EP1495085A4 - Procede et composition de produits de finition de metal - Google Patents

Procede et composition de produits de finition de metal

Info

Publication number
EP1495085A4
EP1495085A4 EP02728642A EP02728642A EP1495085A4 EP 1495085 A4 EP1495085 A4 EP 1495085A4 EP 02728642 A EP02728642 A EP 02728642A EP 02728642 A EP02728642 A EP 02728642A EP 1495085 A4 EP1495085 A4 EP 1495085A4
Authority
EP
European Patent Office
Prior art keywords
silane
adhesion promoter
composition
urethane composition
polyurethane film
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
Application number
EP02728642A
Other languages
German (de)
English (en)
Other versions
EP1495085B1 (fr
EP1495085A1 (fr
Inventor
Qihua Nmi Xu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LACKS ENTPR Inc
Lacks Enterprises Inc
Original Assignee
LACKS ENTPR Inc
Lacks Enterprises Inc
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 LACKS ENTPR Inc, Lacks Enterprises Inc filed Critical LACKS ENTPR Inc
Publication of EP1495085A1 publication Critical patent/EP1495085A1/fr
Publication of EP1495085A4 publication Critical patent/EP1495085A4/fr
Application granted granted Critical
Publication of EP1495085B1 publication Critical patent/EP1495085B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • B05D7/14—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 to metal, e.g. car bodies
    • B05D7/16—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 to metal, e.g. car bodies using synthetic lacquers or varnishes
    • 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
    • B05D7/52—Two layers
    • B05D7/53—Base coat plus clear coat type
    • B05D7/534—Base coat plus clear coat type the first layer being let to dry at least partially before applying the second layer
    • 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
    • B05D2601/00—Inorganic fillers
    • B05D2601/02—Inorganic fillers used for pigmentation effect, e.g. metallic effect
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects

