US3711313A - Process for the deposition of resinous films on aluminum-bearing substrates - Google Patents

Process for the deposition of resinous films on aluminum-bearing substrates Download PDF

Info

Publication number
US3711313A
US3711313A US00027424A US3711313DA US3711313A US 3711313 A US3711313 A US 3711313A US 00027424 A US00027424 A US 00027424A US 3711313D A US3711313D A US 3711313DA US 3711313 A US3711313 A US 3711313A
Authority
US
United States
Prior art keywords
aluminum
coating
water
anodized
parts
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.)
Expired - Lifetime
Application number
US00027424A
Other languages
English (en)
Inventor
K Shibata
T Takahashi
H Mochizuki
Y Aoshima
I Hayashi
T Kato
T Nagano
M Suzuki
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.)
Riken Light Metal Industry Co Ltd
Kuboko Paint Co Ltd
Original Assignee
Riken Light Metal Industry Co Ltd
Kuboko Paint Co Ltd
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
Priority claimed from JP44070287A external-priority patent/JPS4931296B1/ja
Priority claimed from JP7028669A external-priority patent/JPS4931295B1/ja
Priority claimed from JP8564969A external-priority patent/JPS4931297B1/ja
Priority claimed from JP8565069A external-priority patent/JPS4931298B1/ja
Application filed by Riken Light Metal Industry Co Ltd, Kuboko Paint Co Ltd filed Critical Riken Light Metal Industry Co Ltd
Application granted granted Critical
Publication of US3711313A publication Critical patent/US3711313A/en
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

