WO2005108452A2 - Radiation-curable michael addition resins having built-in photoinitiators - Google Patents

Radiation-curable michael addition resins having built-in photoinitiators Download PDF

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Publication number
WO2005108452A2
WO2005108452A2 PCT/US2005/013196 US2005013196W WO2005108452A2 WO 2005108452 A2 WO2005108452 A2 WO 2005108452A2 US 2005013196 W US2005013196 W US 2005013196W WO 2005108452 A2 WO2005108452 A2 WO 2005108452A2
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Prior art keywords
michael
type
acceptor
donor
modified
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PCT/US2005/013196
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French (fr)
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WO2005108452A3 (en
Inventor
Michael L. Gould
Terry E. Hammond
Sridevi Narayan-Sarathy
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Ashland Licensing And Intellectual Property Llc
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Priority to JP2007509548A priority Critical patent/JP2007534800A/en
Priority to EP20050737393 priority patent/EP1740621B1/en
Priority to BRPI0510100A priority patent/BRPI0510100B1/en
Priority to DE200560021773 priority patent/DE602005021773D1/en
Priority to CA 2563358 priority patent/CA2563358A1/en
Priority to CN2005800185878A priority patent/CN101027326B/en
Priority to AU2005241006A priority patent/AU2005241006A1/en
Priority to AT05737393T priority patent/ATE470680T1/en
Publication of WO2005108452A2 publication Critical patent/WO2005108452A2/en
Publication of WO2005108452A3 publication Critical patent/WO2005108452A3/en

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    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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    • C03—GLASS; MINERAL OR SLAG WOOL
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    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
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    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C08G18/2835—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds having less than 5 ether groups
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3215—Polyhydroxy compounds containing aromatic groups or benzoquinone groups
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
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    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
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    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31645—Next to addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood

Definitions

  • the present invention relates to multifunctional acrylate oligomers (Michael addition resins) formed from the reaction of acrylate monomers and oligomers
  • ketoesters ⁇ -diketones, ⁇ -ketoamides and the like that can participate in the
  • the invention relates to improved Michael addition resins with better cure response that have been modified to contain additional photoactive moieties, such as photoinitiators and/or photosensitizers.
  • the improved Michael addition resins have multiple photoactive groups resulting directly from the Michael addition reaction as well as pendant Type I photoactive moieties (e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphine oxides) or Type II photoactive moieties (e.g., substituted benzophenones, thioxanthones, camphorquinones, or bisimidazoles).
  • Type I photoactive moieties e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphine oxides
  • Type II photoactive moieties e.g., substituted benzophenones, thioxanthones, camphorquinones, or bisimidazoles.
  • Multifunctional acrylates and methacrylates are commonly utilized in the preparation of crosslinked films, adhesives, foundry sand binders, composite materials, etc.
  • US 5,945,489 and US 6,025,410 both Ashland, Inc. disclose
  • the present invention comprises liquid, uncrosslinked, UV-curable Michael addition resins prepared
  • Type II e.g., substituted benzophenones, thioxanthones, camphorquinones or bisimidazoles
  • the resulting oligomers thus possess either or both Type I and Type II photoactive functional groups that promote the addition polymerization of acrylic groups upon exposure to UV light.
  • This structural change provides a supplementary chromophore for the initiation of free radical polymerization in addition to the photoactive substituted ketone formed during the Michael reaction.
  • the invention disclosed here demonstrates the advantageous use of these uncrosslinked resins alone or modified by reaction/blending with additional materials in coatings applications on a variety of substrates.
  • additional materials include a variety of acrylic and vinyl monomers and oligomers, primary and secondary amines, organonitro compounds, acid-functional materials, siloxanes, elastomers, waxes and others to modify and improve coatings performance.
  • the oligomers described above can be cured by all methods typically used to crosslink acrylic materials, though most advantageously by exposure to UV radiation. Cure, or crosslinking, is usually accomplished through a free radical chain mechanism, which may require any of a number of free radical- generating species such as peroxides, hydroperoxides, REDOX complexes, etc., which decompose to form radicals when heated, or at ambient temperature in the presence of amines and transition metal promoters. Electron beam ( ⁇ -iB) radiation is another energy source suitable for initiating reaction of acrylic moieties.
  • the resins described in this invention offer significant advantages over traditional multifunctional acrylic monomers and oligomers in that they can be cured upon exposure to UV radiation without additional photoinitiator.
  • Traditional multifunctional acrylates and/or oligomers will not cure upon exposure to UV radiation unless a photoinitiator, often at relatively high levels, is added to coating formulations.
  • Traditional photoinitiators e.g., benzophenone
  • decomposition of some traditional photoinitiators results in cleavage products (e.g. benzaldehyde) that are of concern from a health perspective.
  • Cleavage fragments may "bloom" to the surface of cured coatings where they can come into contact with skin.
  • the invention disclosed here allows for the expeditious use of these traditional chromophore moieties while anchoring or "tethering" the largest fragments to the thermoset coating matrix.
  • novel resins and blends disclosed herein exhibit performance properties that make them very effective coating materials. These properties can be modified greatly depending upon composition. Resins can be produced that show excellent adhesion to metals, plastics, wood, paper and glass. They exhibit wide ranges of hardness, toughness, flexibility, tensile strength, stain resistance, scratch resistance, impact resistance, solvent resistance, etc. Almost any desired coating performance parameter can be attained by proper selection of raw material building blocks.
  • ⁇ -ketoesters e.g., acetoacetates
  • ⁇ -diketones e.g., 2, 4-pentanedione
  • ⁇ -keto amides e.g., acetoacetanilide, acetoacetamide
  • ⁇ -keto amides e.g., acetoacetanilide, acetoacetamide
  • the Michael addition resins of the invention are modified to contain photoactive moieties that function as photoinitiators. That is, the resulting Michael oligomer has multiple photoactive ketone groups directly resulting from the Michael Addition reaction, as disclosed in U.S. 5,945,489 and 6,025,410, as well as pendant Type I photoactive moieties (e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphine oxides) or Type II photoactive moieties (e.g., substituted benzophenones, thioxanthones, camphorquinones or
  • novel oligomers described above will cure at low doses of UV radiation under standard UV-cure conditions.