Definitions

  • This invention relates to a process for depositing a polymer film on a metal surface, and more particularly to a process for applying a durable ur ethane film to a metal surface.
  • chrome plating creates a smooth, bright chrome finish. It has long been desired to have other finishes, such as black chrome, gold-tinted chrome, and other tinted or colored metallic finishes for decorative purposes. More specifically, there is a desire for clear polymeric decorative coatings that allow the brightness and luster of chrome plating to be seen, while modifying the appearance by imparting a color or tint to the chrome plating.
  • PND physical vapor deposition
  • a process for adhering a relatively thick layer, e.g., 5 millimeters, of polyurethane elastomer to a metal, such as steel, iron or aluminum, is disclosed in U.S. Patent No. 4,542,070.
  • the process involves coating the surface of the metal with a primer composition containing a polyepoxy compound and a polyamine compound, further coating the surface with a composition containing an isocyanate compound having an isocyanate group concentration of 15-50% by weight, and casting a layer of polyurethane elastomer onto the double coated surface of the metal followed by hardening the whole system.
  • a silane-coupling agent may be added to the primer composition to improve adhesive properties and water resistance.
  • silane-coupling agents include gamma-glycidoxypropyltrimethoxysilane and gamma- aminopropyltriethoxysilane.
  • Color pigments may be added to the composition.
  • Solvents that may be used for the primer composition are those which dissolve both the polyamine compound and the polyepoxy compound, with examples including toluene, xylene, ethylbenzene, methylethylketone, methylcellosolve, ethylcellosolve and acetate esters of a cellosolve compound.
  • the polyurethane elastomer is used to improve the durability of steel, iron and aluminum surfaces of metal articles.
  • a clear polyurethane film is adhered to a bright metal surface using a primer containing a silane-coupling agent.
  • the polymer film may contain a coloring or tinting agent that modifies the perceived color of the underlying chrome surface.
  • the invention offers a process of creating unique surface finishes on chrome- plated substrates. More specifically, the process provides an economical way of creating surface finishes similar to black chrome, PVD finishes, and other colored metallic finishes, such as blue, red, green, yellow, etc. The colors and the gloss level can be varied as desired.
  • the process employs an adhesion enhancer that can be applied as a primer or as an additive to a polyurethane composition. The adhesion performance between the chrome surface and the film is improved so that both the film and the adhesion between the film and the chrome plating are durable enough for practical applications such as in the automotive industry and in electronic devices such as cellular phones.
  • a clear, hard polyurethane polymer film is deposited on a chrome plating by first applying an aqueous primer composition to the chrome plating, and applying a two part urethane composition over the primer composition.
  • the primer composition is comprised, and more preferably consists essentially of, water, methanol, and a silane-coupling agent.
  • the primer composition may be applied to a bright metal surface by spraying, dipping or wiping techniques. Preferably, the bright metal surface is cleaned prior to application of the primer composition.
  • the applied primer composition is allowed to dry. After the primer composition has dried, a liquid urethane composition is applied over the dried primer composition, and is allowed to cure.
  • the urethane composition can be applied by any of various techniques, including spraying, dipping or wiping techniques, with spraying being preferred.
  • a suitable thermal cure can be achieved in about 60 minutes at 180°F (about 82°C).
  • the polyurethane films of this invention generally have a thickness of from about 5-200 microns, more typically from 10-100 microns, and preferably from 20-50 microns.
  • the two-part urethane composition preferably includes a dye, pigment or other colorant or a mixture of colorants to create a desired tinted film.
  • the urethane composition may be either a one-component urethane system, or preferably a two-component urethane system.
  • a two-component urethane system is a urethane system in which the isocyanate and polyol components are kept separate from one another until just prior to use at which time those components are mixed together and applied to a surface. Upon mixing the two components, a full urethane polymerization reaction occurs.
  • any of a variety of two-component polyurethane systems that are suitable for forming continuous films may be used in this invention.
  • preferred polyurethane systems include those comprising, as the polyol component, al ⁇ ha,omega-polymethacrylate polyols.
  • Suitable alpha,omega- polymethacrylate polyols are commercially available, or can be obtained by reacting terminally hydroxy-functional polymethacrylates, obtained by free-radical polymerization in the presence of a hydroxy-functional molecular weigh regulator, with polyols, with the addition of non-basic transesterification catalysts, in a molar ratio of polymethacrylate to polyol of from 1 : 1 to 1 : 10.
  • Examples of monomers that may be used for forming the polymethacrylate sequence of the terminally hydroxy-functional polymethacrylate polyols include diols such as methylmethacrylate, ethy -methacrylate, propy -methacrylate, n-buty -methacrylate, isobutylmethacrylate, tert-buty -methacrylate, n-pentylmethacrylate, amylmethacrylate, n-hexylmethacrylate, n-octylmethacrylate, 2- ethylhexylmethacrylate, n-decylmethacrylate, cyclopentylmethacrylate, cy clohexylmethacrylate , 4-tert-butylcyclohexylmethacrylate , cyclooctylmethacry late , pheny -methacrylate, isoborny -meth
  • suitable diols for the transesterification reaction include ethylene glycol, propane- 1,2-diol, propane- 1, 3 -diol, butane-l,2-diol, butane- 1, 3 -diol, butane- 1,4-diol, neopentylglycol, hexane-l,6-diol, octane-l,8-diol, decane-l,10-diol, doceane-l,12-diol, cyclopentane-l,2-diol, cyclohexane-l,2-diol, cyclohexane- 1,4-diol, diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, poly oxy ethy lene-polyoxypr opylene-diols , 2,3 -but
  • the polyol components of the two-component urethane system may have a number-average molecular weight of from about 1,000 to about 30,000 Daltons, a hydroxyl number of between 20 and 200 mg of KOH/g, and an acid number of between 5 and 150 mg of KOH/g.
