EP1358947A1 - Process for applying on a support a varnish comprising or not a solvent, especially on a vehicle headlamp reflector - Google Patents

Process for applying on a support a varnish comprising or not a solvent, especially on a vehicle headlamp reflector Download PDF

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Publication number
EP1358947A1
EP1358947A1 EP03290953A EP03290953A EP1358947A1 EP 1358947 A1 EP1358947 A1 EP 1358947A1 EP 03290953 A EP03290953 A EP 03290953A EP 03290953 A EP03290953 A EP 03290953A EP 1358947 A1 EP1358947 A1 EP 1358947A1
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EP
European Patent Office
Prior art keywords
varnish
approximately
temperature
application
radiation
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Granted
Application number
EP03290953A
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German (de)
French (fr)
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EP1358947B1 (en
Inventor
Frédéric Cote
Michel Mountaudouin
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Valeo Vision SAS
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Valeo Vision SAS
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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
    • B05D3/00—Pretreatment 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
    • B05D3/02—Pretreatment 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
    • B05D3/0218—Pretreatment, e.g. heating the substrate
    • 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
    • B05D3/00—Pretreatment 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
    • B05D3/02—Pretreatment 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
    • B05D3/0254—After-treatment
    • 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
    • B05D3/00—Pretreatment 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
    • B05D3/06—Pretreatment 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
    • B05D3/061—Pretreatment 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.
    • B05D3/062—Pretreatment
    • 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
    • B05D3/00—Pretreatment 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
    • B05D3/06—Pretreatment 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
    • B05D3/061—Pretreatment 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.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V7/00—Reflectors for light sources
    • F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
    • F21V7/24—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors characterised by the material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V7/00—Reflectors for light sources
    • F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
    • F21V7/28—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors characterised by coatings
    • 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
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • 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
    • B05D5/067—Metallic effect
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21W—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO USES OR APPLICATIONS OF LIGHTING DEVICES OR SYSTEMS
    • F21W2107/00—Use or application of lighting devices on or in particular types of vehicles

Definitions

  • the present invention relates to a method of applying a varnish comprising a solvent or not on a part, in particular a vehicle headlamp reflector.
  • the Applicant has set itself in particular as objective of ensuring excellent performance when applying a varnish on reflector type parts of vehicle headlamps while limiting its propensities to sink on the surface after application and without reducing the appearance qualities of the coating film basic.
  • the present invention provides a method of applying a varnish comprising a solvent or not on a part, in particular a vehicle headlight reflector, characterized in that it comprises the following steps consisting in (i ) choose a varnish with a viscosity at room temperature of around 500 mPa.s to around 2000 mPa.s and a viscosity at application temperature lower than around 200 mPa.s with a viscosity substantially independent of the temperature variation in the application range (ii) heating the surface of the part before the varnish wetting step to a chosen temperature ⁇ p1, (iii) heating the varnish at the time of application to a chosen temperature ⁇ v and ( iv) maintain the part during the tensioning at a chosen temperature ⁇ p 2 and a chosen duration tp 2 .
  • Varnishes containing a solvent or not are generally made up of resins whose viscosity is directly related to temperature.
  • the process according to the invention which can be implemented indifferently in the case of a varnish with or without solvent allows, by the choice of appropriate varnish temperatures, to guarantee excellent application performance, in particular by spraying.
  • the choice of room temperatures to be varnished before application and during the stretch, also allows control and optimize in particular the wettability and the "Mobility" of the varnish.
  • the viscosity varnish practically reaches its optimal value. Applied on a hot surface, on the one hand excellent wettability is obtained and on the other hand the boiling of the varnish is accelerated. At cooling, viscosity increasing rapidly, the risks are reduced.
  • step (ii) of the method according to the invention consists of heating by radiation, convection or conduction, for example using a formatting tool and step (iv) consists of heating by radiation or convection.
  • This kind of heating ensures correct tension, i.e. an optical surface as smooth as possible.
  • the varnish being with solvent ⁇ v is from approximately 20 ° C to approximately 40 ° C
  • ⁇ p 1 is from approximately 20 ° C to approximately 50 ° C
  • ⁇ p 2 and tp 2 from about 20 ° C to about 50 ° C and about 0.5 min to 3 min, respectively.
  • the solvent typically represents about 20% to about 75% by weight of the overall composition of varnish
  • the solvent does not represent more than 10% by weight of the overall composition of the varnish used in the process the invention.
  • the process desolvation times according to the invention are therefore considerably reduced, which greatly lowers its cost.
  • the varnish being solvent-free
  • the temperature ⁇ v is approximately 40 ° C to approximately 60 ° C
  • the temperature ⁇ p 1 is approximately 70 ° C to approximately 110 ° C
  • the temperature ⁇ p 2 is approximately 50 ° C to approximately 90 ° C
  • the duration tp 2 is approximately 0.5 min to approximately 1.5 min.
  • an application method of a UV varnish includes the classic steps of washing with water of the part, drying, UV pretreatment, application of varnish heated or so-called “wetting”, “stretched”, polymerization step UV and metallization.
  • the method according to the invention can be applied to any room able to withstand transient temperatures up to around 110 ° C.
  • thermosetting material useful in the process of the invention, mention may be made of solid molding mixtures or BMC for “bulk molding compounds” (or their variants such as that CIC, for “continuous impregnated compounds”, TMC, for “Thick molding compounds” or even SMC for “sheet molding compounds ”) which are resin-based compositions unsaturated polyester reinforced with glass fibers. Pieces in phenolic, vinyl or epoxy resins or even melamines urea-formalin may also be suitable.
  • UV varnish useful in the process of the invention, may cite the compositions conventionally comprising a acrylic resin or a mixture of acrylic resins and optionally one or more solvents.
  • the suitable solvents are for example the solvents ester type, such as for example ethyl acetate vinyl or butyl acetate or glycol ester type such as methoxypropylene acetate (MPA) or, of ketone type, such as for example methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK) or of alcohol type such as butyl alcohol or of aromatic type such as toluene, xylenes by example.
  • solvents ester type such as for example ethyl acetate vinyl or butyl acetate or glycol ester type such as methoxypropylene acetate (MPA) or, of ketone type, such as for example methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK) or of alcohol type such as butyl alcohol or of aromatic type such as toluene, xylenes by example.
  • MIBK methyl
  • the thickness of the layer of varnish obtained is of the order from 10 to 25 ⁇ m.
  • the above application range allows production a part with the necessary optical qualities to a headlight reflector of a motor vehicle (the gloss, the tense and respect for the optical surface).
  • the thermal resistance properties (30 min at 200 ° C) and resistance to humid heat (7 days at 70 ° C and 95% residual humidity) are such that after the tests the appearance of the metallization remains unchanged.
  • the thickness of the base coating layer obtained is about 10 ⁇ m minimum and can reach about 15 ⁇ m about 50 ⁇ m in a single gun pass.