  • Other materials both reactive (conventional polyacrylates) and non-reactive (e.g., solvents) may also be incorporated into the system to enhance the coatings properties.
  • These additives include a variety of acrylic and vinyl monomers and oligomers, primary and secondary amines, organonitro compounds, acid-functional monomers and oligomers, organic and inorganic fillers, silicones, waxes and elastomers, among others.
  • the resins exhibit excellent performance when used as coatings for a variety of substrates including metal, plastic, wood, paper and glass. These coatings may be cured via chemical means, thermally, or by exposure to UV or electron beam radiation.
  • TMPTA Trimethylol propane triacrylate
  • EAA ethyl acetoacetate
  • DBU 1 , 8- diazabicyclo[5.4.0]undec-7-ene
  • TMPTA is combined with benzophenone.
  • Methyl diethanolamine is added as a synergist to improve the efficiency of the polymerization.
  • the mixture cures to a very brittle, highly crosslinked film upon exposure to UV radiation.
  • FIG. 3 A traditional benzyl ketal class photoinitiator (4-(2- hydroxyethoxy)phenyl-2-hydroxy-2-propyl ketone) is reacted with functionalizing reagents to yield the product molecules as shown.
  • the product molecules, being acetoacetoxy functional (A), or acrylic functional (B, C) are then utilized in the reaction scheme detailed in Figure 4.
  • Figure 5 Illustrates contrasting chromophores that comprise traditional Type I ⁇ -cleavage photoinitiator, Michael adduct self-initiating oligomer and hybrid dual chromophore (Type I photoactive moiety plus Michael product substituted ketone). Circled areas indicate the point of homolytic bond cleavage to produce initiating radical species.
  • H-abstraction photoinitiator hydroxy benzophenone
  • the invention relates to liquid, uncrosslinked, UV-curable Michael addition resins that have been modified to contain Type I and/or Type II photoactive moieties.
  • a Michael addition resin is equivalents termed a Michael polyacrylate resin, a Michael oligomer, a Michael adduct, or a Michael addition product.
  • the Michael addition resins of the present invention can be prepared in the presence of catalysts.
  • Other components known in the art can be added to the liquid, uncrosslinked, UV- curable Michael addition resin such as amine synergists, reactive diluents, silicones, waxes, and the like.
  • the liquid, uncured Michael addition resin is a polyacrylate oligomer formed from a multifunctional acrylate Michael acceptor and a ⁇ -dicarbonyl Michael donor.
  • a small amount of mono-functional acrylate can be incorporated along with the multifunctional acrylates to modify the product oligomers, for instance, to enhance adhesion, toughness or other characteristics of the final Michael adduct.
  • This technology is described in U.S. Patents 5,945,489 and 6,025,410, both assigned to Ashland Inc., the entire contents of which are incorporated by reference.
  • the ⁇ -dicarbonyl Michael donor is suitably chosen from among ⁇ -ketoesters,
  • the multifunctional acrylate Michael acceptor is suitably chosen from among onoacrylates, diacrylates,
  • mono- or multifunctional acrylate acceptors affords the composition designer the opportunity to exercise a great range of selectivity in the properties of the final product.
  • Monoacrylates include, but are not limited to: 2-phenoxyethyl acrylate (PEA) and/or higher order alkoxylated products, isobornyl acrylate, tetrahydrofurfuryl acrylate (THFFA), glycidyl acrylate, dodecyl acrylate, phenylthioethyl acrylate, acrylate-functional polysiloxanes, perfluoroalkyl ethyl acrylate esters and mixtures thereof.
  • PDA 2-phenoxyethyl acrylate
  • TFFA tetrahydrofurfuryl acrylate
  • glycidyl acrylate dodecyl acrylate
  • phenylthioethyl acrylate acrylate-functional polysiloxanes
  • perfluoroalkyl ethyl acrylate esters and mixtures thereof.
  • the monoacrylate is present in amounts up to about 20 wt%, preferably up
  • Diacrylates include, but are not limited to: ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, tertraethylene glycol diacrylate, tetrapropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, bisphenol A diglycidyl ether diacrylate, resorcinol diglycidyl ether diacrylate, 1,3- propanediol diacrylate, 1 ,4-butanediol diacrylate, 1 ,5-pentanediol diacrylate, 1 ,6-hexanediol diacrylate, neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate, ethoxylated neopentyl glycol diacryl
  • Triacrylates include, but are not limited to: trimethylol propane triacrylate, glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, aryl urethane triacrylates, aliphatic urethane triacrylates, melamine triacrylates, epoxy novolac triacrylates, aliphatic epoxy triacrylate, polyester triacrylate, and mixtures thereof.
  • Tetraacrylates include, but are not limited to: di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol tetraacrylate, aryl urethane tetraacrylates, aliphatic urethane tetraacrylates, polyester tetraacrylates, melamine tetraacrylates, epoxy novolac tetraacrylates, acrylate-functional polysiloxanes and mixtures thereof.
  • the present invention can be practiced with a ⁇ -ketoester (e.g., ethyl)
  • acetoacetate a ⁇ -ketoanilide (e.g., acetoacetanilide), a ⁇ -ketoamide (e.g.,
  • Suitable ⁇ -dicarbonyl donor compounds having functionality of 2 include, but are not limited to: ethyl acetoacetate, methyl acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate, t-butyl acetoacetate, acetoacetanilide, N- alkyl acetoacetanilide, acetoacetamide, 2-acetoacetoxylethyl acrylate, 2- acetoacetoxylethyl methacrylate, allyl acetoacetate, benzyl acetoacetate, 2, 4- pentanedione, isobutyl acetoacetate, and 2-methoxyethyl acetoacetate.
  • Suitable ⁇ -dicarbonyl donor compounds having functionality of 4 include, but are not limited to: 1, 4-butanediol diacetoacetate, 1 , 6-hexanediol diacetoacetate, neopentyl glycol diacetoacetate, cyclohexane dimethanol diacetoacetate, and ethoxylated bisphenol A diacetoacetate.