  • alpha, omega-polymethacry late polyols other polyols may be employed.
  • aliphatic, cycloaliphatic, arylaliphatic and/or aromatic diols and/or polyols having a molecular weight of from about 60 to about 4,000 Daltons, may be employed.
  • saturated and/or unsamrated polyester diols and/or polyester polyols and/or polyether diols and/or polyether polyols having a number- average molecular weight of from about 400 to about 5,000 Daltons may be employed.
  • Polyester diols may be prepared by esterifying organic dicarboxylic acids or their anhydrides with organic diols, or from a hydroxy carboxylic acid or from a lactone.
  • Branched polyester polyols may be prepared by employing polyols or polycarboxylic acids having a higher functionality.
  • suitable polyurethane compositions may comprise, as the polyol component, various polyether polyols generally derived from cyclic ethers, and various polyester polyols, such as those obtained from residues of terephthalic acid production or by transesterification of dimethyl terephthalate or poly(ethylene terephthalate) with glycols.
  • suitable polyisocyanate compounds that may be used in the two- component urethane systems include monomeric organic polyisocyanates having a molecular weight of from about 140 to 300 Daltons, lacquer polyisocyanates having a molecular weight of from about 300 to 1,000 Daltons, and isocyanate-functionalized prepolymers containing urethane groups and having a molecular weight above 1,000 Daltons, as well as mixtures thereof.
  • monomeric polyisocyanates examples include 1,4-diisocyanato-butane, 1,6- diisocyanatohexane, 1 ,5-diisocyanato-2,2-dimefhyl-pentane, 2,2,4-trimethyl-l ,6- diisocyanatohexane, 2,4,4-trimethyl-l ,6-diisocyanatohexane, l-isocyanato-3 ,3,5- trimethyl-5-isocyanatomethylcyclohexane, l-isocyanato-l-methyl-4(3)- isocyanatomethylcyclohexane, bis-(4-isocyanatocyclohexyl)methane, 1 , 10- diisocyanatodecane, 1 , 12-diisocyanatododecane, cyclohexane-1 ,3-diisocyanate, cyclohexane-l,4-
  • Lacquer polyisocyanates are obtained by oligomerizing monomeric diisocyanates to form carbodiimide, uretdione (dimers), isocyanurate (trimers), biuret, urea, urethane, allophanate and/or oxadiazine groups. Several of these groups may be formed simultaneously or successively during oligomerization.
  • Examples of isocyanate functionalized prepolymers containing urethane groups having a molecular weight of about 1,000 or above may be prepared by reacting monomeric diisocyanates and/or lacquer polyioscyanates with an organic polyhydroxyl compound having a molecular weight of about 300 or greater.
  • the polyhydroxyl compounds typically used to prepare isocyanate functionalized prepolymers are those having a number average molecular weight that is preferably greater than 500 Daltons, and more preferably from about 500 Daltons to about 4,000 Daltons. These polyhydroxyl compounds typically have from 2 to 6, and more typically from about 2 to 3 hydroxyl groups from molecule, and are generally selected from ether, ester, thioether, carbonate and/or polyacrylate polyols.
  • one or more polyols, and one or more polyisocyanates are mixed together in amounts corresponding to an NCO:OH equivalent ratio of from about 0.5:1 to about 2.0: 1, more typically from about 0.8 : 1 to about 1.5 : 1.
  • Various ingredients conventionally employed in urethane coating compositions may be added. These ingredients include flow control agents, viscosity-controlling additives, pigments, fillers, flatting agents, UV stabilizers and anti-oxidants and catalysts for the cross-linking reaction.
  • One-component urethane systems are those in which a soluble or dispersible urethane prepolymer that is the reaction product of a polyol with a polyisocyanate is provided with moisture curable functionalities or air- drying functionalities that facilitate cross-linking and formation of a film after application to a chrome or other bright metal substrate.
  • Examples of one-component urethane systems include air-curing urethanes systems such as those in which an oligomeric urethane prepolymer is cross-linked by oxidation of unsaturated carbon-carbon double bonds in a long chain aliphatic group.
  • Other one-component urethane systems include moisture curable urethane systems that include silanol terminated urethane prepolymers that are cross-linked by hydrolysis and silane condensation reactions upon contact with moisture.
  • two-component urethane compositions are preferred because they usually exhibit better scratch resistance, and chemical resistance than one-component systems.
  • the principals of this invention may be applied to other applications using a one-component urethane system when scratch-resistance and chemical resistance are not as important as it is with most automotive and electronic applications (e.g., cellular telephone housings).
  • the polyurethane films of this invention are preferably relatively hard and non- elastomeric, and exhibit a pencil hardness of from about 3H to about 6H.
  • the coating composition may be solventless, aqueous-based, or organic solvent-based.
  • polyurethanes and polyisocyanates that may be employed in the practice of this invention.
  • the invention is not limited to any particular two-component polyurethane systems.
  • Two- component urethane systems containing acrylic polyols such as polymeric/oligomeric materials comprised of acrylates, methacrylates, acrylonitrile, methacrylonitrile, or combinations of these monomers etc. are suitable and/or preferred.
  • other polyurethane compositions such as polyether based urethane systems are also believed to be suitable for various automotive, appliance and consumer electronics applications. It is believed that the principles of this invention may also be applied to various applications in which it is desirable to strongly adhere a polyurethane film to the surface of a metal.
  • silane-coupling agent or adhesion enhancer either in a primer that is applied to a metal and dried before application of a two-component urethane system, or added into a two-component urethane system, allows a strong, durable bond to be formed between the metal and a cured polyurethane film.
  • any of a variety of commercially available two-component urethane compositions may be employed in accordance with this invention to provide an aesthetic or functional film that is strongly adhered to a metal surface.
  • the silane adhesion enhancer may be employed in a primer composition in an amount of from about 0.05 to about 5%, and more preferably from about 0.5 to about 2% , by weight of the primer composition, with an amount of 1 % being most preferred.
