EP0643996B1 - Beschichtungsverfahren - Google Patents

Beschichtungsverfahren Download PDF

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Publication number
EP0643996B1
EP0643996B1 EP19940114613 EP94114613A EP0643996B1 EP 0643996 B1 EP0643996 B1 EP 0643996B1 EP 19940114613 EP19940114613 EP 19940114613 EP 94114613 A EP94114613 A EP 94114613A EP 0643996 B1 EP0643996 B1 EP 0643996B1
Authority
EP
European Patent Office
Prior art keywords
substrate
coating layer
temperature
plastics
powder coating
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
EP19940114613
Other languages
English (en)
French (fr)
Other versions
EP0643996A1 (de
Inventor
Koichi Tsutsui
Shannon Libke
Koichi Inoue
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.)
Nippon Paint Co Ltd
Original Assignee
Nippon 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
Application filed by Nippon Paint Co Ltd filed Critical Nippon Paint Co Ltd
Publication of EP0643996A1 publication Critical patent/EP0643996A1/de
Application granted granted Critical
Publication of EP0643996B1 publication Critical patent/EP0643996B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/02Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/045Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field on non-conductive substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00Processes for applying liquids or other fluent materials
    • B05D1/02Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/06Applying particulate materials
    • 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
    • B05D7/02Processes, 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 macromolecular substances, e.g. rubber