  • Suitable ⁇ -dicarbonyl donor compounds having functionality of 6 include, but are not limited to: trimethylol propane triacetoacetate, glycerin triacetoacetate, and polycaprolactone triacetoacetates.
  • the Michael addition reaction is catalyzed by a strong base.
  • a strong base is diazabicycloundecene (DBU), which is sufficiently strong and is readily soluble in the monomer mixtures.
  • DBU diazabicycloundecene
  • Other cyclic amidines for example diazabicyclo-nonene (DBN) and guanidines are also suitable for catalyzing this reaction.
  • Group I alkoxide bases such as potassium tert-butoxide, provided they have sufficient solubility in the reaction medium, and are also typically adequate to promote t e desired reaction.
  • Quaternary hydroxides and alkoxides such as tetrabutyl ammonium hydroxide or benzyltri methyl ammonium methoxide, comprise another class of base catalysts that promote the Michael addition reaction.
  • strong, organophilic alkoxide bases can be generated in situ from the reaction between a halide anion (e.g., quaternary halide) and an epoxide moiety.
  • a halide anion e.g., quaternary halide
  • epoxide moiety e.g., quaternary halide
  • the Michael addition resins disclosed can also be modified to enhance performance by adding an amine synergist.
  • An example of such a modification includes incorporating primary or secondary amines into the uncured Michael addition resin. This technique is disclosed in U.S. Patent No. 6,673,851 the entire teaching of which is incorporated herein by reference.
  • Typical primary amines include ethanolamine, methyl-1 ,6-hexanediamine, 3- aminopropyltrimethoxysilane, diaminopropane, benzyl amine, triethylenetetraamine, isophorone diamine and mixtures thereof.
  • Typical secondary amines include dimethylamine, dibutyl amine, diethanolamine (DEA), piperidine, morpholine and mixtures thereof. If the liquid Michael addition resin is modified with a primary or secondary amine, the modifying amine is simply reacted with the liquid, uncured, Michael addition resin.
  • acceptors are modified to contain pendant Type I (e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphine oxides) or Type II (e.g., substituted benzophenones, thioxanthones, camphorquinones or bisimidazoles) photoactive moieties.
  • Type I e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphine oxides
  • Type II e.g., substituted benzophenones, thioxanthones, camphorquinones or bisimidazoles
  • modified Michael donors include Michael donors containing a Type I photoactive moiety having the mixed structures
  • W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group.
  • W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group.
  • W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group.
  • W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group and the like.
  • the resin products described in the following examples can be diluted with common solvents for spray application to substrates, or applied at 100% solids by means consistent with article shape and constitution. Application of the resins to substrates in these examples was accomplished by the "draw down” technique to produce films of varying thickness, unless otherwise noted. Cure was effected by exposure to a single 600W Fusion "H" bulb at the specified dose. Chemical resistance assessments were done on phosphate-treated steel panels.
  • Resin performance properties were measured by a variety of test methods. For purposes of defining properties by means familiar to others skilled in the art, the following test methods were utilized:
  • Irgacure 2959 Type I photoinitiator Irgacure 2959 from Ciba-Geigy, 224.25 g, was added to 250 ml toluene in a 2-liter, 3-neck round bottom flask equipped with overhead stirrer, thermocouple, condenser and nitrogen inlet. 158.2 g tert-butyl acetoacetate from Eastman Chemical Company was added and the reactor was stirred at room temperature until homogeneous. The reactor contents were then heated to 110 °C and the reactor was held at that temperature for 30 minutes.
  • Glycidyl acetoacetate was prepared according to the method of Witzeman and Nottingham (J. Org. Chem, 1991 , 56, 1713). Glycidol (Dixie Chemical Company, Pasadena, TX), 296 g, t-butyl acetoacetate, 632.8 g, and toluene, 500 ml, were mixed in a 1 -liter reactor equipped with mechanical stirrer, thermocouple, condenser and nitrogen inlet. The reactor contents were heated to 110 °C and held at that temperature for 30 minutes. The reactor was then fitted with a distillation head and the toluene/t-butanol azeotrope was distilled from the reactor over 2 hours under moderate nitrogen flow.
  • Peak temperature reached in the reactor was 120 °C. After 4 hours total time, the reaction mixture was cooled and stripped on a rotary evaporator at 70 °C for 2 hours. The yellow liquid product was analyzed by proton NMR. Essentially quantitative conversion of glycidol to glycidyl acetoacetate was confirmed.
  • Irgacure 2959 Type I photoinitiator 132 g was added to ethyl acetate in a 2- liter, 3-neck round bottom flask equipped with overhead stirrer, thermocouple, condenser and addition funnel with a nitrogen inlet.
  • Cold acryloyl chloride (Aldrich Chemical Company, Milwaukee, Wl), 57.9 g, was added and the reactor was cooled to ⁇ 5 °C with an ice bath.
  • Triethylamine, 65 g was added dropwise over 90 minutes, keeping reactor temperature below 10 °C. The yellow " slurry" was stirred for 2 hours at room temperature and a sample analyzed by FTIR.
  • Methylene diphenyl diisocyanate (Mondur ML, Bayer), 528 g, and hexanediol diacrylate (HDDA), 605 g, were stirred in a 2-liter resin kettle equipped with overhead stirrer, thermocouple, condenser and air inlet.
  • Dibutyltin dilaurate (DABCO T-12, Air Products), 0.81 g, and Irgacure 2959, 448.5 g, were added to the stirring mixture and the reactor was heated to 60 °C.
  • 2-HEA 232.4 g, was then added slowly over 30 minutes, keeping peak temperature below 65 °C. Subsequent reaction was monitored by FTIR.
  • the reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by 13 C NMR. After 4 hours, diethanol amine, 7.9 g, was added to the mixture and the reaction product was cooled to room temperature with stirring.
  • the final product was a low viscosity clear liquid having a cone and plate viscosity of 231 cP.
  • the resin product was applied to a phosphate-treated steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb).
  • the final product was a low viscosity, clear liquid having a cone and plate viscosity of 320 cP.
  • the resin was applied to a phosphate-treated steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb).