Definitions

  • This invention relates to a method of producing on a metal surface a protective, ornamental film. More specifically, the invention relates to a process of this character which permits the formation on an aluminum or aluminum alloy surface a smooth, level and strong resinous film by immersion-deposit of a coating.
  • aluminum alloys find wide utility in fabricating therefrom a variety of useful commercial articles including window sashes, panels and the like.
  • a number of processes have hitherto been proposed for treating and finishing aluminum-bearing substrates so that product aluminum articles are resistant to environmental attack, i.e. corrosion by acidic or alkaline atmosphere and present a continuous, smooth, level surface appearance.
  • a protective coating and/ or an ornamental dye Prior to the application of a protective coating and/ or an ornamental dye, the aluminum surface is anodized and treated to fill or level out the fine pores or cavities which develop in the surface when anodized.
  • the surface is water-rinsed and dried, and thereafter coated by spraying, or electro-deposition with suitable coatings such as solutions of normally dry acrylic resins, thermo-setting acrylic resins, polyurethane resins, watersoluble acrylic resins and the like.
  • the porosity-filling treatment which follows the step of anodization and which is usually made with steam to form gamma-Al O -H o or gamma-Al O -3H O film on the aluminum surface, is intended to prevent entry of corrosive materials into anodized porous surface.
  • the aluminum surface is washed with water and required to be dried when applying thereto the aforesaid normally dry acrylic resins, thermo-setting acrylic resins or polyurethane resins.
  • the Water-soluble acrylic resin coatings are most commonly applied by means of electro-deposition which requires costly equipment and complicated operating procedures including severe pH control, coating potential adjustment and high-purity water requirement.
  • the inventive concept of this invention resides in a process wherein an anodized aluminum or aluminum alloy surface is immersion-deposited with a water-soluble thermo-setting resin coating composition, set for a While and dried by heating at optimum temperature. More specifically, the process according to the invention is characterized in that a starting aluminum surface, after degreasing, cleaning,- waterwashing and anodizing is deposited with a desired film while the surface is still Wet and moist, i.e. Without first being dried.
  • the coating compositions have great affinity to water, and the water present on the aluminum surface is readily miscible with the coatings and, as the coated surface is heated, vaporizes or has part of its particle attached to aluminum oxide on the surface thereby forming A1 0 H O (boehmite)
  • the aluminum surface may be coated also While it is wet upon water-washing and rather without further porosity-filling treatment which has been employed in the art to eliminate numerous pores or cavities developed in the anodized surface and Which has heretofore been considered essential to avoid corrosion attack.
  • Such porosity-filling effect is more effectively achieved by the process of the invention wherein residual water, co-present with appreciable amounts of sulfuric acid radicals and other anion materials resulting from anodization of an aluminum surface and remaining in the anodized porous surface, becomes miscible with a water-soluble, thermo-setting coating and vaporizes or forms an Al O -H O film which in turn provides an increase in the volume of the aluminum surface area sufiicient to fill the cavities and at the same time, assists in the adhesion of the coating composition to the aluminum surface.
  • the water-soluble, thermo-setting resins employed in accordance with the invention include acrylic resins, alkyd resins, acrylalkyd resins and any one of these resins as admixed with amino resins.
  • a successful amino resin example is melamine which may be blended with acrylic resins, alkyd resins or acrylalkyd resins at a ratio of 10-40 to 60-90 percent in solid state.
  • Preferred coating compositions according to the invention typically comprise parts by weight of any one of the resin examples given above, 65-170 parts of watersoluble organic solvent such as alcohol or ether alcohol, 35-60 parts of Water, 0.1-0.5 part of anion-type surfactant and about 7.05 parts of organic amine (stabilizer), the blending proportions being such that the solid content be of the order of 30-50% (of the mass upon heating and hardening the coating composition.
  • the process according to the invention comprises applying to an aluminum or aluminum alloy surface a water-soluble thermo-setting resin coating of the type and composition shown in the above table, causing the coated surface to set for about 1-10 minutes, and drying and hardening the surface at temperature ranging from 150 C. to 200 C. for about 15-30 minutes.
  • EXAMPLE I An aluminum workpiece was subjected to pretreatment in which it was degreased and cleaned by dipping it for 1 minutes in a 5% emulsion-type detergent heated to 70 C.; washed with room temperature water; etched by dipping it for 3 minutes in a 5% NaOH solution maintained at 80 C.; washed with Water; neutralized by dipping for 2 minutes in a 10% NHO solution at room temperature; and washed again with water.
  • the pretreated substrate was subjected to anodization using a H 80 electrolyte operated with a DC 16 volts source at a current density of 1 a./dm. at a bath temperature of 20 C. The substrate was thus anodized for 30 minutes.
  • the present invention contemplates the utilization of the numerous fine pits or pores which develop in the surface of an aluminum bearing substrate as this is electrically anodized in a conventional manner. These pores are known to be generally in the range of 100-600 angstroms. On the assumption, therefore, that such pores may be substantially filled by a relatively low polymerization resin coating which coating is of the same composition as a relatively high polymerization resin coating, it has been found that excellent results may be obtained by applying to anodized porous aluminum surface a first coating having a molecular weight not exceeding 1,000 and then, a second.
  • first and second coatings being of the same type and composition as exemplified in the table above.
  • the first low polymerization resin coating is believed to penetrate into the pores in anodized aluminum surface and thus firmly anchored therein when it hardens. Since the first coating is of the same composition as the second coating, both may be readily miscible and may form a continuous, uniform film on an aluminum surface.
  • Suitable pigments if a colored surface finish is desired, may be admixed with the first low polymerization undercoating which uudercoating may be retained intact, should the second high polymerization coating layer be weathered or worn with time.
  • EXAMPLE II EXAMPLE III The procedure of Example II was repeated except that 0.5 g./l. of a red color organic pigment was admixed with the first low polymerization resin coating which was warmed at 30 C. and inwhich the aluminum workpiece was immersed for 10 minutes.
  • a process for producing a firmly adhered resin film on an aluminum or aluminum-bearing substrate consists in applying to an immersion bath an ultrasonic vibration in the range of 20-50 he in such a manner that the coating in the bath undergoes cavitation which results in accelerated activity of the particle of the coating composition and which at the same time causes the water and other anion materials residual in the pores of the anodized aluminum surface to move out and replace with the coating.
  • the cavitation accompanies the formation of air bubbles which may be eliminated by the use of a less viscous coating having a viscosity of about 15 seconds by Fordcup test #4, or by adding a suitable defoaming agent.
  • such air bubbles may be eliminated by discontinuing the application of ultrasonic vibration to the immersion bath immediately before the workpiece is withdrawn, or by allowing the coating to overflow, or by providing two separate baths, one for ultrasonic vibration and the other for finish-coating.
  • Coat #4 was adjusted to a viscosity of 15 seconds at 30 C. by Fordcup test #4 and applied by immersiondeposit with ultrasonic vibration of 20 kc. to anodized porous aluminum surface for 5 minutes. The aluminum workpiece was then re-immersed in a similar coating without vibration for 30 seconds. The coated workpiece was allowed to set over 10 minutes and dried at a temperature of C. for 20 minutes.
  • Example VI The procedure of Example IV was followed except that the ultrasonic vibration was 25 kc. and the coating viscosity was 20 seconds at 30 C. by Fordcup test #4.
  • a process of coating an aluminum or aluminum alloy surface which comprises:
  • a resin coating composition comprising a water-soluble, thermosetting resin selected from the group consisting of acrylic resins, alkyd resins and acrylalkyd resins and having a solid content of about 20-35 percent by weight;
  • a process for forming on an aluminum or aluminum alloy surface a smooth, level and strong resinous film which comprises:
  • a resin coating composition consisting of 100 parts by weight of a water-soluble, thermosetting resin selected from the group consisting of acrylic resins, alkyd resins and acrylalkyd resins, 65-170 parts of alcohol, 3560 parts of water, 0.1- 0.5 part of anionic surfactant and small amounts of organic amine, said composition being adjusted to contain 20-35 percent in solids; and
  • step (c) is carried out by first immersing the wet workpiece into a first bath of said coating composition, wherein the resin has a molecular weight not exceeding 1,000, permitting the coating thus formed to set and then immersing the coated workpiece into a second bath of said coating composition, wherein the resin has a molecular weight of about 3,000-4,000.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Paints Or Removers (AREA)
US00027424A 1969-09-06 1970-04-10 Process for the deposition of resinous films on aluminum-bearing substrates Expired - Lifetime US3711313A (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP44070287A JPS4931296B1 (enrdf_load_stackoverflow) 1969-09-06 1969-09-06
JP7028669A JPS4931295B1 (enrdf_load_stackoverflow) 1969-09-06 1969-09-06
JP8564969A JPS4931297B1 (enrdf_load_stackoverflow) 1969-10-28 1969-10-28
JP8565069A JPS4931298B1 (enrdf_load_stackoverflow) 1969-10-28 1969-10-28