Abstract

The method involves selecting a varnish having viscosity at ambient temperature between 500 to 2000 mega pascals, and a viscosity at application temperature lower than 200 mega pascals. The surface of a vehicle headlight reflector is then heated prior to moistening the varnish at a selected temperature, after which the varnish is heated to an appropriate temperature at the moment of application. The headlight reflector is kept at a predetermined temperature within the duration of the actual varnish application process.

Description

La présente invention a trait à un procédé d'application d'un vernis comprenant un solvant ou non sur une pièce, notamment un réflecteur de projecteur de véhicule.The present invention relates to a method of applying a varnish comprising a solvent or not on a part, in particular a vehicle headlamp reflector.

La majorité des compositions de base formant vernis qui sont appliquées sur des pièces, de type réflecteurs de projecteurs de véhicule fabriqués à partir de mélanges à mouler solides tels que BMC, CIC..., contiennent d'importantes quantités de solvants. La présence de ces solvants est estimée nécessaire pour réduire la viscosité des produits appliqués et améliorer les performances d'application, par exemple par pulvérisation. Au cours de la pulvérisation puis pendant la période de désolvatation, les solvants s'évaporent, en tout ou partie. De la viscosité des produits utilisés et de la nature et de la concentration résiduelle des solvants dépend le temps pendant lequel les bulles d'air piégées peuvent s'échapper et le film de vernis se tendre. Plus le temps de désolvatation est important plus les risques de coulure du vernis sur la surface des pièces s'accroissent, occasionnant de nombreux rebuts.The majority of base compositions forming varnish which are applied to parts, such as spotlight reflectors vehicles made from solid molding compounds such as that BMC, CIC ..., contain significant quantities of solvents. The presence of these solvents is considered necessary to reduce viscosity of applied products and improve performance application, for example by spraying. During spraying then during the desolvation period, the solvents evaporate, in whole or in part. Viscosity of the products used and the nature and residual concentration of the solvents depends the time that trapped air bubbles can escape and the varnish film will stretch. The longer the desolvation time the greater the risk of the varnish running on the surface of the parts increase, causing numerous rejects.

Aussi la Demanderesse s'est fixé en particulier comme objectif d'assurer d'excellentes performances à l'application d'un vernis sur des pièces de type réflecteurs de projecteurs de véhicule tout en limitant ses propensions à couler sur la surface après application et sans réduire les qualités d'aspect du film de revêtement de base.Also the Applicant has set itself in particular as objective of ensuring excellent performance when applying a varnish on reflector type parts of vehicle headlamps while limiting its propensities to sink on the surface after application and without reducing the appearance qualities of the coating film basic.

Cet objectif est atteint par la présente invention qui procure un procédé d'application d'un vernis comprenant un solvant ou non sur une pièce, notamment un réflecteur de projecteur de véhicule, caractérisé en ce qu'il comporte les étapes suivantes consistant à (i) choisir un vernis présentant une viscosité à température ambiante d'environ 500 mPa.s à environ 2000 mPa.s et une viscosité à la température d'application inférieure à environ 200 mPa.s avec une viscosité sensiblement indépendante de la variation de la température dans la gamme d'application (ii) chauffer la surface de la pièce avant l'étape de mouillage du vernis à une température choisie p1, (iii) chauffer le vernis au moment de l'application à une température choisie v et (iv) maintenir la pièce pendant la réalisation du tendu à une température choisie p2 et une durée choisie tp2.This object is achieved by the present invention which provides a method of applying a varnish comprising a solvent or not on a part, in particular a vehicle headlight reflector, characterized in that it comprises the following steps consisting in (i ) choose a varnish with a viscosity at room temperature of around 500 mPa.s to around 2000 mPa.s and a viscosity at application temperature lower than around 200 mPa.s with a viscosity substantially independent of the temperature variation in the application range (ii) heating the surface of the part before the varnish wetting step to a chosen temperature p1, (iii) heating the varnish at the time of application to a chosen temperature v and ( iv) maintain the part during the tensioning at a chosen temperature p 2 and a chosen duration tp 2 .

Les vernis comprenant un solvant ou non sont généralement constitués par des résines dont la viscosité est directement liée à la température.Varnishes containing a solvent or not are generally made up of resins whose viscosity is directly related to temperature.