  • the primer composition is an aqueous solution that is free, or at least substantially free, of environmentally undesirable volatile organic compounds.
  • the aqueous primer composition is comprised of, and more preferably consists essentially of, water, methanol, and one or more silane adhesion enhancers.
  • the aqueous primer composition may contain from about 50% to about 95% water, and from about 5 to 50% methanol.
  • the silane adhesion enhancer When the silane adhesion enhancer is added directly to a liquid two-component urethane composition, rather than to an aqueous primer composition, the silane adhesion enhancer may be employed in an amount from about 0.05% to about 5%, more preferably from about 0.5% to about 2% , and most preferably about 1 %, by weight of the urethane composition.
  • the silane adhesion enhancer When the silane adhesion enhancer is added directly to the urethane composition, the urethane composition is applied directly to a clean, but otherwise untreated, surface of a chrome plate.
  • epoxy functional silane-coupling agents e.g., gamma- glycidoxypropyltrimethoxy silane
  • aromatic amine functional silane-coupling agents such as N-phenyl-gamma-aminopropyltrimethoxysilane are particularly useful for achieving strong, durable adhesion between a chrome plate and a cured polyurethane film.
  • silane adhesion promoters including the preferred aromatic amine functional silane-coupling agents and epoxy functional coupling-agents
  • suitable silanes include amine silanes such as N-beta-(aminoethyl)-gamma- aminopropyltrimethoxysilane and gamma-aminopropyltriethoxysilane.
  • a particular use of this invention involves application of a tinted or colored decorative polymer film to a chrome plate to impart a desired hue or color to the chrome plate while also allowing the brightness and luster of the chrome plate to be seen through the film. Therefore, in accordance with this aspect of the invention, any of various dyes, pigments, or other colorants, or mixtures of colorants may be added in an amount effective to impart a desired color, tint or hue to a chrome plate. Suitable colorants and amounts thereof are well known and/or can be easily determined by routine experimentation.
  • the tinted urethane compositions of this invention when applied to a chrome plate or other metal surface, create a unique surface finish that is different from conventional paint or traditional chrome plated finishes.
  • the tinted finishes can be generally any color in the spectrum, e.g., gray, gold, red, blue, etc.
  • the principles of this invention may be used for adhering a polyurethane film to various other bright metal surface, such as nickel, nickel alloys, tin, tin alloys (e.g., tin-cobalt alloys) and stainless steel.
  • Adhesion tests were conducted on coated samples using the compositions and processes of this invention (Examples 4-8) and compared with the adhesion results of a conventional urethane coating composition (Example 9).
  • Adhesion testing was conducted by keeping coated samples at ambient temperature for at least 4 hours, then immersing the samples in water at 38° C for 10 days. Thereafter a grid pattern was cut into each sample. The lines in the grid pattern were 2 mm apart from each other. A pressure sensitive adhesive tape was used to evaluate adhesion. The average percentage of coating that remained after the tape was pressed onto the grid and peeled away was used as an indication of adhesive strength or quality.
  • Examples 1-3 describe preparation of primer solutions according to the invention.
  • Example 9 the average percentage of coating that remained after the tape was removed was about 90% , as compared with about 50% for the conventional urethane coating.
  • Example 9 the average percentage of coating that remained after the tape was removed was about 90%, as compared with about 50% for the conventional urethane coating.
  • Example 7 On 4" x 4" chrome-plated plaques, the primer solution 3 was applied by dipping and dried for 5 minutes at room temperature. A two-part urethane clear coating (SL201 from Red Spot Paint & Vanish) was mixed based on the suggested ratio and applied by spray and cured for 1 hour at 180 F. The adhesion tested by adhesion tape was improved after temperature and humidity cycle as compared with a control (Example 9). More specifically, the average percentage of coating that remained after the tape was removed was about 90%, as compared with about 50% for the conventional urethane coating. Example 7
  • a two-part urethane clear coating (SL201 from Red Spot Paint & Vanish) was mixed based on the suggested ratio. Silane A-187 was added at 0.5% to the total mixed paint by volume. The coating was applied by spraying on the chrome-plated plaques and cured for 1 hour at 180 F. The adhesion tested by adhesion tape was improved after temperature and humidity cycle as compared with a control (Example 9). More specifically, the average percentage of coating that remained after the tape was removed was about 90% , as compared with about 50% for the conventional urethane coating.
  • a two-part urethane clear coating (SL201 from Red Spot Paint & Vanish) was mixed based on the suggested ratio.
  • Silane Y-6996 N-phenyl-gamma- aminopropyltrimethoxy silane, available from OSI Specialties, was added at 0.5% to the total mixed paint by volume.
  • the coating was applied by spraying on the chrome-plated plaques and cured for 1 hour at 180 F.
  • the adhesion tested by adhesion tape was improved after temperature and humidity cycle as compared with a control (Example 9) . More specifically, the average percentage of coating that remained after the tape was removed was about 100%, as compared with about 50% for the conventional urethane coating.
  • Example 9 Control
  • a two-part urethane clear coating (SL201 from Red Spot Paint & Vanish) was mixed based on the suggested ratio.
  • the coating was applied by spray on the chrome- plated plaques and cured for 1 hour at 180 F.
  • the adhesion tested by adhesion tape was poor after temperature and humidity cycle. More specifically, the average percentage of coating that remained after the tape was removed was about 50%.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Glass Compositions (AREA)
EP02728642A 2002-04-01 2002-04-01 Produit de finition de metal Expired - Lifetime EP1495085B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2002/010090 WO2003093386A1 (fr) 2002-04-01 2002-04-01 Procede et composition de produits de finition de metal