  • the reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by refractive index measurement.
  • 2-(4- chlorobenzoyl) benzoic acid (CBBA) 14.6 g, was added and held at temperature for approximately two hours. At such time, all of the CBBA had been consumed by reaction with epoxy moieties. After 6 hours total cook time, diethanol amine, 8.0 g, was added and the reaction mixture cooled to room temperature with stirring.
  • the final product was a low viscosity clear liquid having a cone and plate viscosity of 366 cP.
  • the resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb).
  • Hexanediol diacrylate 114.8 g, Actilane 584 (Akzo Nobel Resins), 31.7 g, XZ 92551.00 epoxy acrylate, 28.5 g, glycidyl acetoacetate (GAA), 12.5 g and tetrabutylammonium bromide, 0.96 g, were combined according to the method described in US patent no. 6,706,414.
  • the reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by a refractive index measurement.
  • 2- benzoylbenzoic acid (BBA) 10.3 g, was added and held at temperature for approximately two hours. At such time, all of the BBA had been consumed by reaction with epoxy moieties.
  • diethanol amine 7.6 g, was added to the mixture and the reaction product was cooled to room temperature with stirring.
  • the final product was a low viscosity clear liquid having a cone and plate viscosity of 230 cP.
  • the resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb). The following properties were tabulated for the resin prepared above:
  • Hexanediol diacrylate 192.3 g, trimethylol propane triacrylate, 44.4 g, ethyl acetoacetate, 35.8 g, Irgacure 2959-based acrylate ester, 9.3 g of 75% w/w solution in HDDA from material preparation 3, tetrabutylammonium bromide, 1.45 g and glycidyl methacrylate, 5.8 g were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by 13 C NMR. After 3 hours total reaction time, diethanol amine, 6.0 g, was added to the mixture and the reaction product cooled to room temperature with stirring.
  • the final product was a low viscosity clear liquid having a cone and plate viscosity of 111 cP.
  • the resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb). The following properties were tabulated for the resin prepared above:
  • Hexanediol diacrylate 192.3 g, trimethylol propane triacrylate, 44.4 g, ethyl acetoacetate, 35.8 g, Irgacure 2959-based urethane acrylate, 19.7 g of 75% w/w solution in HDDA, similar to that from material preparation 4, tetrabutylammonium bromide, 1.46 g and glycidyl methacrylate, 5.8 g were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by refractive index. After 4.5 hours total reaction time, diethanol amine, 12.0 g, was added to the mixture and the reaction product cooled to room temperature with stirring.
  • the final product was a low viscosity clear liquid having a cone and plate viscosity of 301 cP.
  • the resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb). The following properties were tabulated for the resin prepared above:
  • Hexanediol diacrylate, 203.6 g, XZ 92551.00 epoxy acrylate, 45.0 g, 2,4- pentanedione, 25.0 g, Ebecryl P-36 acrylic benzophenone ester, 14.5 g, tetrabutylammonium bromide, 1.48 g and glycidyl methacrylate, 5.9 g were combined according to the method described in US patent no. 6,706,414.
  • the reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by refractive index. After 5.5 hours total reaction time, diethanol amine, 4.0 g, was added to the mixture and the reaction product cooled to room temperature with stirring.
  • the final product was a low viscosity clear liquid having a cone and plate viscosity of 180 cP.
  • the resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb). The following properties were tabulated for the resin prepared above:
  • novel resins and blends disclosed here exhibit performance properties that make them very effective coating materials and these properties can be modified greatly depending upon composition.
  • Resins can be produced that show excellent adhesion to metals, plastics, wood, paper and glass. They exhibit wide ranges of hardness, toughness, flexibility, tensile strength, stain resistance, scratch resistance, impact resistance, solvent resistance, etc. Almost any desired coating performance parameter can be attained by proper selection of raw material building blocks.

Abstract

The liquid, uncrosslinked, UV-curable Michael addition resins and blends of the present invention exhibit performance properties that make them very effective coating materials and these properties can be modified greatly depending upon composition. Michael donors and acceptors can be constructed from Type I and/or Type II photoinitiators and can be included in the coating compositions disclosed to make UV-curable coatings with extraordinary photoreactivity and properties. Resins can be produced that show excellent adhesion to metals, plastics, wood, paper and glass. They exhibit wide ranges of hardness, toughness, flexibility, tensile strength, stain resistance, scratch resistance, impact resistance, solvent resistance, etc. Almost any desired coating performance parameter can be attained by proper selection of raw material building blocks.

Description

Radiation Curable Michael Addition Resins Having Built-in iPhotolnitiators
Background of the Invention
The present invention relates to multifunctional acrylate oligomers (Michael addition resins) formed from the reaction of acrylate monomers and oligomers
(Michael acceptors) and β-dicarbonyl compounds (Michael donors) such as β-
ketoesters, β-diketones, β-ketoamides and the like that can participate in the
Michael addition reaction. In particular the invention relates to improved Michael addition resins with better cure response that have been modified to contain additional photoactive moieties, such as photoinitiators and/or photosensitizers. The improved Michael addition resins have multiple photoactive groups resulting directly from the Michael addition reaction as well as pendant Type I photoactive moieties (e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphine oxides) or Type II photoactive moieties (e.g., substituted benzophenones, thioxanthones, camphorquinones, or bisimidazoles).
Multifunctional acrylates and methacrylates are commonly utilized in the preparation of crosslinked films, adhesives, foundry sand binders, composite materials, etc. US 5,945,489 and US 6,025,410 (both Ashland, Inc.) disclose
liquid, uncrosslinked resins prepared via the Michael addition reaction of β-
dicarbonyl compounds with multifunctional acrylates. The present invention comprises liquid, uncrosslinked, UV-curable Michael addition resins prepared
utilizing β-dicarbonyl Michael donors and/or acrylate acceptors that are modified to contain pendant Type I (e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphi'ne oxides ) or Type II (e.g., substituted benzophenones, thioxanthones, camphorquinones or bisimidazoles) photoactive moieties. The resulting oligomers thus possess either or both Type I and Type II photoactive functional groups that promote the addition polymerization of acrylic groups upon exposure to UV light. This structural change provides a supplementary chromophore for the initiation of free radical polymerization in addition to the photoactive substituted ketone formed during the Michael reaction.