Definitions

  • the present invention relates to a method of manufacturing a coated article according to the preamble clause of claim 1.
  • Said coated article may include surface-coated metal or surface-coated plastics products such as for example automotive parts, building materials, constructional members, household appliance parts, and similar coated articles.
  • a method of said type is known from document EP-A-0 372 740.
  • said document discloses a method of coating a plastic substrate comprising the steps of:
  • the times and temperatures for this known preheating step will vary somewhat depending on the identity of the substrate and the powder coating composition. Typically, the temperature will be at least 149° C, and preferably 163 to 204° C, and the preheating time typically will be at least 15 minutes, usually from 15 to 60 minutes.
  • the powder coating composition is immediately (i.e., before the substrate cools below the curing temperature of the powder coating composition) applied to the preheated substrate.
  • the powder coating composition may be applied by electrostatic spraying.
  • the coated substrate is then heated immediately (i.e., before the substrate cools below the curing temperature of the powder coating composition) at a temperature and for a time sufficient to cure the powder coating composition. At no time during the coating process should the temperature of the substrate be allowed to drop below the curing temperature of the powder coating composition.
  • the fore-mentioned coating method (which is also disclosed in Japanese Kokai Publication Hei-2-194878) seeks to avoid said popping by heating the substrate to a temperature sufficient for degassing prior to the application of the coating layer(s).
  • the proposed heating temperature of the plastics substrate is too high, because the powder coating composition will inevitably tend to undergo partial curing, which may deteriorate the appearance of products.
  • Japanese Kokoku Publication Sho-51-43152 discloses a method for applying a top coating layer by means of a powder coating step subsequently to the formation of a base coating layer comprising a thermosetting resin coating layer. Said method includes a step of heating the substrate to reduce the content of volatile components of the base coating layer to an amount not more than 6 % by weight to thereby improve the metallic tone and durability of the coating layer(s) as well as the transfer efficiency of the powder coating process.
  • the above mentioned methods intend to improve the coating processes employing powder coating steps, but, while the content of the volatile component of the base coating layer is limited to, say, 6 % by weight or less on the one hand, an improvement of the transfer efficiency is limited by the remaining content of volatile matters. On the other hand, an excessive heating of the substrate in order to decrease the content of volatile matter may impair the powder coating process and may lead to a deterioration of the appearance of the coated articles. Therefore, the transfer efficiency is not actually improved in an extent as desired. The above-mentioned problem of improving the transfer efficiency remains virtually unsolved.
  • the technical problem (object) of the present invention is to improve the transfer efficiency of the powder coating composition in a method of manufacturing a coated article of the above-stated generic kind, without an undue deterioration of the appearance of the coated article.
  • the article may comprise a substrate made of plastics or metal, and said substrate comprises a base coating layer containing less than 10 % by weight volatile components.
  • said base coating layer may be obtained by an electrodeposition coating process or by an aqueous coating process, and it is preferred that said base coating layer containing less than 2 % by weight of vola-tile amine compound based on the total weight of volatile matter.
  • the coating process according to the present invention may be applied to the surface of plastics substrates. Moreover, the coating process according to the present invention may be applied to the surface of a metal or of plastics substrate subsequently to the deposition of a coating layer forming a base coating layer on said substrate surface.
  • the forming of said base coating layer may be effected by known processes, such as electrodeposition coating process, applying an aqueous coating mixture, solvent type coating process or powder coating process.
  • said metal may be selected for example from a group comprising iron materials and other electrically conductive metallic materials; an especially preferred metallic stubstrate is an iron phosphate-treated steel sheet or a zinc phosphate-treated steel sheet.
  • the surface of a plastics substrate and/or the surface of a base coating layer applied on the surface of said substrate made of metal or plastics forms the surface of the substrate for the application of the coating process according to the present invention. Therefore, and within the present specification said surfaces are collectively referred to as "the surface of the substrate made of plastics or the surface of a base coating layer”.
  • the powder coating material comprises a base material or vehicle and pigments.
  • vehicle for example, may be selected from a group comprising polyester resins, acrylic resins, epoxy resins and other resins.
  • pigments and additives are incorporated in such a manner as to provide a powder comprising a content of 100 % of non-volatile components.
  • the particle size of the powder forming the powder coating material in terms of a bulk average particle diameter may range of from 5 ⁇ m to 50 ⁇ m and may preferably range of from 8 ⁇ m to 40 ⁇ m. In case where the average particle diameter ranges of from 5 ⁇ m to 20 ⁇ m, the amount of particles having a particle diameter less than 5 ⁇ m is preferably less than 25 % by weight. In case where the average particle diameter ranges of from 20 ⁇ m to 50 ⁇ m, the standard deviation of the particle size distribution is preferably not larger than 20 ⁇ m.
  • the standard deviation of a particle size distribution is expressed by the following term: [ ⁇ ⁇ (D - X) 2 F ⁇ / ⁇ F] 1/2 , wherein:
  • the type of plastics material forming the substrate is not critical.
  • the substrate may comprise thermoplastic or a thermosetting plastics material; said plastics material may be reinforced, but there is no need of reinforcement.
  • the plastics material forming the substrate may be selected, for example, from a group of plastics, including phenolic resins inclusive phenol-cellulose versions, silicone resins, amino resins, polyurethanes, polystyrenes, polypropylenes, thermoplastic acrylic resins, polyvinyl chlorides, polyacrylonitriles, polybutadienes and acrylonitrile-butadiene copolymers.
  • said fibers may comprise boron fibers and other fibers, however with the exception of glass fibers.
  • the temperature of the substrate is increased to a temperature of from 40° C to 140° C, but within said temperature range to a temperature
  • the transfer efficiency is poor; a substrate temperature higher than 140° C may cause an advanced partial curing of the powder particles forming the powder coating material, which may deteriorate the appearance of the finished coated product.
  • the substrate can be preheated prior to applying the powder coating material.
  • the subsequent powder coating step may be performed before a renewed cooling step following the baking step in course of a substrate base coating process.
  • the above-mentioned temperature of the heated substrate is preferably not higher than the upper limit of the baking temperature of the powder coating process.
  • the upper limit of said temperature is preferably not higher than the upper limit of a baking temperature of a process for preparing said base coating layer and not higher than the upper limit of the baking temperature for the powder coating process.
  • the upper limit of the fore-mentioned temperature is preferably lower than the deformation temperature of said plastics material.
  • the content of volatile components of said base coating layer is controlled such that said base coating layer does not contain more than 10 % by weight volatile components based on the weight of said base coating layer. If this limit of 10 % by weight volatile components is exceeded, foaming, surface roughness and yellowing may occur, which may deteriorate the appearance of the final product.
  • the preferred limit of volatile components is 5 % by weight or less.
  • said base coating layer may contain a volatile amine compound.
  • the content of said volatile amine compound is controlled such that said base coating layer does not contain more than 2.0 % by weight of said volatile amine compound based on the weight of the non-volatile matters contained within said base coating layer. If this limit of 2.0 % by weight volatile amine compound is exceeded, the appearance of the final product will not be as good as desired.
  • the preferred limit of said volatile amine compound is 1.5 % by weight, and still more preferred is an upper limit of 1.2 % by weight.
  • the surface of the substrate being made of a plastics material and/or comprising a base coating layer containing at least one resin component
  • said surface is first heated to the above-mentioned temperature, and then an electrostatic coating process is performed in order to deposit a powder coating layer.
  • the electrostatic coating process as such can be carried out in a conventional manner.
  • an electrically conductive particulate substance such as graphite powder
  • the plastics material may be incorporated in the plastics material forming the substrate in order to impart electric conductivity.
  • an electrically conductive reinforcing fiber as a component of the substrate material.
  • the plastics substrate may be coated with an electrically conductive primer or with an electically conductive wash solution to impart electric conductivity.
  • a composition is prepared by adding 30 parts by weight of Cymel 303 (methoxylated methylolmelamine, Mitsui Toatsu Chemicals, Inc.) to 140 parts by weight of an aqueous acrylic resin having a hydroxyl value of 20 and an acid value of 58 (amine-neutralized, non-volatile matter 50%). Thereafter, 15 parts by weight of an aluminum pigment paste (AW-666, Asahi Chemical Industry Co., Ltd.) are added to this composition, in order to obtain a mixture. The mixture is stirred in order to obtain an aqueous metallic coating mixture.
  • Cymel 303 methoxylated methylolmelamine, Mitsui Toatsu Chemicals, Inc.
  • a composition is prepared by adding 80.5 parts by weight of decane-dicarboxylic acid, 4 parts by weight of a surface conditioner and 2 parts by weight of benzoin to 315 parts by weight of a glycidyl group-containing acrylic resin (glass transition temperature (Tg): 52° C). Following a melt-compounding step, the composition is finely divided in order to provide an acrylic powder coating material.
  • a composition is prepared by adding 7.5 parts by weight of triglycidyl isocyanurate, 60 parts by weight of titanium dioxide, 0.4 parts by weight of a surface conditioner and 1.1 parts by weight of benzoin to 100 parts by weight of a carboxyl group-containing polyester resin (Tg: 63° C). Following a melt-compounding step, the composition is finely divided in order to provide a polyester powder coating material.
  • An iron phosphate-treated steel sheet is electro-coated (Powertop, U Series, Nippon Paint Co., Ltd.) providing a base coating layer having a coating thickness of 20 ⁇ m.
  • a further coating step (OTOH Series, Nippon Paint Co., Ltd.) an intermediate coating layer is deposited having a coating thickness of 35 ⁇ m.
  • the steel sheet comprising the base coaring layer and the intermediate coating layer is then coated with the aqueous metallic coating mixture as prepared in Reference Example 1 and is baked at 80° C for 10 min., at 100° C for 10 min. and at 120° C for 10 min. Thereafter, samples of this coated and baked sheet are brought to the different temperatures as stated in Table 1.
  • a plastics blank intended for the use of an automotive bumper and made of a plastics material having a glass transition temperature (Tg) of 90°C (Mitsui Petrochemical Co., Ltd.) is treated with trichloroethane and coated with a conductive primer (RB-1140 CD primer, Nippon Paint Chemical Co., Ltd.).
  • This plastics blank is brought to the different temperatures as shown in Table 2.
  • an electrostatical coating step is performed using the acrylic powder coating material as prepared in Reference Example 2.
  • the coating conditions are the same as stated in Example 1.
  • the transfer efficiency is evaluated for each sample. The results are shown in Table 2.
  • Transfer efficiency 48 % 60 % 82 %
  • an iron phosphate-treated steel sheet is electrocoated, then intermediate-coated and further coated with the aqueous metallic coating mixture as prepared in Reference Example 1.
  • samples of the coated sheet are preheated at 80° C for 5 min., at 80° C for 10 min., at 90° C for 5 min., at 100° C for 5 min., at 130° C for 5 min., and at 140° C for 5 min.
  • the sheet samples are coated with the acrylic powder coating material as prepared in Reference Example 2.
  • the coating conditions are the same as stated in Example 1.
  • each sample is baked at 150° C for 25 min.
  • the content of the non-volatile components (% by weight) and the content of the volatile amine compound (% by weight based on the total content of non-volatile matters) of the intermediate coating layer obtained from the aqueous metallic coat are determined, following the pre-heating step.
  • the appearance of the final product is rated. The appearance is indicated by the value of NSIC measured by portable measuring instrument of sharpness of the reflection (Sugai Shikenki Co.). The results are stated in Table 3.
  • Non-volatile matter (% by weight) 85 90 88 90 95 99 Volatile amine compound (% by weight based on the content of total nonvolatile matter) 2.5 2.1 1.5 1.2 0.6 0.3 Appearance (NSIC) 58 70 71 73 74 75
  • a final product comprising a good appearance may be obtained by controlling the content of volatile components of the intermediate coating layer to be not larger than 10 % by weight, and/or controlling the amine content of said intermediate coating layer to be not larger than 2 % by weight based on the weight of the total content of non-volatile matters forming said intermediate layer.
  • a zinc phosphate-treated steel sheet having a thickness of 0.6 mm is coated with the same intermediate coating layer as used in Example 1, providing an intermediate coating layer having a coating thickness of 35 ⁇ m.
  • Samples of this coated sheet are brought to the different temperatures as indicated in Table 4.
  • An electrostatical coating step is performed using the polyester powder coating material as prepared in Reference Example 3. The coating conditions are the same as stated in Example 1. Thereafter, the transfer efficiency is evaluated for each sample. The results are stated in Table 4.
  • the transfer efficiency of a powder coating process is enhanced and the coating powder recovery is improved by preheating the substrate to a temperature not below the glass transition temperature (Tg) of the resin component of the powder coating material.
  • the invention is of value for the prevention of pollution and management of wastes.
  • the present invention provides advantages inter alia in saving labor and energy.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Claims (3)