Publications (3)

Publication Number Publication Date
EP1495085A1 EP1495085A1 (fr) 2005-01-12
EP1495085A4 true EP1495085A4 (fr) 2005-11-02
EP1495085B1 EP1495085B1 (fr) 2008-10-15

Family

ID=29398906

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02728642A Expired - Lifetime EP1495085B1 (fr) 2002-04-01 2002-04-01 Produit de finition de metal

Country Status (5)

Country Link
EP (1) EP1495085B1 (fr)
AT (1) ATE411370T1 (fr)
AU (1) AU2002258686A1 (fr)
DE (1) DE60229442D1 (fr)
WO (1) WO2003093386A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005089480A2 (fr) 2004-03-19 2005-09-29 Stuart Arthur Bateman Procede d'activation
KR101264450B1 (ko) * 2005-01-21 2013-05-15 더 보잉 컴파니 변형제를 이용한 활성화 방법
US10703927B2 (en) 2014-04-10 2020-07-07 3M Innovative Properties Company Adhesion promoting and/or dust suppression coating

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05156499A (ja) * 1991-12-02 1993-06-22 Takasago Tekko Kk 塗料密着性に優れた金属材料の表面処理方法
EP1134251A1 (fr) * 2000-03-08 2001-09-19 Kaneka Corporation Composition primaire

