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EP1252242A2 - Compositions reticulables sous l'effet d'uv pour la production de revetements metalliques de decoration - Google Patents

Compositions reticulables sous l'effet d'uv pour la production de revetements metalliques de decoration

Info

Publication number
EP1252242A2
EP1252242A2 EP00992185A EP00992185A EP1252242A2 EP 1252242 A2 EP1252242 A2 EP 1252242A2 EP 00992185 A EP00992185 A EP 00992185A EP 00992185 A EP00992185 A EP 00992185A EP 1252242 A2 EP1252242 A2 EP 1252242A2
Authority
EP
European Patent Office
Prior art keywords
metallic composition
weight
composition
metallic
amount
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.)
Withdrawn
Application number
EP00992185A
Other languages
German (de)
English (en)
Inventor
Roy C. Krohn
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.)
Allied Photochemical Inc
Original Assignee
Flexodeco Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Flexodeco Inc filed Critical Flexodeco Inc
Publication of EP1252242A2 publication Critical patent/EP1252242A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate

Definitions

  • the present invention relates to ultraviolet light curable compositions that may be utilized to produce a decorative metallic coating on a substrate.
  • UV radiation curable paint compositions are applied to a substrate through spraying, screen printing, dipping or brushing for the protection or decoration of the substrate.
  • a substrate such as metals, glass, or plastics is coated with the paint composition and then UV light is introduced to complete the curing process.
  • the UV curable paint compositions offer many advantages over typical heat curable compositions.
  • Heat curable compositions require the use of organic solvents that contain a significant amount of volatile organic compounds (VOCs). These VOCs escape into the atmosphere while the heat curable composition dries. Such solvent based systems are undesirable because of the hazards and expenses associated with VOCs. The hazards include water and air pollution and the expenses include the cost of complying with strict government regulation on solvent emission levels. In contrast, UV curable compositions contain reactive monomers instead of solvents; thus eliminating the detrimental effects of the VOCs.
  • VOCs volatile organic compounds
  • heat curable compositions not only raises environmental concerns but other disadvantages exist with their use as well. Heat curable compositions suffer from slow cure times which lead to decreased productivity. These compositions require high energy for curing due to energy loss as well as the energy required to heat the substrate. Additionally, many heat curable compositions yield poor film properties that result in decreased value of the end product. Although UV curable compositions exhibit superior properties and performance over their heat curable counterparts, UV curable compositions themselves suffer from certain disadvantages. Generally, UV compositions have high molecular weights and a substantial degree of cross linkage due to the highly reactive nature of the composition. As a result, many of these compositions suffer from low durability and resin shrinkage. With the use of many such compositions, an inordinately high amount of UV light is required to cure. New formulations that lessen these problems typically suffer from diminished abrasion, chemical, and scratch resistance as well as low thermal stability and adhesion.
  • the present invention discloses an ultraviolet light curable decorative metallic composition and method for making such a composition that may be used to produce a decorative metallic layer.
  • the disclosed composition does not contain any significant amount of volatile organic solvents that do not become incorporated in the active layer after curing.
  • the decorative metallic composition contains 5 % or less volatile organic solvents by weight.
  • an ultraviolet light curable decorative metallic composition comprises an acrylated epoxy oligomer in an amount of about 20% to 45 % , an isobornyl acrylate monomer in an amount of about 15 % to 40% of the decorative metallic composition, a photo initiator in an amount of about 4% to 14% of the decorative metallic composition, a flow promoting agent in an amount of 0% to 8 % of the decorative metallic composition, and a metallic pigment in an amount of 5 % to 40% . All percentages of the decorative metallic composition as expressed in this document refer to the weight percentage of the stated component to the total weight of the decorative metallic composition in its fluid state at standard temperature and pressure.
  • a method for depositing a decorative metallic coating on a substrate.
  • the method comprises a first step of applying to the substrate a decorative metallic fluid-phase composition ("decorative metallic composition").
  • the decorative metallic composition includes an acrylated epoxy oligomer in an amount of about 20% to 45 % , an isobornyl acrylate monomer in an amount of about 15 % to 40% of the decorative metallic composition, a photoinitiator in an amount of about 4% to 14% of the decorative metallic composition, a flow promoting agent in an amount of 0 % to 8 % of the decorative metallic composition, and a metallic pigment in an amount of 5 % to 40% .
  • the method also includes a second step of illuminating the decorative metallic composition on the substrate with an ultraviolet light to cause the decorative metallic composition to cure into the decorative metallic coating.
  • the decorative metallic composition can be selectively deposited on the substrate at specific locations where decorative metallic plating is desired. It need not be applied to the entire substrate.
  • the decorative metallic composition includes an acrylated epoxy oligomer.
  • the acrylated epoxy oligomer is present in an amount of about 20 % to 45 % .
  • the acrylated epoxy oligomer is more preferably present in an amount of about 35 % to 45 % , and most preferably about 40% .
  • Suitable acrylated epoxy oligomers include Radcure Ebecryl 3603 (novolac epoxy acrylate diluted 20% by weight with tripropylene glycol diacrylate), commercially available from Radcure UCB Corp.
  • the preferred acrylated epoxy oligomer is Ebecryl 3603, which is a tri-functional acrylated epoxy novolac.
  • the preferred decorative metallic composition also includes an isobornyl acrylate monomer in an amount of about 15% to 40% .
  • the isobornyl acrylate monomer is more preferably present in an amount of about 25 % to 35 % , and most preferably about 28% .
  • Suitable isobornyl acrylate monomers include
  • Radcure IBOA isobornyl acrylate
  • IBOA and IBOMA commercially available from CPS Chemical
  • Genomer 1121 commercially available from Rahn Radiation Curing.
  • the preferred isobornyl acrylate monomers is Radcure IBOA, commercially available from Radcure Corp. Radcure IBOA is a high purity, low color monomer. Combinations of these materials may also be employed herein.
  • This preferred decorative metallic composition also includes a photoinitiator in an amount of about 4% to 14% of the decorative metallic composition.
  • the photoinitiator is more preferably present in an amount of about 8% to 12% , and most preferably about 10% .
  • Suitable photoinitiators include Irgacure 184 (1-hydroxycyclohexyl phenyl ketone); Irgacure 907 (2-methyl-l-[4- (methylthio)phenyl]-2-morpholino propan-1-one); Irgacure 369 (2-benzyl-2-N,N- dimethylamino-l-(4-morpholinophenyl)-l-butanone); Irgacure 500 (the combination of 50 % by weight 1-hydroxy cyclohexyl phenyl ketone and 50 % by weight benzophenone); Irgacure 651 (2,2-dimethoxy-2-phenyl acetophenone) ; Irga