The invention disclosed here demonstrates the advantageous use of these uncrosslinked resins alone or modified by reaction/blending with additional materials in coatings applications on a variety of substrates. These additional materials include a variety of acrylic and vinyl monomers and oligomers, primary and secondary amines, organonitro compounds, acid-functional materials, siloxanes, elastomers, waxes and others to modify and improve coatings performance.
The oligomers described above can be cured by all methods typically used to crosslink acrylic materials, though most advantageously by exposure to UV radiation. Cure, or crosslinking, is usually accomplished through a free radical chain mechanism, which may require any of a number of free radical- generating species such as peroxides, hydroperoxides, REDOX complexes, etc., which decompose to form radicals when heated, or at ambient temperature in the presence of amines and transition metal promoters. Electron beam (ϊ-iB) radiation is another energy source suitable for initiating reaction of acrylic moieties.
The resins described in this invention offer significant advantages over traditional multifunctional acrylic monomers and oligomers in that they can be cured upon exposure to UV radiation without additional photoinitiator. Traditional multifunctional acrylates and/or oligomers will not cure upon exposure to UV radiation unless a photoinitiator, often at relatively high levels, is added to coating formulations. Traditional photoinitiators (e.g., benzophenone) can be insoluble, toxic, expensive, and contribute to film color, which can limit applicability of the coating over white and light-colored substrates. Furthermore, decomposition of some traditional photoinitiators results in cleavage products (e.g. benzaldehyde) that are of concern from a health perspective. Cleavage fragments may "bloom" to the surface of cured coatings where they can come into contact with skin. The invention disclosed here allows for the expeditious use of these traditional chromophore moieties while anchoring or "tethering" the largest fragments to the thermoset coating matrix.
The novel resins and blends disclosed herein exhibit performance properties that make them very effective coating materials. These properties can be modified greatly depending upon composition. Resins can be produced that show excellent adhesion to metals, plastics, wood, paper and glass. They exhibit wide ranges of hardness, toughness, flexibility, tensile strength, stain resistance, scratch resistance, impact resistance, solvent resistance, etc. Almost any desired coating performance parameter can be attained by proper selection of raw material building blocks.
Summary of the Invention
The invention detailed herein comprises a family of novel multifunctional acrylate oligomers formed by the reaction of acrylate monomers and oligomers
with β-ketoesters (e.g., acetoacetates), β-diketones (e.g., 2, 4-pentanedione),
β-keto amides (e.g., acetoacetanilide, acetoacetamide), and/or other β-
dicarbonyl compounds that can participate in the Michael addition reaction as Michael donors, and the use of these resins in coatings. The Michael addition resins of the invention are modified to contain photoactive moieties that function as photoinitiators. That is, the resulting Michael oligomer has multiple photoactive ketone groups directly resulting from the Michael Addition reaction, as disclosed in U.S. 5,945,489 and 6,025,410, as well as pendant Type I photoactive moieties (e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphine oxides) or Type II photoactive moieties (e.g., substituted benzophenones, thioxanthones, camphorquinones or
bisimidazoles). This allows for a much lower loading of β-dicarbonyl Michael
donor, resulting in oligomers with reduced viscosity and better cure response than those previously disclosed.
The novel oligomers described above will cure at low doses of UV radiation under standard UV-cure conditions. Other materials, both reactive (conventional polyacrylates) and non-reactive (e.g., solvents) may also be incorporated into the system to enhance the coatings properties. These additives include a variety of acrylic and vinyl monomers and oligomers, primary and secondary amines, organonitro compounds, acid-functional monomers and oligomers, organic and inorganic fillers, silicones, waxes and elastomers, among others. The resins exhibit excellent performance when used as coatings for a variety of substrates including metal, plastic, wood, paper and glass. These coatings may be cured via chemical means, thermally, or by exposure to UV or electron beam radiation.
Brief Description of the Several Drawings
Figure 1. Trimethylol propane triacrylate (TMPTA) is reacted in a 2:1 molar ratio with ethyl acetoacetate (EAA) in the presence of 1 , 8- diazabicyclo[5.4.0]undec-7-ene (DBU). The resulting polyacrylate oligomer has dual functionality. It has both acrylic functionality (tetra) and a substituted ketone group that is capable of dissociating to initiate free radical polymerization of the oligomer upon exposure to UV light.
Figure 2. TMPTA is combined with benzophenone. Methyl diethanolamine is added as a synergist to improve the efficiency of the polymerization. The mixture cures to a very brittle, highly crosslinked film upon exposure to UV radiation.
Figure 3. A traditional benzyl ketal class photoinitiator (4-(2- hydroxyethoxy)phenyl-2-hydroxy-2-propyl ketone) is reacted with functionalizing reagents to yield the product molecules as shown. The product molecules, being acetoacetoxy functional (A), or acrylic functional (B, C) are then utilized in the reaction scheme detailed in Figure 4.
Figure 4. Creation of a novel "hybrid chromophore" Michael adduct from Type
I α-cleavage acetoacetate Michael donor and TMPTA.
Figure 5 Illustrates contrasting chromophores that comprise traditional Type I α-cleavage photoinitiator, Michael adduct self-initiating oligomer and hybrid dual chromophore (Type I photoactive moiety plus Michael product substituted ketone). Circled areas indicate the point of homolytic bond cleavage to produce initiating radical species.
Figure 6. Creation of novel "hybrid chromophore" Michael adduct from Type II
H-abstraction photoinitiator (hydroxy benzophenone), glycidyl acetoacetate
Michael donor and TMPTA.
Detailed Description of the Invention
The invention relates to liquid, uncrosslinked, UV-curable Michael addition resins that have been modified to contain Type I and/or Type II photoactive moieties. For purposes of this invention a Michael addition resin is equivalents termed a Michael polyacrylate resin, a Michael oligomer, a Michael adduct, or a Michael addition product. The Michael addition resins of the present invention can be prepared in the presence of catalysts. Other components known in the art can be added to the liquid, uncrosslinked, UV- curable Michael addition resin such as amine synergists, reactive diluents, silicones, waxes, and the like.