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2307794A1 (de) * 1972-02-17 1973-08-23 Mitsui Toatsu Chemicals Polyurethanzusammensetzung
US4481160A (en) * 1979-12-17 1984-11-06 The D. L. Auld Company Manufacture of decorative emblems
JPS57184475A (en) * 1981-05-08 1982-11-13 Ihara Chem Ind Co Ltd Method of bonding urethane elastomer to metal
JP2772002B2 (ja) * 1988-11-28 1998-07-02 サンスター技研株式会社 プライマー組成物
US5578347A (en) * 1994-05-24 1996-11-26 E. I. Du Pont De Nemours And Company Process for applying a finish to a metal substrate
US6413588B1 (en) * 1999-01-11 2002-07-02 E. I. Du Pont De Nemours And Company Method of producing durable layered coatings

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05156499A (ja) * 1991-12-02 1993-06-22 Takasago Tekko Kk 塗料密着性に優れた金属材料の表面処理方法
EP1134251A1 (fr) * 2000-03-08 2001-09-19 Kaneka Corporation Composition primaire

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199329, Derwent World Patents Index; Class M11, AN 1993-232842, XP002324974 *

Also Published As

Publication number Publication date
DE60229442D1 (de) 2008-11-27
AU2002258686A1 (en) 2003-11-17
ATE411370T1 (de) 2008-10-15
EP1495085B1 (fr) 2008-10-15
WO2003093386A1 (fr) 2003-11-13
EP1495085A1 (fr) 2005-01-12

Similar Documents

Publication Publication Date Title
US4315970A (en) Adhesion of metals to solid substrates
US6749946B1 (en) Method and composition for metallic finishes
AU758660B2 (en) Method of producing durable layered coatings
KR100397713B1 (ko) 금속기재에마무리제를도포하는방법
US8309228B2 (en) Coatings containing polysilazanes for metal and polymer surfaces
AU2013280834B9 (en) Coating compositions with an isocyanate-functional prepolymer derived from a tricyclodecane polyol, methods for their use, and related coated substrates
US4551387A (en) Colored resinous articles with concealed metallic luster
CN108641515B (zh) 高附着力底漆涂料
TW558454B (en) Hydraulic transfer method
CN109370400B (zh) 一种水性双组分硅改性聚氨酯树脂及其制备方法
CN107936814A (zh) 一种poss 改性的高硬度聚氨酯净味木器漆
EP1495085B1 (fr) Produit de finition de metal
KR940002329A (ko) 환경부식 저항성, 일-성분, 코우팅 조성물, 그로 코우팅하는 방법 및 이로부터 얻어진 코우팅
CN109777292B (zh) 用于基材表面的高硬度高光泽度疏水涂饰材料及其应用方法
KR101795032B1 (ko) 건식도금용 다층 코팅, 그 제조방법 및 이를 포함하는 플라스틱 소재
CN118401616A (zh) 用于聚碳酸酯基材的多层涂层体系
CN114466705A (zh) 具有哑光和/或结构化金属效果的高光泽、可抛光的涂层及其制备方法
CN100999644A (zh) 银色聚酯面漆
KR101803437B1 (ko) 자가 치유용 투명 도료 조성물 및 이를 사용한 투명 도막의 형성방법
CN112143276B (zh) 用于汽车清漆的防污助剂及其制备方法和应用
EP1869131B1 (fr) Composition de peinture, procede de mise en peinture et de finition et articles peints
CA2388581A1 (fr) Revetements minces resistant aux salissures
KR20120045074A (ko) 탄성변성과 우레탄 변성 그리고 이소시아네이트 블로킹을 동시 개질한 폴리에스테르와 이를 이용한 프리 코티드용 자동차 강판 도료의 제조 방법
JPH04367766A (ja) 塗装方法
JPH0326771A (ja) 塗装方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041019

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 09K 3/00 A

Ipc: 7B 05D 7/16 B

Ipc: 7B 05D 7/00 B

Ipc: 7B 32B 27/40 B

A4 Supplementary search report drawn up and despatched

Effective date: 20050919

17Q First examination report despatched

Effective date: 20051128

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

RTI1 Title (correction)

Free format text: METALLIC FINISH

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60229442

Country of ref document: DE

Date of ref document: 20081127

Kind code of ref document: P

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081015

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081015

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090316

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081015

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081015

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081015

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090115

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081015

26N No opposition filed

Effective date: 20090716

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090430

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090401

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20090116

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090401

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081015

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081015

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20210324

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20210331

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20210318

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60229442

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20220331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20220331