  • CYRACURE UVI-6974 mixed triaryl sulfonium hexafluoroantimonate salts
  • CYRACURE UVI-6990 mixed triaryl sulfonium hexafluorophosphate salts
  • the preferred photoinitiator is IRGACURE 1700 commercially available from Ciba-Geigy of Tarrytown, New York. Combinations of these materials may also be employed herein.
  • the composition still further includes a flow promoting agent in an amount of about 0.0% to 8.0 % , and preferably about 6.0 % , of the topcoat composition.
  • Suitable flow promoting agents include Genorad 17, commercially available from Rahn Radiation Curing; and Modaflow, commercially available from Monsanto Chemical Co. , St. Louis, Missouri.
  • the preferred flow promoting agent is Modaflow which is an ethyl acrylate and 2-ethylhexyl acrylate copolymer that improves the flow of the composition. Combinations of these materials may also be employed herein.
  • the preferred paint composition also includes a pigmented composition in an amount of about 5% to 40% of the decorative metallic composition.
  • the pigmented composition is more preferably present in an amount of about 10% to 25%, and most preferably about 20% .
  • Suitable pigmented compositions includeVenus #91 pigment and Palegold #400 available from NazDar; and Al #200 pigment available from Silberlne. The preferred pigment used will depend on the desired color of the paint. Combinations of these materials may also be employed herein.
  • Example 1 To illustrate, the following example sets forth a presently preferred decorative metallic composition according to this aspect of the invention.
  • Example 1
  • This example provides a preferred gold decorative metallic composition according to the invention.
  • the decorative metallic composition was made from the following components:
  • the IBOA and Irgacure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
  • the Modaflow and the Ebecryl 3603 are introduced into the pan and mixed for 1 to 2 minutes at a speed of 2000 rpm.
  • the Venus #91 is introduced into the pan and mixed for 1 to 2 minutes at a speed of 2000 rpm. The temperature during mixing is monitored. The mixing is temporarily suspended if the temperature exceed 100°F.
  • This example provides a preferred aluminum decorative metallic composition according to the invention.
  • the decorative metallic composition was made from the following components:
  • the IBOA and Irgacure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
  • the Modaflow and the Ebecryl 3603 are introduced into the pan and mixed for 1 to 2 minutes at a speed of 2000 rpm.
  • the Aluminum #200 is introduced into the pan and mixed for 1 to 2 minutes at a speed of 2000 rpm. The temperature during mixing is monitored. The mixing is temporarily suspended if the temperature exceed 100°F.
  • This example provides a preferred copper decorative metallic composition according to the invention.
  • the decorative metallic composition was made from the following components:
  • the IBOA and Irgacure 1700 are mixed in a pan with a propeller blade mixer for 30 seconds at a speed of 500 to 1000 rpm.
  • the Modaflow and the Ebecryl 3603 are introduced into the pan and mixed for 1 to 2 minutes at a speed of 2000 rpm.
  • the Palegold #400 is introduced into the pan and mixed for 1 to 2 minutes at a speed of 2000 rpm. The temperature during mixing is monitored. The mixing is temporarily suspended if the temperature exceed 100°F.
  • a method for depositing an decorative metallic coating on a suitable substrate.
  • the method comprises a first step of applying a decorative metallic fluid-phase composition ("decorative metallic composition") to the substrate.
  • the decorative metallic composition comprises an acrylated epoxy oligomer in an amount of about 20% to 45 % , an isobornyl acrylate monomer in an amount of about 15% to 40% of the decorative metallic composition, a photoinitiator in an amount of about 4% to 14% of the decorative metallic composition, a flow promoting agent in an amount of 0% to 8% of the decorative metallic composition, and a metallic pigment in an amount of 5 % to 40 % .
  • the preferred decorative metallic compositions according to this method are those described herein, for example, including the compositions described in examples 1, 2, and 3.
  • the decorative metallic composition may be applied to the substrate using a number of different techniques.
  • the decorative metallic composition may be applied, for example, by direct brush application, dipping, or it may be sprayed onto the substrate surface. It also may be applied using a screen printing technique. In such screen printing technique, a "screen" as the term is used in the screen printing industry is used to regulate the flow of liquid composition onto the substrate surface.
  • the decorative metallic composition typically would be applied to the screen as the latter contacts the substrate. The decorative metallic composition flows through the silk screen to the substrate, whereupon it adheres to the substrate at the desired film thickness.
  • Screen printing techniques suitable for this purpose include known techniques, but wherein the process is adjusted in ways known to persons of ordinary skill in the art to accommodate the viscosity, flowability, and other properties of the liquid-phase composition, the substrate and its surface properties, etc.
  • Flexographic techniques for example, using pinch rollers to contact the decorative metallic composition with a rolling substrate, also may be used.
  • the method includes a second step of illuminating the decorative metallic fluid-phase composition on the substrate with an ultraviolet light to cause the decorative metallic fluid-phase composition to cure into the decorative metallic coating.
  • This illumination may be carried out in any number of ways, provided the ultraviolet light or radiation impinges upon the decorative metallic composition so that the decorative metallic composition is caused to polymerize to form the coating, layer, film, etc., and thereby cures.
  • Curing preferably takes place by free radical polymerization, which is initiated by an ultraviolet radiation source.
  • the photoinitiator preferably comprises a photoinitiator, as described above.
  • ultraviolet light sources may be used, depending on the application.
  • Preferred ultraviolet radiation sources for a number of applications include known ultraviolet lighting equipment with energy intensity settings of, for example, 125 watts, 200 watts, and 300 watts per square inch.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une composition métallique de décoration réticulable sous l'effet des ultraviolets et un procédé pour réaliser une telle composition, procédé pouvant être utilisée pour produire un revêtement métallique de décoration à appliquer sur un substrat. Ladite composition ne contient aucune quantité significative de solvants organiques volatils qui ne s'incorporent pas à la couche active après réticulation.
EP00992185A 1999-12-06 2000-12-06 Compositions reticulables sous l'effet d'uv pour la production de revetements metalliques de decoration Withdrawn EP1252242A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US16924799P 1999-12-06 1999-12-06
US169247P 1999-12-06
PCT/US2000/042605 WO2001040387A2 (fr) 1999-12-06 2000-12-06 Compositions reticulables sous l'effet d'uv pour la production de revetements metalliques de decoration