The liquid, uncured Michael addition resin is a polyacrylate oligomer formed from a multifunctional acrylate Michael acceptor and a β-dicarbonyl Michael donor. A small amount of mono-functional acrylate can be incorporated along with the multifunctional acrylates to modify the product oligomers, for instance, to enhance adhesion, toughness or other characteristics of the final Michael adduct. This technology is described in U.S. Patents 5,945,489 and 6,025,410, both assigned to Ashland Inc., the entire contents of which are incorporated by reference.
The β-dicarbonyl Michael donor is suitably chosen from among β-ketoesters,
β-diketones, β-ketoamides, and β-ketoanilides. The multifunctional acrylate Michael acceptor is suitably chosen from among onoacrylates, diacrylates,
triacrylates, tetraacrylates and the like. The range of β-dicarbonyl donors and
mono- or multifunctional acrylate acceptors affords the composition designer the opportunity to exercise a great range of selectivity in the properties of the final product.
Monoacrylates include, but are not limited to: 2-phenoxyethyl acrylate (PEA) and/or higher order alkoxylated products, isobornyl acrylate, tetrahydrofurfuryl acrylate (THFFA), glycidyl acrylate, dodecyl acrylate, phenylthioethyl acrylate, acrylate-functional polysiloxanes, perfluoroalkyl ethyl acrylate esters and mixtures thereof. When used the monoacrylate is present in amounts up to about 20 wt%, preferably up to about 10 wt%, based on the total weight of the Michael addition resin.
Diacrylates include, but are not limited to: ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, tertraethylene glycol diacrylate, tetrapropylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, bisphenol A diglycidyl ether diacrylate, resorcinol diglycidyl ether diacrylate, 1,3- propanediol diacrylate, 1 ,4-butanediol diacrylate, 1 ,5-pentanediol diacrylate, 1 ,6-hexanediol diacrylate, neopentyl glycol diacrylate, cyclohexane dimethanol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated cyclohexanedimethanol diacrylate, propoxylated cyclohexanedimethanol diacrylate, thiodiglycol diacrylate, acrylate-functional polysiloxanes, epoxy diacrylate, aryl urethane diacrylate, aliphatic urethane diacrylate, polyester diacrylate, and mixtures thereof.
Triacrylates include, but are not limited to: trimethylol propane triacrylate, glycerol triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, tris (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated glycerol triacrylate, propoxylated glycerol triacrylate, pentaerythritol triacrylate, aryl urethane triacrylates, aliphatic urethane triacrylates, melamine triacrylates, epoxy novolac triacrylates, aliphatic epoxy triacrylate, polyester triacrylate, and mixtures thereof.
Tetraacrylates include, but are not limited to: di-trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol tetraacrylate, aryl urethane tetraacrylates, aliphatic urethane tetraacrylates, polyester tetraacrylates, melamine tetraacrylates, epoxy novolac tetraacrylates, acrylate-functional polysiloxanes and mixtures thereof. The present invention can be practiced with a β-ketoester (e.g., ethyl
acetoacetate), a β-ketoanilide (e.g., acetoacetanilide), a β-ketoamide (e.g.,
acetoacetamide) or a mixture of Michael donors according to the desired resin quality.
Suitable β-dicarbonyl donor compounds having functionality of 2 include, but are not limited to: ethyl acetoacetate, methyl acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate, t-butyl acetoacetate, acetoacetanilide, N- alkyl acetoacetanilide, acetoacetamide, 2-acetoacetoxylethyl acrylate, 2- acetoacetoxylethyl methacrylate, allyl acetoacetate, benzyl acetoacetate, 2, 4- pentanedione, isobutyl acetoacetate, and 2-methoxyethyl acetoacetate.
Suitable β-dicarbonyl donor compounds having functionality of 4 include, but are not limited to: 1, 4-butanediol diacetoacetate, 1 , 6-hexanediol diacetoacetate, neopentyl glycol diacetoacetate, cyclohexane dimethanol diacetoacetate, and ethoxylated bisphenol A diacetoacetate.
Suitable β-dicarbonyl donor compounds having functionality of 6 include, but are not limited to: trimethylol propane triacetoacetate, glycerin triacetoacetate, and polycaprolactone triacetoacetates.
The Michael addition reaction is catalyzed by a strong base. An example of such a base is diazabicycloundecene (DBU), which is sufficiently strong and is readily soluble in the monomer mixtures. Other cyclic amidines, for example diazabicyclo-nonene (DBN) and guanidines are also suitable for catalyzing this reaction. Group I alkoxide bases such as potassium tert-butoxide, provided they have sufficient solubility in the reaction medium, and are also typically adequate to promote t e desired reaction. Quaternary hydroxides and alkoxides, such as tetrabutyl ammonium hydroxide or benzyltri methyl ammonium methoxide, comprise another class of base catalysts that promote the Michael addition reaction. Finally, strong, organophilic alkoxide bases can be generated in situ from the reaction between a halide anion (e.g., quaternary halide) and an epoxide moiety. Such in situ catalysts are disclosed in U.S. Patent No.6, 706,414 assigned to Ashland, Inc. the entire contents of which are specifically incorporated herein by reference.
The Michael addition resins disclosed can also be modified to enhance performance by adding an amine synergist. An example of such a modification includes incorporating primary or secondary amines into the uncured Michael addition resin. This technique is disclosed in U.S. Patent No. 6,673,851 the entire teaching of which is incorporated herein by reference. Typical primary amines include ethanolamine, methyl-1 ,6-hexanediamine, 3- aminopropyltrimethoxysilane, diaminopropane, benzyl amine, triethylenetetraamine, isophorone diamine and mixtures thereof. Typical secondary amines include dimethylamine, dibutyl amine, diethanolamine (DEA), piperidine, morpholine and mixtures thereof. If the liquid Michael addition resin is modified with a primary or secondary amine, the modifying amine is simply reacted with the liquid, uncured, Michael addition resin.