Publications (1)

Publication Number Publication Date
US3711313A true US3711313A (en) 1973-01-16

Family

ID=27465224

Family Applications (1)

Application Number Title Priority Date Filing Date
US00027424A Expired - Lifetime US3711313A (en) 1969-09-06 1970-04-10 Process for the deposition of resinous films on aluminum-bearing substrates

Country Status (4)

Country Link
US (1) US3711313A (enrdf_load_stackoverflow)
DE (1) DE2045521A1 (enrdf_load_stackoverflow)
FR (1) FR2048380A5 (enrdf_load_stackoverflow)
GB (1) GB1270502A (enrdf_load_stackoverflow)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3832812A (en) * 1972-06-06 1974-09-03 Annapolis Yacht Yard Inc Fire retardant insulated modular building panels
US3930964A (en) * 1971-12-25 1976-01-06 Toshiro Takahashi Method for painting aluminum or aluminum-based alloy material
US3935349A (en) * 1972-10-06 1976-01-27 Sumitomo Light Metal Industries, Ltd. Process of coating an aluminum article
US4024039A (en) * 1972-08-31 1977-05-17 Honny Chemicals Company, Ltd. Coloring methods for aluminum and aluminum alloys
US4158079A (en) * 1973-08-13 1979-06-12 Swiss Aluminium Ltd. Composite material and a process and device for its manufacture
US4288469A (en) * 1978-11-25 1981-09-08 Agfa-Gevaert Aktiengesellschaft Anodized aluminium rollers with improved electrical conductivity and a process for their manufacture
US4310390A (en) * 1977-08-10 1982-01-12 Lockheed Corporation Protective coating process for aluminum and aluminum alloys
US4465562A (en) * 1979-01-08 1984-08-14 Honny Chemicals Company, Limited Process for surface treatment of aluminum article
US4483751A (en) * 1981-02-02 1984-11-20 Fujikura Cable Works, Ltd. Process of treating a nodic oxide film, printed wiring board and process of making the same
EP0202392A3 (en) * 1985-05-20 1987-06-16 The Boeing Company Plated metallic article with overlying polymeric coating
US5242972A (en) * 1989-04-05 1993-09-07 Kansai Paint Co., Ltd. Fluorine based aqueous dispersion, process for preparing the same, and fluorine based matte anionic electrodeposition coating composition containing the same
US5591318A (en) * 1996-02-01 1997-01-07 Motorola Energy Systems, Inc. Method of fabricating a conductive polymer energy storage device
US5961810A (en) * 1997-11-05 1999-10-05 Motorola, Inc Method for fabricating a conductive polymer energy storage device
US20150191604A1 (en) * 2014-01-03 2015-07-09 The Boeing Company Composition and Method for Inhibiting Corrosion of an Anodized Material
US9810423B2 (en) 2009-03-10 2017-11-07 Bastian Family Holdings, Inc. Laser for steam turbine system
CN115322626A (zh) * 2022-10-08 2022-11-11 杜娜丽 一种水性涂料组合物的制备方法