  1. Verfahren zur Herstellung eines beschichteten Gegenstandes, mit den Verfahrensschritten:
    es wird ein Gegenstand bereitgestellt,
    -- der ein Substrat aus Kunststoffmaterial aufweist, oder
    -- der ein Substrat aus Kunststoff oder Metall aufweist, das mit einer Grundanstrichschicht versehen ist, die eine Kunststoffkomponente enthält,
    dieses Substrat wird auf eine vorgegebene Temperatur vorgewärmt,
    auf dem vorgewärmten Substrat wird mit Hilfe eines elektrostatischen Beschichtungsverfahrens ein eine Kunstharzkomponente enthaltendes Pulverbeschichtungsmaterial aufgebracht, um eine Pulverbeschichtung zu erzeugen,
    dadurch gekennzeichnet, daß
    zur Steigerung der Übertragbarkeit des Pulverbeschichtungsmaterials beim elektrostatischen Beschichtungsverfahren das Substrat vorgewärmt wird auf eine Temperatur im Bereich von 40 bis 140° C, jedoch innerhalb dieses Temperaturbereiches auf eine Temperatur
    oberhalb der Glasübergangstemperatur des Kunststoffmaterials, welches das Substrat bildet, oder
    oberhalb der Glasübergangstemperatur der Kunststoffkomponente der Grundanstrichschicht;
    oberhalb der Glasübergangstemperatur der Kunstharzkomponente des Pulverbeschichtungsmaterials; und
    unterhalb der Vernetzungstemperatur der Kunstharzkomponente des Pulverbeschichtungsmaterials;
    unterhalb der Vernetzungstemperatur der Kunststoffkomponente der Grundanstrichschicht, wenn ein Substrat eingesetzt wird, das aus Kunststoff oder aus Metall besteht und das eine Grundanstrichschicht aufweist.
  2. Verfahren nach Anspruch 1,
    dadurch gekennzeichnet, daß
    ein Substrat verwendet wird, das eine Grundanstrichschicht aufweist; und
    diese Grundanstrichschicht weniger als 10 Gew.-% flüchtige Komponenten enthält.
  3. Verfahren nach Anspruch 1 oder 2,
    dadurch gekennzeichnet, daß
    ein Substrat verwendet wird, das eine Grundanstrichschicht aufweist, die durch galvanische oder elektrolytische Abscheidung erhalten worden ist, oder die mit Hilfe eines wässrigen Beschichtungsverfahrens erzeugt worden ist; und
    diese Grundanstrichschicht weniger als 2 Gew.-% flüchtige Aminoverbindung enthält, bezogen auf das Gesamtgewicht der nichtflüchtigen Anteile.
EP19940114613 1993-09-17 1994-09-16 Beschichtungsverfahren Expired - Lifetime EP0643996B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP25501493 1993-09-17
JP255014/93 1993-09-17