Le procédé conforme à l'invention qui peut être mis en oeuvre indifféremment dans le cas d'un vernis avec ou sans solvant permet, par le choix de températures appropriées de vernis, de garantir une excellente performance à l'application, notamment par pulvérisation. Le choix des températures de pièce à vernir avant l'application et pendant le tendu, permet en outre de contrôler et d'optimiser en particulier la mouillabilité et la « mobilité » du vernis. A ces températures choisies, la viscosité du vernis atteint pratiquement sa valeur optimale. Appliqué sur une surface chaude, d'une part une excellente mouillabilité est obtenue et d'autre part le débullage du vernis est accéléré. Au refroidissement, la viscosité augmentant rapidement, les risques de coulure sont réduits.The process according to the invention which can be implemented indifferently in the case of a varnish with or without solvent allows, by the choice of appropriate varnish temperatures, to guarantee excellent application performance, in particular by spraying. The choice of room temperatures to be varnished before application and during the stretch, also allows control and optimize in particular the wettability and the "Mobility" of the varnish. At these selected temperatures, the viscosity varnish practically reaches its optimal value. Applied on a hot surface, on the one hand excellent wettability is obtained and on the other hand the boiling of the varnish is accelerated. At cooling, viscosity increasing rapidly, the risks are reduced.

De préférence, l'étape (ii) du procédé selon l'invention consiste à chauffer par rayonnement, convection ou conduction, par exemple grâce à un outil de mise en forme et l'étape (iv) consiste à chauffer par rayonnement ou convection. Ce type de chauffage permet d'assurer un tendu correct soit une surface optique la plus lisse possible.Preferably, step (ii) of the method according to the invention consists of heating by radiation, convection or conduction, for example using a formatting tool and step (iv) consists of heating by radiation or convection. This kind of heating ensures correct tension, i.e. an optical surface as smooth as possible.

Selon un premier mode de réalisation, le vernis étant avec solvant, v est d'environ 20°C à environ 40°C, p1 est d'environ 20°C à environ 50°C, et p2 et tp2 d'environ 20°C à environ 50 °C et environ 0,5 min à 3 min, respectivement.According to a first embodiment, the varnish being with solvent, v is from approximately 20 ° C to approximately 40 ° C, p 1 is from approximately 20 ° C to approximately 50 ° C, and p 2 and tp 2 from about 20 ° C to about 50 ° C and about 0.5 min to 3 min, respectively.

Par comparaison avec les procédés avec solvant(s) traditionnels, où le solvant représente de manière classique d'environ 20 % à environ 75 % en poids de la composition globale de vernis, le solvant ne représente pas plus de 10 % en poids de la composition globale du vernis mis en oeuvre dans le procédé de l'invention. Les temps de désolvatation du procédé conforme à l'invention sont donc nettement diminués, ce qui abaisse fortement son coût.Compared with traditional solvent-based processes, where the solvent typically represents about 20% to about 75% by weight of the overall composition of varnish, the solvent does not represent more than 10% by weight of the overall composition of the varnish used in the process the invention. The process desolvation times according to the invention are therefore considerably reduced, which greatly lowers its cost.

Selon un deuxième mode de réalisation du procédé de l'invention, le vernis étant sans solvant, la température v est d'environ 40°C à environ 60°C, la température p1 est d'environ 70°C à environ 110°C, la température p2 est d'environ 50°C à environ 90°C et la durée tp2 est d'environ 0,5 min à environ 1,5 min.According to a second embodiment of the process of the invention, the varnish being solvent-free, the temperature v is approximately 40 ° C to approximately 60 ° C, the temperature p 1 is approximately 70 ° C to approximately 110 ° C, the temperature p 2 is approximately 50 ° C to approximately 90 ° C and the duration tp 2 is approximately 0.5 min to approximately 1.5 min.

Un des avantages majeurs de ce mode de réalisation est d'abord de simplifier les formulations de vernis et d'opérer en l'absence de solvants. Outre leur caractère volatile, les solvants présentent un niveau de toxicité plus ou moins acceptable ainsi qu'un risque d'inflammabilité marqué. Ces contraintes nécessitent habituellement la mise en place d'installations de traitement des volatiles ainsi que d'équipements anti-déflagrants dans toutes les zones concernées. Ce mode de réalisation permet donc de réaliser des économies d'investissement et d'exploitation par la simplification des installations, car seule la zone d'application est équipée en anti-déflagrants par nécessité de nettoyage du matériel. Il présente en outre l'avantage de mettre les installations en conformité avec les normes de respect de l'environnement toujours plus strictes.One of the major advantages of this embodiment is first to simplify the varnish formulations and to operate in the absence of solvents. In addition to their volatility, solvents have a more or less acceptable level of toxicity as well than a marked risk of flammability. These constraints require usually the establishment of processing facilities as well as explosion-proof equipment in all affected areas. This embodiment therefore makes it possible to carry out investment and operating savings through simplification installations, because only the area of application is equipped with explosion-proof for the need to clean the equipment. It also has the advantage of putting the facilities in compliance with environmental standards always more stringent.

