CA1241931A - Process for producing multiple coat systems - Google Patents

Process for producing multiple coat systems

Info

Publication number
CA1241931A
CA1241931A CA000472869A CA472869A CA1241931A CA 1241931 A CA1241931 A CA 1241931A CA 000472869 A CA000472869 A CA 000472869A CA 472869 A CA472869 A CA 472869A CA 1241931 A CA1241931 A CA 1241931A
Authority
CA
Canada
Prior art keywords
primer
coating
additional coating
binder
irradiation
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
Application number
CA000472869A
Other languages
French (fr)
Inventor
Helmut Honig
Georg Pampouchidis
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.)
Allnex Austria GmbH
Original Assignee
Vianova Resins AG
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 Vianova Resins AG filed Critical Vianova Resins AG
Application granted granted Critical
Publication of CA1241931A publication Critical patent/CA1241931A/en
Expired legal-status Critical Current

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209Multistage baking
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/52Two layers
    • B05D7/54No clear coat specified
    • B05D7/546No clear coat specified each layer being cured, at least partially, separately
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/44Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254After-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/06Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
    • B05D3/061Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using U.V.
    • B05D3/065After-treatment
    • B05D3/067Curing or cross-linking the coating

Abstract

ABSTRACT OF DISCLOSURE

A process for producing multiple-coat paint systems is described wherein a cathodically electro-depositable primer containing thermically polymerizable synthetic resins as the binder, immediately prior to the application of an additional coating, is irradiated with ionizing irradiation for a period of from one to 20 seconds. The irradiation for the short per-iod of time cures the primer so that subsequent coatings applied to the primer do not detrimentally affect the primer coating or the finished paint system.

Description

FIELD OF INVENTION

The invention is directed to a process for producing a multiple-coat paint system based on cathodically electro-depositable (CED) primers which contain thermic211y polymeri-zable synthetic resins as binders, and to the paint system-obtained. I~ore particularly, the process of the present in-vention includes treating CED-primers with ionizing irradia-tion before a subsequent coating.

_ACKGROUND AND PRIOR ART

U.S. Patent Nos. 4,320,220; 4,238,594, and 4,174,332;
and Austrian Pant 366 082 disclosebinderS for catllodically deposit-able coating compositions (CED-paints) which, due to their chain end double bonds, crosslink on stoving substantially by ethylenic polymerization. Binders of this type have been used in practice on a large scale, particularly by the automobile industry, whereby thermic crosslinking has to he effected with an object, i.e., a car body, at a temperature of from ahout 170 to 180~C in order to attain the high protection against corrosion as required by the industry. For technological reason5 and to save energy, inrlustry now demanc3.s to a rising extent the redllction of the necessary curing temperatures for * issued to Vianova Kunstharz, 10 March 1981.
-2-'I-lZ41931 the primer to a temperature of from about 150C to a maximum of 170C. It is essential, however, that the corrosion re-sistance of the primer coating obtained or of the total paint coating system not be decreased.

In general, the binders disclosed in the above-mentioned references provide satisfactory crosslinking of the paint film at reduced stoving temperature. In practice, how-ever, it has been found that with the reduced stoving tempera-tures of between ahout 140C and a maximum of 170C, coatings subsequently applied to the CED-primer cause the primer to swell at the surface of the primer. The tendency to swell at the surface of the primers, which increases with decreasing stoving temperature, is believed to be caused by the strong solvency power of the organic solvents contained in the coatings applied to the primer. This effect shows strongest when the coating is applied immediately after baking of the primer, and diminishes on storage of the primer coated objects before application of an additional coating. For example, a primer cured at 150C is totally resistant to such solvents after a maximum storage of three weeks. These changes in the properties at the surface of the primer upon storage, in many cases, are the reason for the improvement in the multiple-coat system through hardening of the subsequent filler and finish--ing coatings which results in an increased impact resistance of the final paint system. Intercoat adhesion is also essen-tially enhanced for materials used as protective materials for car underbodies or to sealants used on car bodies with aging of the primer. It is evident, however, that such long storage times cannot be realized in practice. Normally, the following coats are applied to the primer within a maximum period of one hour after stoving.