Publications (2)

Publication Number Publication Date
EP0643996A1 EP0643996A1 (de) 1995-03-22
EP0643996B1 true EP0643996B1 (de) 1998-03-11

Family

ID=17273002

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19940114613 Expired - Lifetime EP0643996B1 (de) 1993-09-17 1994-09-16 Beschichtungsverfahren

Country Status (2)

Country Link
EP (1) EP0643996B1 (de)
DE (1) DE69408925T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577660A (zh) * 2019-08-14 2019-12-17 佛山宜可居新材料有限公司 一种有机高分子材料及其涂装方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996032529A1 (en) * 1995-04-12 1996-10-17 Alliedsignal Inc. Polymer substrate with additives and thermally induced diffusion process for making
WO2003020505A1 (fr) * 2001-08-28 2003-03-13 Toray Industries, Inc. Materiau en plaque de cfrp et procede de preparation correspondant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1265945A (fr) * 1960-05-25 1961-07-07 Rhone Poulenc Sa Nouveau procédé de revêtement à l'aide de poudres de matières plastiques
DE3324726A1 (de) * 1983-07-08 1985-01-17 Bosch-Siemens Hausgeräte GmbH, 7000 Stuttgart Verfahren zum herstellen eines mehrschichtigen ueberzuges auf einem durch pulverlackieren im elektrostatischen feld zu beschichtenden traeger
US5021297A (en) * 1988-12-02 1991-06-04 Ppg Industries, Inc. Process for coating plastic substrates with powder coating compositions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110577660A (zh) * 2019-08-14 2019-12-17 佛山宜可居新材料有限公司 一种有机高分子材料及其涂装方法
CN110577660B (zh) * 2019-08-14 2020-07-31 佛山宜可居新材料有限公司 一种有机高分子材料及其涂装方法

Also Published As

Publication number Publication date
DE69408925T2 (de) 1998-09-24
DE69408925D1 (de) 1998-04-16
EP0643996A1 (de) 1995-03-22

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