Les caractéristiques complémentaires ou alternatives du procédé selon l'invention sont les suivantes :

  • le vernis est appliqué par aspersion sous pression (« airless »), au pistolet à air comprimé ou électrostatique ; de manière avantageuse le pistolet est équipé d'une boucle de circulation thermorégulée : ce qui permet d'abaisser la viscosité du vernis et d'avoir une température v et un débit de vernis constants au moment de la pulvérisation au pistolet. Sans cette boucle, comme le pistolet fonctionne par intermittence, se posent des problèmes de contrôle de température ; l'épaisseur de la couche de vernis est obtenue en un seul passage du pistolet : le vernis se dépose parfaitement sur la pièce, il n'y a pas de retouche à faire ; lorsque le vernis appliqué au pistolet est un vernis sans solvant, cela permet des variations d'épaisseurs importantes compatibles avec la géométrie complexe de la surface à couvrir, ce qui augmente la robustesse du procédé ; à épaisseur identique, deux passages de pistolet sont en général nécessaires dans le cas d'un vernis avec solvant.
  • le vernis est un vernis UV : comparé aux vernis dits thermiques, les vernis UV assurent un gain de temps certain car une fois l'aspect recherché obtenu ce dernier est « figé » pratiquement instantanément comparé aux durées de l'ordre de 5 min à 10 min nécessaires avec les vernis thermiques, durées pendant lesquelles l'atmosphère des installations doit rester très propre « hors poussière ».
  • appliqué sur une pièce telle qu'un BMC, le procédé comporte une étape de prétraitement par rayonnement UV d'environ 1 J/cm2 à environ 4 J/cm2 avec une puissance maximale d'environ 130 mW à environ 250 mW, mesurée dans la bande UVA et dans un plan sensiblement perpendiculaire au rayonnement moyen de la zone d'éclairage UV. L'efficacité de traitement de la surface de la pièce et l'adhérence du vernis sur le BMC sont ainsi garanties.
  • le procédé comporte une étape de polymérisation par rayonnement UV entre environ 4 J/cm2 et environ 8 J/cm2, de préférence d'environ 2 J/cm2 à environ 4 J/cm2 avec une puissance d'environ 80 mW à environ 200 mW, mesurée dans la bande UVA, et dans un plan sensiblement perpendiculaire au rayonnement moyen de la zone d'éclairage UV. On obtient ainsi une surface brillante, tendue, apte à être métallisée.
  • il est prévu une optimisation de l'orientation du rayonnement de chaque émetteur ou la mise en mouvement de la pièce à traiter, ce qui permet de garantir un éclairement homogène quelle que soit la complexité de la surface insolée ; dans la pratique les émetteurs sont inclinés pour prendre en compte l'orientation des faces de la pièce ;
  • à l'étape de polymérisation UV, la température de vernis p2 étant élevée, le vernis est plus réactif. Cette augmentation de réactivité permet de réduire de façon notable le nombre d'émetteurs UV tout en polymérisant des zones généralement difficiles à insoler ;
  • le procédé comporte une étape de mise en rotation de la pièce selon un axe horizontal au cours de l'étape de tendu et/ou de polymérisation, ce qui permet d'éviter les coulures et d'augmenter à l'application l'épaisseur maximale de la couche déposée et ce quelle que soit la forme de la pièce à traiter. Ainsi est augmentée la robustesse du procédé d'application.
The complementary or alternative characteristics of the process according to the invention are as follows:
  • the varnish is applied by spraying under pressure ("airless"), with a compressed air or electrostatic spray gun; advantageously, the gun is equipped with a thermoregulated circulation loop: this makes it possible to lower the viscosity of the varnish and to have a constant temperature v and varnish flow at the time of spraying with the gun. Without this loop, as the gun operates intermittently, there are problems with temperature control; the thickness of the layer of varnish is obtained in a single pass of the gun: the varnish is deposited perfectly on the part, there is no retouching to be done; when the varnish applied with a spray gun is a solvent-free varnish, this allows significant thickness variations compatible with the complex geometry of the surface to be covered, which increases the robustness of the process; for the same thickness, two gun passages are generally necessary in the case of a solvent-based varnish.
  • the varnish is a UV varnish: compared to the so-called thermal varnishes, the UV varnishes ensure a certain time saving because once the desired appearance obtained the latter is "frozen" practically instantly compared to the durations of the order of 5 min to 10 min necessary with thermal varnishes, durations during which the atmosphere of the installations must remain very clean "free of dust".
  • applied to a part such as a BMC, the method comprises a step of pretreatment by UV radiation of approximately 1 J / cm 2 to approximately 4 J / cm 2 with a maximum power of approximately 130 mW to approximately 250 mW, measured in the UVA band and in a plane substantially perpendicular to the average radiation of the UV lighting area. The effectiveness of the surface treatment of the part and the adhesion of the varnish to the BMC are thus guaranteed.
  • the process comprises a step of polymerization by UV radiation between approximately 4 J / cm 2 and approximately 8 J / cm 2 , preferably from approximately 2 J / cm 2 to approximately 4 J / cm 2 with a power of approximately 80 mW at around 200 mW, measured in the UVA band, and in a plane substantially perpendicular to the average radiation of the UV lighting area. This gives a shiny, taut surface capable of being metallized.
  • there is provision for optimization of the orientation of the radiation from each emitter or setting in motion of the part to be treated, which makes it possible to guarantee uniform illumination whatever the complexity of the exposed surface; in practice the transmitters are inclined to take into account the orientation of the faces of the part;
  • at the UV polymerization stage, the varnish temperature p 2 being high, the varnish is more reactive. This increase in reactivity makes it possible to significantly reduce the number of UV emitters while polymerizing areas which are generally difficult to expose;
  • the method comprises a step of rotating the part along a horizontal axis during the stretching and / or polymerization step, which makes it possible to avoid sagging and to increase the maximum thickness on application regardless of the shape of the part to be treated. This increases the robustness of the application process.

La présente invention va maintenant être décrite de manière plus détaillée dans ses caractéristiques générales puis à l'aide d'un exemple de réalisation donné à titre illustratif et non limitatif.The present invention will now be described in a manner more detailed in its general characteristics then to using an exemplary embodiment given by way of illustration and not limiting.