PRIMARY OBJECTS AND GENERAL DESCRIPTION OF INVENTION

It is a primary ob ject of the present invention, therefore, to improve the surface hardness of primers cured at from 140 to 170C in order that swelling by organic solvents is reduced to an extent which allows immediate application of the next coating without impairing the quality of the primer.

lS Surprisingly, it has been determined that the disad-vantages of solvent impairment of the primer coatings can be avoided if the CED-primers based on binders crosslinked through thermal polymerization at from 140 to 180C are sub-jected for a short period of time to an ionizing irradiation, particularly UV-irradiation, prior to the application of the next coat.

Curing of electro-deposition (ED) paints by ionizing g `` 1241931 irradiation has been known from the literature. For example, U.S. Patent Nos. 4,035,274 and 4,066,523 disclose the combina-tion of baking and crosslinking by ionizing irradiation. In these cases, during the first phase of baking the deposited film is allowed to flow out, crosslinking being effected through uv-irradiation. The binders disclosed in the patents are adjusted to such method of crosslinking. The methods disclosed, however, are not suitable for objects having difficulty accessible or inaccess-ible parts. Thus, methods such as described in the above and other patents describing curing with irradiation techniques cannot be used for coating of objects such as car bodies, etc., which have cavities and shielded areas not affected by irradiation.
The present invention provides a process for producing a multiple-coat paint system which includes a CED-primer contai-ning thermically polymerizable synthetic resins as the binder and at least an additional coating based on solvent-dissolved resins, comprising the steps of a) coating an electrically conductive substrate sur-face by cathodic deposition with a primer containing a thermically polymerizable binder resin system, b) curing the deposited primer at a temperature of from 140 to 180C., c) irradiating the cured primer with ionizing ra-diation for a period of one to 20 seconds, d) applying a solvent based additional coating, and e) curing the additional coating.

- "` 1241931 23110~69 Thus, the present invention is concerned with a process for producing multiple-coat paint systems which utilize a CED-primer containing thermically polymerizable synthetic resins as the binder and at least one additional coat based on solvent-dissolved resins, the process being characterized in that the cathodically deposited primer is substantially totally cured at a temperature from 140 to 180C and, immediately prior to the application of the next coat, is irradiated with ionizing irrad-iation for a period of time from one to 20 seconds. It was unexpected that with only a slight -5a-.. . .
..; ., irradiation the film surface could be rendered resistant to the influence of solvents in the next coating, including sur-face swelling, and thereby avoiding the deficiencies in film formation caused by the swelling. Furthermore, adverse influ-ences due to the basic character of the cationic primer on thecuring process in the following coat, which in most cases is catalyzed by acids, are prevented. A further effect achieved by the method of the invention is a marked improvement in ad-hesion to polyvinylchloride (PVC) materials which are used for protection of car underbodies; and adhesion to sealants or to metal-bonding compounds as are used mainly in the automobile industry.

The primers used according to the present invention contain as the binder synthetic resins such as those disclosed in the references referred to above, i.e., U.S. Patent Nos.
4,320,220; 4,238,594, and 4,174,332; and AT-PS 366 082. These resins are water-dilutable cationic binders carrying a suf-ficient number of chain end double bonds which crosslink on stoving by thermal polymerization. Preferably modified epoxy resins based on Bisphenol-A or on phenol novolaks serve as components of these CED-systems. The preparation and applica-tion of these resins are described in detail in the references noted above.

The disadvantage of curing by irradiation as noted above in that shielded sections, including cavities, cannot be irradiated, is not critical in accordance with the present invention since the subsequent coats to be applied are sub-stantially applied to visible surfaces which are easily acces-sible to irradiation. The remaining surfaces, uncoated by the second coating, to the extent coated with primer will cure to a hard coating with time.