In the present invention the β-dicarbonyl Michael donor and/or Michael
acceptors are modified to contain pendant Type I (e.g., substituted benzoins, benzyl ketals, acetophenones or acyl phosphine oxides) or Type II (e.g., substituted benzophenones, thioxanthones, camphorquinones or bisimidazoles) photoactive moieties. The resulting liquid, uncrosslinked Michael addition resins possess either or both Type I and Type II photoactive functional groups that promote the addition polymerization of acrylic groups upon exposure to UV light in addition to a substituted ketone resulting from the Michael addition reaction. Examples of modified Michael donors include Michael donors containing a Type I photoactive moiety having the mixed structures
Figure imgf000012_0001
Michael donors containing a Type II photoactive moiety having the structure, including isomers
Figure imgf000012_0002
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group. Michael donors containing a Type II photoactive moiety having the structure, including isomers
Figure imgf000012_0003
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group. Michael donors containing a Type II photoactive moiety having the structure,
including isomers
Figure imgf000013_0001
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group, and R is a simple alkyl or aryl group. Michael donors containing a Type II photoactive moiety having the structure, including isomers
Figure imgf000013_0002
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group. Michael donors containing a Type II photoactive moiety having the structure, including formula isomers
Figure imgf000013_0003
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group and the like.
The resin products described in the following examples can be diluted with common solvents for spray application to substrates, or applied at 100% solids by means consistent with article shape and constitution. Application of the resins to substrates in these examples was accomplished by the "draw down" technique to produce films of varying thickness, unless otherwise noted. Cure was effected by exposure to a single 600W Fusion "H" bulb at the specified dose. Chemical resistance assessments were done on phosphate-treated steel panels.
Resin performance properties were measured by a variety of test methods. For purposes of defining properties by means familiar to others skilled in the art, the following test methods were utilized:
Dynamic Viscosity - value in Poise at the defined temperature based on constant shear cone and plate measurement
Cure Response - value assignment of 1 (wet; uncured), 2 (sticky), 3 ("greasy surface", easily marred), 4 (tack-free, can be marred with cotton swab), or 5 (tack-free/mar-free) based on assessment of coating following exposure to a "benchmark" dose of 500 mJ/cm2 total radiation.
Minimum Dose to Tack-Free / Mar-Free Cure - total dose in mJ/cm2 to achieve a "5" rating on the above scale.
MEK resistance - # of MEK double rubs required to break through or
significantly mar the coating The following examples illustrate the constitution, application, cure and performance properties of the novel multifunctional acrylate oligomers detailed in this disclosure.
Material Preparation 1 : Irgacure 2959 Acetoacetate
Irgacure 2959 Type I photoinitiator Irgacure 2959 from Ciba-Geigy, 224.25 g, was added to 250 ml toluene in a 2-liter, 3-neck round bottom flask equipped with overhead stirrer, thermocouple, condenser and nitrogen inlet. 158.2 g tert-butyl acetoacetate from Eastman Chemical Company was added and the reactor was stirred at room temperature until homogeneous. The reactor contents were then heated to 110 °C and the reactor was held at that temperature for 30 minutes.
After 1 hour of total heating time, the reactor was fitted with a distillation head and the toluene/t-butanol azeotrope was stripped off under moderate nitrogen flow until the pot temperature reached 125 °C. At such time, the reactor contents were decanted into a 1 -liter single neck round bottom flask and the yellow liquid was stripped on a rotary evaporator for 2 hours at 70 °C with a slight nitrogen sparge. 309 g of viscous yellow liquid were recovered. Analysis by NMR suggested near quantitative conversion of the Irgacure 2959 as a mixture of primary or tertiary esters. For easier handling, the resin was diluted with trimethylol propane (ethoxy) triacrylate (TMPEOTA) to 52% w/w active acetoacetate. Material Preparation 2: Glycidyl Acetoacetate
Glycidyl acetoacetate was prepared according to the method of Witzeman and Nottingham (J. Org. Chem, 1991 , 56, 1713). Glycidol (Dixie Chemical Company, Pasadena, TX), 296 g, t-butyl acetoacetate, 632.8 g, and toluene, 500 ml, were mixed in a 1 -liter reactor equipped with mechanical stirrer, thermocouple, condenser and nitrogen inlet. The reactor contents were heated to 110 °C and held at that temperature for 30 minutes. The reactor was then fitted with a distillation head and the toluene/t-butanol azeotrope was distilled from the reactor over 2 hours under moderate nitrogen flow. Peak temperature reached in the reactor was 120 °C. After 4 hours total time, the reaction mixture was cooled and stripped on a rotary evaporator at 70 °C for 2 hours. The yellow liquid product was analyzed by proton NMR. Essentially quantitative conversion of glycidol to glycidyl acetoacetate was confirmed.
Material Preparation 3: 2959 Acrylate Ester
Irgacure 2959 Type I photoinitiator, 132 g, was added to ethyl acetate in a 2- liter, 3-neck round bottom flask equipped with overhead stirrer, thermocouple, condenser and addition funnel with a nitrogen inlet. Cold acryloyl chloride (Aldrich Chemical Company, Milwaukee, Wl), 57.9 g, was added and the reactor was cooled to <5 °C with an ice bath. Triethylamine, 65 g, was added dropwise over 90 minutes, keeping reactor temperature below 10 °C. The yellow "slurry" was stirred for 2 hours at room temperature and a sample analyzed by FTIR. Very little hydroxyl functionality was observed and the reaction was judged to be complete. The product was suction filtered at room temperature and the filter cake rinsed with ethyl acetate twice. The product liquor was then poured into a 500 ml single neck flask and stripped on a rotary evaporator with light sparge of dry air at 40 °C for 2 hours. 163 g of viscous yellow liquid were recovered. Analyses by NMR and FTIR suggested near quantitative conversion (>97%) of the Irgacure 2959. For easier handling, the resin was diluted with hexanediol diacrylate (HDDA) to 75 % w/w active 2959 acrylate ester.