De manière générale après moulage par injection d'une pièce en matière thermodurcissable, un procédé d'application d'un vernis UV comprend les étapes classiques de lavage à l'eau de la pièce, séchage, prétraitement UV, application du vernis chauffé ou étape dite de « mouillage », « tendu », polymérisation UV et métallisation.Generally after injection molding of a part made of thermosetting material, an application method of a UV varnish includes the classic steps of washing with water of the part, drying, UV pretreatment, application of varnish heated or so-called "wetting", "stretched", polymerization step UV and metallization.

Le procédé selon l'invention peut s'appliquer à toute pièce capable de supporter des températures transitoires jusqu'à environ 110°C.The method according to the invention can be applied to any room able to withstand transient temperatures up to around 110 ° C.

Dans le cas des réflecteurs pour projecteurs de véhicule, comme pièces en matière thermodurcissable utiles dans le procédé de l'invention, on peut citer les mélanges à mouler solide ou BMC pour « bulk molding compounds » (ou leurs variantes telles que CIC, pour « continuous impregnated compounds », TMC, pour « thick molding compounds » ou encore SMC pour « sheet molding compounds ») qui sont des compositions à base de résine polyester insaturée renforcée en fibres de verre. Des pièces en résines phénoliques, vinyliques ou époxydes ou encore des mélamines urée-formol peuvent également convenir.In the case of reflectors for vehicle headlights, as parts of thermosetting material useful in the process of the invention, mention may be made of solid molding mixtures or BMC for “bulk molding compounds” (or their variants such as that CIC, for “continuous impregnated compounds”, TMC, for "Thick molding compounds" or even SMC for "sheet molding compounds ") which are resin-based compositions unsaturated polyester reinforced with glass fibers. Pieces in phenolic, vinyl or epoxy resins or even melamines urea-formalin may also be suitable.

Comme vernis UV, utiles dans le procédé de l'invention on peut citer les compositions comprenant de manière classique une résine acrylique ou un mélange de résines acryliques et éventuellement un ou plusieurs solvants.As UV varnish, useful in the process of the invention, may cite the compositions conventionally comprising a acrylic resin or a mixture of acrylic resins and optionally one or more solvents.

Les résines acryliques mises en oeuvre dans le procédé selon l'invention peuvent comprendre un ou plusieurs des composés suivants :

  • polymères ou copolymères d'esters de l'acide acrylique tels que des oligomères acrylate multifonctionnels, par exemple de type époxy acrylate, uréthanne acrylate aliphatique ou aromatique, polyester acrylate, acrylique acrylate ; ces composés sont typiquement des liquides visqueux présentant à 25°C une viscosité d'environ plusieurs milliers à environ plus d'un million de centipoise (cP), présentent en général de 2 à 6 groupes acrylates par molécule et possèdent un poids moléculaire d'environ 500 à environ 20000,
  • monomères acrylates multifonctionnels possédant en général de 1 à 4 groupes acrylate par molécule et un poids moléculaire d'environ 150 à environ 500, leur viscosité à 25°C étant d'environ 5 à environ 200 cP,
  • l'hexanedioldiacrylate (HDDA), le tripropylèneglycoldiacrylate (TPGDA), le triéthylèneglycoldiacrylate (TEGDA) et le dipropylèneglycoldiacrylate (DPGDA) et des monomères du type acide acrylique,
  • un ou plusieurs photo-initiateurs du type arylcétones, par exemple la benzophénone, l'hydroxycyclohexylphénylcétone (HCPK), la 2,2-diméthoxy-1,2-diphénylméthan-1-one ;
  • Un ou plusieurs agents tensioactifs du type alkylpolysiloxane tel que le diméthylpolysiloxane ou encore le méthacrylatesiloxane, un polyethersiloxane ou polyestersiloxane.
  • D'autres additifs peuvent être ajoutés aux composés précédents, comme par exemple un ou plusieurs agents antimousse, promoteurs d'adhérence, agents thixotropes, stabilisants, colorants, etc.
The acrylic resins used in the process according to the invention can comprise one or more of the following compounds:
  • polymers or copolymers of acrylic acid esters such as multifunctional acrylate oligomers, for example of the epoxy acrylate, urethane aliphatic or aromatic acrylate, polyester acrylate, acrylic acrylate type; these compounds are typically viscous liquids having at 25 ° C a viscosity of about several thousand to about more than a million centipoise (cP), generally have from 2 to 6 acrylate groups per molecule and have a molecular weight of about 500 to about 20,000,
  • multifunctional acrylate monomers generally having 1 to 4 acrylate groups per molecule and a molecular weight of approximately 150 to approximately 500, their viscosity at 25 ° C. being approximately 5 to approximately 200 cP,
  • hexanedioldiacrylate (HDDA), tripropylene glycoldiacrylate (TPGDA), triethylene glycoldiacrylate (TEGDA) and dipropylene glycoldiacrylate (DPGDA) and monomers of the acrylic acid type,
  • one or more photo-initiators of the aryl ketone type, for example benzophenone, hydroxycyclohexylphenyl ketone (HCPK), 2,2-dimethoxy-1,2-diphenylmethan-1-one;
  • One or more surfactants of the alkylpolysiloxane type such as dimethylpolysiloxane or also methacrylatesiloxane, a polyethersiloxane or polyestersiloxane.
  • Other additives can be added to the above compounds, such as for example one or more anti-foaming agents, adhesion promoters, thixotropic agents, stabilizers, dyes, etc.