The subsequent coatings applied onto the primer nor-mally include a filler coating as an intermediate coat, fol-lowed by a finish coating; or, optionally, a finishing coat only can be utilized. Filler coatings are normally based on alkyd/amino resin systems dissolved in solvents; whereas the finishing coatings normally contain as the binders either an alkyd/amino resin in combination with, for example, an acrylic resin or an acrylic resin/amino resin combination. It is known that the crosslinking reaction of these systems is cata-lyze~ with acids. The compositions of these systems are known to one skilled in the art and are described in the literature, for example Ullmanns Encyklopadie der Technischen Chemie, 4th Edition, Volume 15; or H. Kittel, Lehrbuch der Lacke und hichtungen, W. A. Colomb. -Another type of subsequent coatings to be applied to the primer are materials which are applied for the protection 124~931 of car underbodies or as sealants or as metal-bonding com-pounds. In most cases, these materials are plastisols, i.e., dispersions of plastic materials, in particular PVC, in plasticizers.

The primer is applied in known manner by the CED pro-cess to a normally pretreated substrate, anA in the automobile industry in particular to phosphated steel. In this method, the object to be coated is wired as the cathode of the electro-deposition system and the paint, containing as the binder at least a portion of a cationic resin, is deposited by applying direct current. After rinsing the adherent bath material, the primer is cured by thermic polymerization at from 140 to 180C.
Prior to the application of the next coat, the stoved primer according to the invention is subjected to a short irradiation with UV-light. Irradiation time is from one to 20 seconds.
Suitable sources of irradiation include from available low, medium, or high pressure mercury lamps, as are described in the literature, for example UV-Curing, Science and Technology, S. P. Papas, Technol. Market Corp., Stamford, Connecticut USA, 1978. The use of UV-sensitizers is not necessary for the pro-cess of the invention since the substantial crosslinking reac-tion is a thermic polymerization reaction. In place of UV-light, irradiation can be carried out with other ionizing rays, - `~

lZ41931 such as electron rays. The subsequent coating is applied in known manner through spraying and is cured by stoving.

PREFERRED EMBODIMENTS OF INVENTION

The following examples illustrate presently preferred embodiments of the invention without intent to limit the scope thereof.

Example 1:

Zinc-phosphated steel panels, as are used in the automobile industry, are coated in the conventional manner with a cathodically depositable electro-deposition paint. The paint was formulated based on a binder according to Example 7 of U.S, Patent No. 4,174,332 utilizing the following ingre-dients:

100.0 parts by weight binder, 100% solids content 0.3 parts by weight carbon black
3.0 parts by weight lead silicate 36.7 parts by weight titanium dioxide The coated panels were rinsed with water in the conventional manner and cured for 17 minutes with an object temperature of 150C. The film thickness of the primer is 22 + 2~um. About one hour after cure the panels were irradiated for 6, 12, and 18 seconds each with an available UV-irradiation source devel-1~1931 oped for the curing of paints. The irradiation source used in this example was a lamp marketed as "Primarc Minicure, Mark 2"
by Primarc (Jigs and Lamps) Ltd., Henley-on-Thames, England, which is a medium-pressure mercury lamp (200 watt/inch = 78.7 watt/cm).

The panels after curing were evaluated in the fol-lowing way:
1. Acetone test:
A cotton pad soaked with acetone was pressed onto the paint surface for 60 seconds. Immediately after removing the pad, the paint was scratched and the results recorded based on a scale of 1 to 5, wherein 1 is no attack; 2 is where it can be scratched; and 5 is where it can easily be scratched.

2. Recoatability and adhesion of finishing coat:
Onto the primed panel, a commercial acid catalyzed automohile finish based on an acrylic resin/amino resin combination was applies and stoved for 30 minutes at 120C
(dry film thickness 70 + 5 Jim).
The chip resistance of the total coating system is recorded on impact of steel gravel. The degree of peel-off of the upper coat is recorded based on a scale of 1 to 5, wherein 1 is no peel-off, and 5 is total peel-off.

