 80 ⁇ m, preferably between 50 and 60 ⁇ m.
- the powder topcoat is based on a powder clearcoat binder / crosslinking system known per se, as described above, for example, in connection with the powder clearcoats.
- the powder topcoat contains coloring and / or effect pigments, such as those described above for the basecoats.
- the method according to the invention allows the production of multi-layer coatings, in particular automotive coatings with an overall level of properties comparable to that of the prior art and an improved gloss and topcoat level. It has been shown that excellent properties are achieved by the procedure according to the invention, although this makes it possible to dispense with conventional spray filler layers. Despite the high layer thickness when applying the clear lacquer, the total layer thicknesses of the multi-layer lacquers produced by the process according to the invention are very small. They are in particular 90 to 130 ⁇ m.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Laminated Bodies (AREA)
- Reinforced Plastic Materials (AREA)
- Production Of Multi-Layered Print Wiring Board (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19519665A DE19519665C1 (en) | 1995-05-30 | 1995-05-30 | Multi-coat lacquering process for vehicle or component |
DE19519665 | 1995-05-30 | ||
PCT/EP1996/002234 WO1996038235A1 (en) | 1995-05-30 | 1996-05-24 | Multi-coat painting process |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0839073A1 true EP0839073A1 (en) | 1998-05-06 |
EP0839073B1 EP0839073B1 (en) | 1999-09-22 |
Family
ID=7763138
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96919803A Expired - Lifetime EP0839073B1 (en) | 1995-05-30 | 1996-05-24 | Multi-coat painting process |
Country Status (11)
Country | Link |
---|---|
US (1) | US5882734A (en) |
EP (1) | EP0839073B1 (en) |
JP (1) | JPH11505767A (en) |
KR (1) | KR100394579B1 (en) |
AT (1) | ATE184814T1 (en) |
BR (1) | BR9608598A (en) |
CA (1) | CA2222803A1 (en) |
DE (2) | DE19519665C1 (en) |
ES (1) | ES2140864T3 (en) |
WO (1) | WO1996038235A1 (en) |
ZA (1) | ZA964394B (en) |
Families Citing this family (19)
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DE19525375A1 (en) * | 1995-07-12 | 1997-01-16 | Herberts Gmbh | Coating agents, their use and process for the production of multilayer coatings |
DE19643082C2 (en) * | 1995-10-18 | 2003-10-30 | Volkswagen Ag | Process for the interior and exterior coating of a body with cavities |
DE19633173C1 (en) * | 1996-08-17 | 1997-10-02 | Herberts Gmbh | Multilayered lacquering, e.g. of vehicles |
DE19648517A1 (en) * | 1996-11-23 | 1998-06-04 | Herberts & Co Gmbh | Process for multi-layer painting |
DE19733312A1 (en) * | 1997-08-01 | 1999-02-04 | Herberts Gmbh | Process for applying a protective and decorative layer composite |
US6423425B1 (en) | 1998-05-26 | 2002-07-23 | Ppg Industries Ohio, Inc. | Article having a chip-resistant electrodeposited coating and a process for forming an electrodeposited coating |
US6248225B1 (en) | 1998-05-26 | 2001-06-19 | Ppg Industries Ohio, Inc. | Process for forming a two-coat electrodeposited composite coating the composite coating and chip resistant electrodeposited coating composition |
US20020056641A1 (en) * | 1999-12-15 | 2002-05-16 | December Timothy S. | Cured multilayer coating providing improved edge corrosion resistance to a substrate and a method of making same |
US6368719B1 (en) * | 2000-06-12 | 2002-04-09 | E. I. Du Pont De Nemours And Company | Process for preparing multi-layer coatings on automotive bodies or automotive body parts |
US6676820B2 (en) * | 2001-03-02 | 2004-01-13 | Ppg Industries Ohio, Inc. | Process for electrocoating metal blanks and coiled metal substrates |
US6508922B2 (en) | 2001-05-10 | 2003-01-21 | E. I. Du Pont De Nemours And Company | Process for multi-layer coating |
US20040118695A1 (en) * | 2002-08-29 | 2004-06-24 | Ding-Yu Chung | Two-coat electrocoating process |
US20050250416A1 (en) * | 2004-04-23 | 2005-11-10 | Barthold Mark J | Toy and card package |
US20050250415A1 (en) * | 2004-04-23 | 2005-11-10 | Barthold Mark J | Toy and card package |
US20060076735A1 (en) * | 2004-10-08 | 2006-04-13 | Nathan Proch | Wheel having a translucent aspect |
US20060078684A1 (en) * | 2004-10-08 | 2006-04-13 | Neo Tian B | Paint process for toys |
US20060079149A1 (en) * | 2004-10-08 | 2006-04-13 | Nathan Proch | Cut-out logo display |
US20060079150A1 (en) * | 2004-10-08 | 2006-04-13 | Miva Filoseta | Toy for collecting and dispersing toy vehicles |
US7959981B2 (en) * | 2007-08-27 | 2011-06-14 | Ppg Industries Ohio, Inc. | Process for depositing multiple coatings layers on a substrate |
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DE4011633A1 (en) * | 1990-04-11 | 1991-10-17 | Herberts Gmbh | METHOD FOR PRODUCING MULTILAYER COATINGS |
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DE4134290A1 (en) * | 1991-10-17 | 1993-09-23 | Herberts Gmbh | METHOD OF MULTILAYER LACQUERING |
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DE4331673A1 (en) * | 1993-09-17 | 1995-05-11 | Herberts Gmbh | Process for the production of multi-layer coatings |
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1995
- 1995-05-30 DE DE19519665A patent/DE19519665C1/en not_active Expired - Fee Related
-
1996
- 1996-05-24 CA CA002222803A patent/CA2222803A1/en not_active Abandoned
- 1996-05-24 DE DE59603174T patent/DE59603174D1/en not_active Expired - Fee Related
- 1996-05-24 AT AT96919803T patent/ATE184814T1/en not_active IP Right Cessation
- 1996-05-24 WO PCT/EP1996/002234 patent/WO1996038235A1/en active IP Right Grant
- 1996-05-24 BR BR9608598A patent/BR9608598A/en not_active IP Right Cessation
- 1996-05-24 KR KR1019970708569A patent/KR100394579B1/en not_active IP Right Cessation
- 1996-05-24 EP EP96919803A patent/EP0839073B1/en not_active Expired - Lifetime
- 1996-05-24 JP JP8536162A patent/JPH11505767A/en active Pending
- 1996-05-24 ES ES96919803T patent/ES2140864T3/en not_active Expired - Lifetime
- 1996-05-24 US US08/952,728 patent/US5882734A/en not_active Expired - Fee Related
- 1996-05-29 ZA ZA964394A patent/ZA964394B/en unknown
Non-Patent Citations (1)
Title |
---|
See references of WO9638235A1 * |
Also Published As
Publication number | Publication date |
---|---|
EP0839073B1 (en) | 1999-09-22 |
US5882734A (en) | 1999-03-16 |
ZA964394B (en) | 1996-12-09 |
DE19519665C1 (en) | 1996-09-05 |
BR9608598A (en) | 1999-01-05 |
ES2140864T3 (en) | 2000-03-01 |
WO1996038235A1 (en) | 1996-12-05 |
KR100394579B1 (en) | 2003-10-30 |
DE59603174D1 (en) | 1999-10-28 |
MX9709224A (en) | 1998-03-31 |
JPH11505767A (en) | 1999-05-25 |
ATE184814T1 (en) | 1999-10-15 |
KR19990022090A (en) | 1999-03-25 |
CA2222803A1 (en) | 1996-12-05 |
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