Lorsqu'ils sont présents dans la mise en oeuvre du procédé de l'invention, les solvants appropriés sont par exemple les solvants de type ester, tels que par exemple l'acétate d'éthyle l'acétate de vinyle ou de butyle ou encore de type ester de glycol tel le méthoxypropylèneacétate (MPA) ou, de type cétone, tels que par exemple la méthylisobutylcétone (MIBK) ou la méthyléthylcétone (MEK) ou encore de type alcool tels que l'alcool butylique ou encore de type aromatique tels que le toluène, xylènes par exemple.When they are present in the implementation of the process of the invention, the suitable solvents are for example the solvents ester type, such as for example ethyl acetate vinyl or butyl acetate or glycol ester type such as methoxypropylene acetate (MPA) or, of ketone type, such as for example methyl isobutyl ketone (MIBK) or methyl ethyl ketone (MEK) or of alcohol type such as butyl alcohol or of aromatic type such as toluene, xylenes by example.

EXEMPLE 1EXAMPLE 1 Procédé d'application d'un vernis avec solvant sur pièces BMCMethod of applying a solvent-based varnish to parts BMC

Les étapes caractéristiques essentielles du procédé selon l'invention sont les suivantes :

  • nature du vernis : résine acrylique comportant de l'acétate de vinyle à raison de 5% en poids de la composition globale du vernis) ; le vernis présentant une viscosité à température ambiante d'environ 500 mPa.s à 2000 mPa.s et une viscosité à la température d'application inférieure à environ 200 mPa.s avec une viscosité sensiblement indépendante de la variation de la température dans la gamme d'application ;
  • prétraitement UV (Dose : 4 J/cm2 ; puissance : 160 mW/cm2, mesurée en UVA) ;
  • chauffage des pièces à 40°C avant mouillage;
  • chauffage du vernis (température de pulvérisation au pistolet à air comprimé avec boucle de thermorégulation: 35 °C) ;
  • maintien de la température pendant le tendu (température de « flash off» : 35°C pendant 1 min ; pièces en rotation : 2 RPM) ;
  • polymérisation UV (Dose 6 J/cm2 ; puissance 160 mW/cm2, mesurée en UVA)
  • aluminiage
The essential characteristic steps of the method according to the invention are as follows:
  • nature of the varnish: acrylic resin comprising vinyl acetate at a rate of 5% by weight of the overall composition of the varnish); the varnish having a viscosity at ambient temperature of approximately 500 mPa.s to 2000 mPa.s and a viscosity at the application temperature less than approximately 200 mPa.s with a viscosity substantially independent of the temperature variation in the range of application;
  • UV pretreatment (Dose: 4 J / cm2; power: 160 mW / cm2, measured in UVA);
  • heating the rooms to 40 ° C before wetting;
  • varnish heating (spraying temperature with compressed air gun with thermoregulation loop: 35 ° C);
  • maintaining the temperature during the stretch (“flash off” temperature: 35 ° C for 1 min; rotating parts: 2 RPM);
  • UV polymerization (Dose 6 J / cm2; power 160 mW / cm2, measured in UVA)
  • aluminizing

L'épaisseur de la couche de vernis obtenue est de l'ordre de 10 à 25 µm. La gamme d'application ci-dessus permet la production d'une pièce présentant les qualités optiques nécessaires à un réflecteur de phare de véhicule automobile (le brillant, le tendu et le respect de la surface optique).The thickness of the layer of varnish obtained is of the order from 10 to 25 µm. The above application range allows production a part with the necessary optical qualities to a headlight reflector of a motor vehicle (the gloss, the tense and respect for the optical surface).

EXEMPLE 2EXAMPLE 2 Procédé d'application d'un vernis sans solvant sur pièces BMCMethod of applying a solvent-free varnish to parts BMC

Les étapes caractéristiques essentielles du procédé selon l'invention sont les suivantes :

  • nature du vernis : résine acrylique (% de volatiles inférieur à 1%) ; le vernis présentant une viscosité à température ambiante d'environ 500 mPa.s à 2000 mPa.s et une viscosité à la température d'application inférieure à environ 200 mPa.s avec une viscosité sensiblement indépendante de la variation de la température dans la gamme d'application ;
  • chauffage ou maintien des pièces à 90°C
  • prétraitement UV (Dose : 2 J/cm2 ; puissance : 160 mW/cm2, mesurée en UVA) ;
  • chauffage ou maintien des pièces à 90°C avant mouillage ;
  • chauffage du vernis (température de pulvérisation au pistolet à air comprimé avec boucle de thermorégulation: 45 °C ;
  • maintien de la température pendant le tendu (température de « flash off» : 70°C pendant 1,5 min ; pièces en rotation : 2 RPM) ;
  • polymérisation UV (Dose 2 J/cm2 ; puissance 160 mW/cm2, mesurée en UVA) ;
  • aluminiage
The essential characteristic steps of the method according to the invention are as follows:
  • nature of the varnish: acrylic resin (% volatile less than 1%); the varnish having a viscosity at ambient temperature of approximately 500 mPa.s to 2000 mPa.s and a viscosity at the application temperature less than approximately 200 mPa.s with a viscosity substantially independent of the temperature variation in the range of application;
  • heating or keeping parts at 90 ° C
  • UV pretreatment (Dose: 2 J / cm2; power: 160 mW / cm2, measured in UVA);
  • heating or keeping the parts at 90 ° C before wetting;
  • varnish heating (spraying temperature with a compressed air gun with thermoregulation loop: 45 ° C;
  • maintaining the temperature during the stretch ("flash off" temperature: 70 ° C for 1.5 min; rotating parts: 2 RPM);
  • UV polymerization (Dose 2 J / cm2; power 160 mW / cm2, measured in UVA);
  • aluminizing

On constate qu'ayant contrôlé la température de surface, selon le procédé de l'invention on assure la maítrise de la mouillabilité et de l'étalement.We note that having controlled the surface temperature, according to the method of the invention, control of wettability is ensured and sprawl.