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3930964A (en) * 1971-12-25 1976-01-06 Toshiro Takahashi Method for painting aluminum or aluminum-based alloy material
US3832812A (en) * 1972-06-06 1974-09-03 Annapolis Yacht Yard Inc Fire retardant insulated modular building panels
US4024039A (en) * 1972-08-31 1977-05-17 Honny Chemicals Company, Ltd. Coloring methods for aluminum and aluminum alloys
US3935349A (en) * 1972-10-06 1976-01-27 Sumitomo Light Metal Industries, Ltd. Process of coating an aluminum article
US4158079A (en) * 1973-08-13 1979-06-12 Swiss Aluminium Ltd. Composite material and a process and device for its manufacture
US4310390A (en) * 1977-08-10 1982-01-12 Lockheed Corporation Protective coating process for aluminum and aluminum alloys
US4288469A (en) * 1978-11-25 1981-09-08 Agfa-Gevaert Aktiengesellschaft Anodized aluminium rollers with improved electrical conductivity and a process for their manufacture
US4465562A (en) * 1979-01-08 1984-08-14 Honny Chemicals Company, Limited Process for surface treatment of aluminum article
US4483751A (en) * 1981-02-02 1984-11-20 Fujikura Cable Works, Ltd. Process of treating a nodic oxide film, printed wiring board and process of making the same
EP0202392A3 (en) * 1985-05-20 1987-06-16 The Boeing Company Plated metallic article with overlying polymeric coating
US5242972A (en) * 1989-04-05 1993-09-07 Kansai Paint Co., Ltd. Fluorine based aqueous dispersion, process for preparing the same, and fluorine based matte anionic electrodeposition coating composition containing the same
US5591318A (en) * 1996-02-01 1997-01-07 Motorola Energy Systems, Inc. Method of fabricating a conductive polymer energy storage device
US5961810A (en) * 1997-11-05 1999-10-05 Motorola, Inc Method for fabricating a conductive polymer energy storage device
US9810423B2 (en) 2009-03-10 2017-11-07 Bastian Family Holdings, Inc. Laser for steam turbine system
US20150191604A1 (en) * 2014-01-03 2015-07-09 The Boeing Company Composition and Method for Inhibiting Corrosion of an Anodized Material
US9771481B2 (en) * 2014-01-03 2017-09-26 The Boeing Company Composition and method for inhibiting corrosion of an anodized material
CN115322626A (zh) * 2022-10-08 2022-11-11 杜娜丽 一种水性涂料组合物的制备方法
CN115322626B (zh) * 2022-10-08 2023-08-18 中远关西涂料（上海）有限公司 一种水性涂料组合物的制备方法

Also Published As

Publication number Publication date
GB1270502A (en) 1972-04-12
DE2045521A1 (de) 1971-05-06
FR2048380A5 (enrdf_load_stackoverflow) 1971-03-19

Similar Documents

Publication Publication Date Title
US3711313A (en) Process for the deposition of resinous films on aluminum-bearing substrates
US3709743A (en) Acidic deposition process
USRE29739E (en) Process for forming an anodic oxide coating on metals
US3977839A (en) Coated metal article and method of coating
US4136070A (en) Cathodic electrodeposition of paints
US3592747A (en) Method of forming a decorative and protective coating on a surface
US3775266A (en) Process for forming resinous films on anodized aluminum substrates
US3408278A (en) Painting process wherein a conductive undercoat is electrophoretically deposited
US7597935B2 (en) Process for preparing chrome surface for coating
EP0421247B1 (en) Coating method
EP1654403A1 (en) Protective coating for automotive trim pieces and method of making the same
US3449222A (en) Metal coating process
WO2017183336A1 (ja) アルミニウム塗装材およびその製造方法
US3772161A (en) Method of selectively electroplating thermoplastic substrates using a strippable coating mask
US3899370A (en) Method for producing coated and age hardened aluminum or aluminum-based alloy molded materials
US3449229A (en) Electrophoretic deposition on zinc enriched metal surface
US3988217A (en) Process for producing a protective film on an aluminum surface
US4023986A (en) Chemical surface coating bath
US3798143A (en) Electrophoretic deposition of acrylic copolymers
JP6499930B2 (ja) アルミニウム塗装材およびその製造方法
US3420762A (en) Electrocoating process with pretreatment of articles
US3467589A (en) Method of forming a copper containing protective coating prior to electrodeposition of paint
US3909371A (en) Process for producing a protective film on an aluminum surface
US3961993A (en) Coated metal article and method of coating
US3880727A (en) Method of pretreating bands and sheets of steel for one-layer enameling, and electrolytic bath for use in connection therewith