* Trade Mark --1 (J--41g3:1 3. Adhesion to PVC:
A cornmercially available PVC-plastisol paste is ap-plies to the panel in a width of 3 cm and a thickness of 2 mm; and is cure for 7 minutes at 125~C, object tempera-ture. The ease of tear-off of the PVC layer is recorded based on a scale of 1 to 5, wherein 1 is peel-off with difficulty only, and 5 is where the coating can be easily peeled off.

Results of Testinc1:
_V-Irradiation Time In Seconds _ 0 6 12 18 acetone Test 5 1-2 Recoatability and Chip Resistance 5 2-3 15 PVC-adhesion I) 5 2 1-2 +) The following products were tested:
Car underbody protection: Intercol, Thermocoat 01779, which is a PVC-plastisol marketed by Intercoat fob und Riechstoff GmbH, Bodenheim/Rhein Coarse sealing compound: Teroson AKD 475000, which is a sealant marketed by Teroson GmbH, Heidelberg Fine sealiny compound: Teroson AKD 473001, which is a sealant marketed by Teroson GmbH, Heidelbery * Trade Mark I.
....

~241931 Example 2:

In a test series a variety of paint systems were tested for the effect of UV-irradiation on intercoat adhesion.
The CED-paints used had the formulation as follows:

5100.0 parts by weight binder (100~ resin solids) 0.3 parts by weight carbon black 3.0 parts by weight silicate 36.7 parts by weight titanium dioxide The binder used in the CED-paints consisted of the following resin combinations:

Binder A: Binder combination according to Example 4 of EP-B1-00 49 369 Binder B: Combination of 30 parts (100% resin solids) of a binder according to Example 29 of U.S. Patent 15No. 4,174,332; and 70 parts (100% resin solids) according to Example 8 of EP-Bl-00 12 463.

The CED-primers were applied and irradiated as described in Example 1. The irradiation source was an UV-radiator Hanovia, Type 8512 A 431 (radiation intensity 80 W/cm, at 365 nm; pro-ducer Ulrich Steinemann AG, St. Gallen, Switzerland). Dis-tance to the object: 8 cm.

A PVC layer was applied to the primed panels at the dimensions of 2 mm thickness and 1 cm breadth, thirty minutes -~~ 1793/US-2430 124193~

after cure of the CED-primer and stoved for 7 minutes at 140C, object temperature. The adhesion was tested one hour after cure. The PVC materials were available PVC-plastisol car underbody protective materials marketed under the trademark Stankiewicz 2252 by Stankiewicz GmbH, Celle, West Germany; and a sealant for welding seams used in the automobile industry marketed under the trademark Dekalin 9003 by Dekalin, Deutsche Klebstoff Werke, Hanau, West Germany. The results, showing the evident influences of UV-cure on the cured films, are listed in the following table:

Irradiation Time In Seconds CED-Paint 0 5 10 15 -Car Underbody Protection Binder A 5 2 Binder B 5 2-3 = = = = = = = = = = = = = = = = = = = = = = = = = = = = =
Welding Seam Sealant Binder A 5 3 1-2 Binder B 5 3-4 2 2-2 , Irradiation under N2-atmosphere does not change the results.

20 As will be apparent to one skilled in the art, var-ious modifications can be made within the scope of the afore-said description. Such modifications being within the ability ~1241931 of one skilled in the art form a part of the present invention and are embraced by the appended claims.

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. Process for producing a multiple-coat paint system which includes a CED-primer containing thermically polymerizable syn-thetic resins as the binder and at least an additional coating based on solvent-dissolved resins, comprising the steps of (a) coating an electrically conductive substrate surface by cathodic deposition with a primer containing a thermically polymerizable binder resin system, (b) curing the desposited primer at a temperature of from 140° to 180°C., (c) irradiating the cured primer with ionizing radiation for a period of one to 20 seconds, (d) applying a solvent based additional coating, and (e) curing the additional coating.
2. The process according to claim 1 wherein the primer is irradiated with UV-light.
3. The multiple-coat paint system produced by the process of claim 2.
4. The process according to claim 1 wherein said additional coating is an alkyd resin/amino resin combination.
5. The process according to claim 4 wherein said alkyd resin/amino resin combination is catalyzed with an acid catalyst.
6. The process according to claim 1 wherein said additional coating is a PVC-plastisol.
7. The multiple-coat paint system produced by the process of claim 1.
8. The process of claim 1 wherein said additional coating is applied by spraying.
9. The process of claim 1 wherein said additional coating is cured by application of heat.
10. The process of claim 1 wherein the primer coating is rinsed prior to curing.
CA000472869A 1984-01-27 1985-01-25 Process for producing multiple coat systems Expired CA1241931A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0026884A AT379414B (en) 1984-01-27 1984-01-27 METHOD FOR PRODUCING MULTI-LAYER PAINTINGS
ATA268/84 1984-01-27