Le choix de la température de flash-off permet de maítriser l'aspect de la surface (tendu, débullage, coulure).The choice of the flash-off temperature allows you to control the appearance of the surface (stretched, bubbling, sagging).

Les propriétés de tenue thermique (30 min à 200°C) et de tenue à la chaleur humide (7 jours à 70°C et 95% d'humidité résiduelle) sont telles qu'après les essais l'aspect de la métallisation reste inchangé.The thermal resistance properties (30 min at 200 ° C) and resistance to humid heat (7 days at 70 ° C and 95% residual humidity) are such that after the tests the appearance of the metallization remains unchanged.

L'épaisseur de la couche de revêtement de base obtenue est d'environ 10 µm au minimum et peut atteindre environ 15 µm à environ 50 µm en un seul passage de pistolet.The thickness of the base coating layer obtained is about 10 µm minimum and can reach about 15 µm about 50 µm in a single gun pass.

Outre les excellentes performances mentionnées ci-dessus que permet d'atteindre le procédé selon l'invention, ce dernier conduit très avantageusement à une simplification notable des installations. Une réduction drastique de la pollution et des coûts de retraitement des fumées, en termes d'investissements et de maintenance, est aussi assurée.Besides the excellent performance mentioned above that achieves the method according to the invention, the latter very advantageously leads to a significant simplification of the facilities. Drastic reduction in pollution and costs smoke reprocessing, in terms of investments and maintenance is also provided.

Claims (11)

Procédé d'application d'un vernis comprenant un solvant ou non sur une pièce, notamment un réflecteur de projecteur de véhicule, caractérisé en ce qu'il comporte les étapes suivantes consistant à (i) choisir un vernis présentant une viscosité à température ambiante d'environ 500 mPa.s à 2000 mPa.s et une viscosité à la température d'application inférieure à environ 200 mPa.s avec une viscosité sensiblement indépendante de la variation de la température dans la gamme d'application (ii) chauffer la surface de la pièce avant l'étape de mouillage du vernis à une température choisie p1, (iii) chauffer le vernis au moment de l'application à une température choisie v et (iv) maintenir la pièce pendant la réalisation du tendu à une température choisie p2 et une durée choisie tp2.Method for applying a varnish comprising a solvent or not on a part, in particular a vehicle headlamp reflector, characterized in that it comprises the following steps consisting in (i) choosing a varnish having a viscosity at room temperature d '' approximately 500 mPa.s to 2000 mPa.s and a viscosity at the application temperature lower than approximately 200 mPa.s with a viscosity substantially independent of the variation of the temperature in the range of application (ii) heating the surface of the part before the varnish wetting step at a chosen temperature p 1 , (iii) heating the varnish at the time of application to a chosen temperature v and (iv) maintaining the part during the production of the tension a chosen temperature p 2 and a chosen duration tp 2 . Procédé selon la revendication 1, caractérisé en ce que l'étape (ii) consiste à chauffer par rayonnement, convection ou conduction et l'étape (iv) consiste à chauffer par rayonnement ou convection.A method according to claim 1, characterized in that step (ii) consists in heating by radiation, convection or conduction and step (iv) consists in heating by radiation or convection. Procédé selon la revendication 1 ou 2, caractérisé en ce que le vernis comprenant un solvant, v est d'environ 20°C à environ 40°C, p1 est d'environ 20°C à environ 50°C, et p2 et tp2 d'environ 20°C à environ 50 °C et environ 0,5 min à 3 min, respectivement.Method according to claim 1 or 2, characterized in that the varnish comprising a solvent, v is from approximately 20 ° C to approximately 40 ° C, p1 is from approximately 20 ° C to approximately 50 ° C, and  p2 and tp2 from about 20 ° C to about 50 ° C and about 0.5 min to 3 min, respectively. Procédé selon la revendication 1 ou 2, caractérisé en ce que vernis étant sans solvant, la température v est d'environ 40°C à environ 60°C, la température p1 est d'environ 70°C à environ 110°C, la température p2 est d'environ 50°C à environ 90°C et la durée tp2 est d'environ 0,5 min à environ 1,5 min.Method according to claim 1 or 2, characterized in that the varnish being solvent-free, the temperature v is from about 40 ° C to about 60 ° C, the temperature p 1 is from about 70 ° C to about 110 ° C, the temperature p 2 is from about 50 ° C to about 90 ° C and the duration tp 2 is from about 0.5 min to about 1.5 min. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'application est réalisée par aspersion sous pression (« airless »), au pistolet à air comprimé ou électrostatique.Process according to any one of Claims 1 to 4, characterized in that the application is carried out by spraying under pressure ("airless"), with a compressed air or electrostatic spray gun. Procédé selon la revendication 5, caractérisé en ce que le pistolet à air comprimé est équipé d'une boucle de circulation thermorégulée.Method according to claim 5, characterized in that the compressed air gun is equipped with a thermoregulated circulation loop. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce que le vernis est un vernis UV.Method according to any one of the preceding claims, characterized in that the varnish is a UV varnish. Procédé selon la revendication 7, caractérisé en ce qu'il est appliqué sur une pièce telle qu'un BMC et en ce qu'il comporte une étape de prétraitement par rayonnement UV d'environ 1 J/cm2 à environ 4 J/cm2 avec une puissance maximale d'environ 130 mW à environ 250 mW, mesurée dans la bande UVA et dans un plan sensiblement perpendiculaire au rayonnement moyen de la zone d'éclairage UV.Method according to claim 7, characterized in that it is applied to a part such as a BMC and in that it comprises a step of pretreatment by UV radiation of approximately 1 J / cm 2 to approximately 4 J / cm 2 with a maximum power of approximately 130 mW to approximately 250 mW, measured in the UVA band and in a plane substantially perpendicular to the average radiation of the UV lighting zone. Procédé selon la revendication 7 ou 8, caractérisé en ce qu'il comporte une étape de polymérisation par rayonnement UV d'environ 2 J/cm2 à environ 4 J/cm2 avec une puissance d'environ 80 mW à environ 200 mW, mesurée dans la bande UVA, et dans un plan sensiblement perpendiculaire au rayonnement moyen de la zone d'éclairage UV.Method according to claim 7 or 8, characterized in that it comprises a step of polymerization by UV radiation of approximately 2 J / cm 2 to approximately 4 J / cm 2 with a power of approximately 80 mW to approximately 200 mW, measured in the UVA band, and in a plane substantially perpendicular to the average radiation of the UV lighting area. Procédé selon l'une quelconque des revendications précédentes caractérisé en ce qu'il comporte une étape de mise en rotation de la pièce selon un axe horizontal au cours de l'étape de tendu et/ou de polymérisation.Method according to any one of the preceding claims, characterized in that it includes a step of rotating the part along a horizontal axis during the stretching and / or polymerization step. Procédé selon l'une quelconque des revendications 5 à 10, caractérisé en ce que l'épaisseur de la couche de vernis est obtenue en un seul passage du pistolet.Method according to any one of claims 5 to 10, characterized in that the thickness of the layer of varnish is obtained in a single pass of the gun.
EP03290953A 2002-04-30 2003-04-16 Process for applying on a support a varnish comprising or not a solvent, especially on a vehicle headlamp reflector Expired - Lifetime EP1358947B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004039506A2 (en) * 2002-10-28 2004-05-13 Nordson Corporation Can lid score repair with uv curable material