Publications (1)

Publication Number Publication Date
EP1252242A2 true EP1252242A2 (fr) 2002-10-30

Family

ID=22614814

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00992185A Withdrawn EP1252242A2 (fr) 1999-12-06 2000-12-06 Compositions reticulables sous l'effet d'uv pour la production de revetements metalliques de decoration

Country Status (5)

Country Link
EP (1) EP1252242A2 (fr)
AU (1) AU4139601A (fr)
CA (1) CA2392515A1 (fr)
MX (1) MXPA02005284A (fr)
WO (1) WO2001040387A2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8630678B2 (en) 2006-11-06 2014-01-14 Google Inc. Modifying a signal by controlling transmit diversity parameters

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2864077C (fr) * 2012-02-07 2017-08-01 Actega Kelstar, Inc. Compositions decoratives metalliques sechant sous uv

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4959178A (en) * 1987-01-27 1990-09-25 Advanced Products Inc. Actinic radiation-curable conductive polymer thick film compositions and their use thereof
US5180757A (en) * 1987-12-16 1993-01-19 Michael Lucey Photopolymerizable compositions used in electronics
US6290881B1 (en) * 1999-04-14 2001-09-18 Allied Photochemical, Inc. Ultraviolet curable silver composition and related method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0140387A2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8630678B2 (en) 2006-11-06 2014-01-14 Google Inc. Modifying a signal by controlling transmit diversity parameters

Also Published As

Publication number Publication date
WO2001040387A3 (fr) 2001-12-13
AU4139601A (en) 2001-06-12
MXPA02005284A (es) 2003-09-22
WO2001040387A2 (fr) 2001-06-07
CA2392515A1 (fr) 2001-06-07

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