Publications (1)

Publication Number Publication Date
CA1241931A true CA1241931A (en) 1988-09-13

Family

ID=3486018

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000472869A Expired CA1241931A (en) 1984-01-27 1985-01-25 Process for producing multiple coat systems

Country Status (10)

Country Link
US (1) US4652353A (en)
EP (1) EP0154771B1 (en)
JP (1) JPS60161771A (en)
AT (1) AT379414B (en)
AU (1) AU567202B2 (en)
BR (1) BR8500349A (en)
CA (1) CA1241931A (en)
DE (1) DE3560085D1 (en)
ES (1) ES539815A0 (en)
ZA (1) ZA85157B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0581133U (en) * 1992-04-03 1993-11-02 村田機械株式会社 Automated guided vehicle
DE10022750A1 (en) * 2000-05-10 2001-11-22 Wolfgang Schuhmann Preparing surface with immobilized recognition elements, useful e.g. in biosensors, by electrodeposition of resin from emulsion containing active substances
US7632386B2 (en) * 2003-08-28 2009-12-15 E.I. Du Pont De Nemours And Company Process for producing coatings on electrically conductive substrates by cathodic electrodeposition coating
US7211182B2 (en) * 2003-09-23 2007-05-01 E. I. Du Pont De Nemours And Company Process for producing coatings on electrically conductive substrates by cathodic electrodeposition coating
US20180155846A1 (en) * 2015-07-28 2018-06-07 Hewlett-Packard Development Company, L.P. Magnesium Alloy Substrate

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3501391A (en) * 1966-10-03 1970-03-17 Ford Motor Co Electrocoatacure process and paint binders therefor
US3761371A (en) * 1970-12-21 1973-09-25 Ford Motor Co Electrodeposition of coating materials comprising particulate elastomers
JPS5139900B2 (en) * 1973-10-20 1976-10-30
US4039414A (en) * 1974-06-19 1977-08-02 Scm Corporation Ultraviolet curing of electrocoating compositions
US4025409A (en) * 1975-07-14 1977-05-24 Scm Corporation Dual cure cathodic electrocoating process
US4029561A (en) * 1976-01-22 1977-06-14 Scm Corporation Photocurable cathodic electrocoating
US4035274A (en) * 1976-05-24 1977-07-12 Scm Corporation Dual cure cathodic electrocoating
US4166017A (en) * 1976-05-24 1979-08-28 Scm Corporation Process for cathodic electrocoating and photocuring
DE2707405B2 (en) * 1976-07-19 1982-09-16 Vianova Kunstharz AG, 8402 Werndorf Process for the production of binders for electrocoating
AT377774B (en) * 1980-12-18 1985-04-25 Vianova Kunstharz Ag METHOD FOR PAINTING CONDUCTIVE OBJECTS

Also Published As

Publication number Publication date
AT379414B (en) 1986-01-10
ES8600787A1 (en) 1985-11-01
EP0154771A1 (en) 1985-09-18
US4652353A (en) 1987-03-24
AU3758885A (en) 1985-08-01
EP0154771B1 (en) 1987-03-11
DE3560085D1 (en) 1987-04-16
JPS60161771A (en) 1985-08-23
ZA85157B (en) 1985-08-28
ATA26884A (en) 1985-05-15
ES539815A0 (en) 1985-11-01
AU567202B2 (en) 1987-11-12
BR8500349A (en) 1985-09-10

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