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4899291B2 (en) * 2004-04-13 2012-03-21 住友ベークライト株式会社 Coating method
JP4805628B2 (en) * 2005-08-03 2011-11-02 豊田合成株式会社 MULTILAYER COATING FORMATION METHOD, COATING AND COATED ARTICLE USED FOR THE METHOD
BRPI0600493B1 (en) * 2006-02-16 2015-07-21 Magneti Marelli Sist S Automotivos Indústria E Comércio Ltda Lens and reflector varnishing process of a lighting component of a vehicle.
US8801860B1 (en) * 2008-10-01 2014-08-12 Thomas M. Wall Method and kit for restoring a vehicle headlight lens
DE102011100737A1 (en) * 2011-05-06 2012-11-08 Baumer Hhs Gmbh Method for applying paint for producing Braille-dots on pharmaceutical package to inform about package contents to blind patient, involves heating medium with specific temperature by heating device while passing via coating head
RU2518624C2 (en) * 2012-07-27 2014-06-10 Сергей Романович Исламов Coal thermal benefication and device to this end
DE102012017538A1 (en) * 2012-09-05 2014-03-06 Heidelberger Druckmaschinen Ag Process for imaging and / or varnishing the surface of objects
JP6602358B2 (en) * 2017-05-16 2019-11-06 関西ペイント株式会社 Coating method
US10544499B1 (en) * 2018-08-13 2020-01-28 Valeo North America, Inc. Reflector for vehicle lighting

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1436606A (en) * 1964-02-04 1966-04-29 Herberts & Co Gmbh Dr Kurt Process for the preparation of glazed coatings from unsaturated polyesters and graftable vinyl compounds
GB1386324A (en) * 1971-07-21 1975-03-05 Gen Electric Method for coating substrates and apparatus employed in such method
FR2447794A1 (en) * 1979-02-05 1980-08-29 Valentine Cie Vernis PROCESS FOR COATING THERMOSETTING PLASTIC MATERIALS AND PRODUCTS OBTAINED ACCORDING TO THIS PROCESS
FR2483267A2 (en) * 1977-12-27 1981-12-04 Vianova Kunstharz Ag Water based spray painting applicator - preheats water used in auxiliary nozzles for main mixing nozzle
EP0681000A1 (en) * 1994-04-29 1995-11-08 BASF Aktiengesellschaft Objects from bulk moulding compositions based on unsaturated polyesters having an improved surface

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT355161B (en) 1977-12-27 1980-02-25 Vianova Kunstharz Ag PAINT PROCESS

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1436606A (en) * 1964-02-04 1966-04-29 Herberts & Co Gmbh Dr Kurt Process for the preparation of glazed coatings from unsaturated polyesters and graftable vinyl compounds
GB1386324A (en) * 1971-07-21 1975-03-05 Gen Electric Method for coating substrates and apparatus employed in such method
FR2483267A2 (en) * 1977-12-27 1981-12-04 Vianova Kunstharz Ag Water based spray painting applicator - preheats water used in auxiliary nozzles for main mixing nozzle
FR2447794A1 (en) * 1979-02-05 1980-08-29 Valentine Cie Vernis PROCESS FOR COATING THERMOSETTING PLASTIC MATERIALS AND PRODUCTS OBTAINED ACCORDING TO THIS PROCESS
EP0681000A1 (en) * 1994-04-29 1995-11-08 BASF Aktiengesellschaft Objects from bulk moulding compositions based on unsaturated polyesters having an improved surface

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004039506A2 (en) * 2002-10-28 2004-05-13 Nordson Corporation Can lid score repair with uv curable material
WO2004039506A3 (en) * 2002-10-28 2004-11-04 Nordson Corp Can lid score repair with uv curable material

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