Material Preparation 4: 2959 / HEA MDI Diacrylate
Methylene diphenyl diisocyanate (Mondur ML, Bayer), 528 g, and hexanediol diacrylate (HDDA), 605 g, were stirred in a 2-liter resin kettle equipped with overhead stirrer, thermocouple, condenser and air inlet. Dibutyltin dilaurate (DABCO T-12, Air Products), 0.81 g, and Irgacure 2959, 448.5 g, were added to the stirring mixture and the reactor was heated to 60 °C. 2-HEA, 232.4 g, was then added slowly over 30 minutes, keeping peak temperature below 65 °C. Subsequent reaction was monitored by FTIR. The constituents were heated for a total of 25 hours at which time, the reaction was deemed complete by both NMR and FTIR. An additional 605 g of HDDA were added, creating a 50% w/w concentration of 2959 urethane acrylate in monomer. Example 1 "Benchmark Example": No Built-in Type I or Type II Photoinitiator
Hexanediol diacrylate, 126.6 g, trimethylol propane triacrylate (TMPTA), 9.8 g, XZ 92551.00 epoxy acrylate (The Dow Chemical Company, Midland, Ml), 29.6 g, ethyl acetoacetate (EAA), 21.4 g, tetrabutylammonium bromide, 0.96 g and glycidyl methacrylate, 3.8 g were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by 13C NMR. After 4 hours, diethanol amine, 7.9 g, was added to the mixture and the reaction product was cooled to room temperature with stirring.
The final product was a low viscosity clear liquid having a cone and plate viscosity of 231 cP. The resin product was applied to a phosphate-treated steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb).
The following properties were tabulated for the resin prepared above:
Figure imgf000018_0001
Example 2
Hexanediol diacrylate, 113.8 g, trimethylol propane triacrylate, 8.8 g, XZ 92551.00 epoxy acrylate, 26.6 g, ethyl acetoacetate, 16.1 g, Irgacure 2959- based acetoacetate, 22.8 g of 50% w/w solution from material preparation 1 , tetrabutylammonium bromide, 0.96 g and glycidyl methacrylate, 3.9 g were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by 13C NMR. After 4 hours, diethanol amine, 7.1 g, was added to the mixture and the reaction product cooled to room temperature with stirring.
The final product was a low viscosity, clear liquid having a cone and plate viscosity of 320 cP. The resin was applied to a phosphate-treated steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb).
The following properties were tabulated for the resin prepared above:
Figure imgf000019_0001
Figure imgf000020_0001
Example 3
Hexanediol diacrylate, 129.3 g, trimethylol propane triacrylate, 10.0 g, XZ 92551.00 epoxy acrylate, 30.2 g, glycidyl acetoacetate (GAA), 17.7 g and tetrabutylammonium bromide, 0.96 g, were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by refractive index measurement. 2-(4- chlorobenzoyl) benzoic acid (CBBA), 14.6 g, was added and held at temperature for approximately two hours. At such time, all of the CBBA had been consumed by reaction with epoxy moieties. After 6 hours total cook time, diethanol amine, 8.0 g, was added and the reaction mixture cooled to room temperature with stirring.
The final product was a low viscosity clear liquid having a cone and plate viscosity of 366 cP. The resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb).
The following properties were tabulated for the resin prepared above:
Figure imgf000021_0001
Example 4
Hexanediol diacrylate, 114.8 g, Actilane 584 (Akzo Nobel Resins), 31.7 g, XZ 92551.00 epoxy acrylate, 28.5 g, glycidyl acetoacetate (GAA), 12.5 g and tetrabutylammonium bromide, 0.96 g, were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by a refractive index measurement. 2- benzoylbenzoic acid (BBA), 10.3 g, was added and held at temperature for approximately two hours. At such time, all of the BBA had been consumed by reaction with epoxy moieties. After 7 hours total cook time, diethanol amine, 7.6 g, was added to the mixture and the reaction product was cooled to room temperature with stirring.
The final product was a low viscosity clear liquid having a cone and plate viscosity of 230 cP. The resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb). The following properties were tabulated for the resin prepared above:
Figure imgf000022_0001
Example 5
Hexanediol diacrylate, 192.3 g, trimethylol propane triacrylate, 44.4 g, ethyl acetoacetate, 35.8 g, Irgacure 2959-based acrylate ester, 9.3 g of 75% w/w solution in HDDA from material preparation 3, tetrabutylammonium bromide, 1.45 g and glycidyl methacrylate, 5.8 g were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by 13C NMR. After 3 hours total reaction time, diethanol amine, 6.0 g, was added to the mixture and the reaction product cooled to room temperature with stirring.
The final product was a low viscosity clear liquid having a cone and plate viscosity of 111 cP. The resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb). The following properties were tabulated for the resin prepared above:
Figure imgf000023_0001
Example 6
Hexanediol diacrylate, 192.3 g, trimethylol propane triacrylate, 44.4 g, ethyl acetoacetate, 35.8 g, Irgacure 2959-based urethane acrylate, 19.7 g of 75% w/w solution in HDDA, similar to that from material preparation 4, tetrabutylammonium bromide, 1.46 g and glycidyl methacrylate, 5.8 g were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by refractive index. After 4.5 hours total reaction time, diethanol amine, 12.0 g, was added to the mixture and the reaction product cooled to room temperature with stirring.
The final product was a low viscosity clear liquid having a cone and plate viscosity of 301 cP. The resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb). The following properties were tabulated for the resin prepared above:
Figure imgf000024_0001
Example 7
Hexanediol diacrylate, 203.6 g, XZ 92551.00 epoxy acrylate, 45.0 g, 2,4- pentanedione, 25.0 g, Ebecryl P-36 acrylic benzophenone ester, 14.5 g, tetrabutylammonium bromide, 1.48 g and glycidyl methacrylate, 5.9 g were combined according to the method described in US patent no. 6,706,414. The reactor temperature was set to 95 °C and held at that temperature until 100% disubstitution of the Michael donor was achieved, as defined by refractive index. After 5.5 hours total reaction time, diethanol amine, 4.0 g, was added to the mixture and the reaction product cooled to room temperature with stirring.
The final product was a low viscosity clear liquid having a cone and plate viscosity of 180 cP. The resin product was applied to a steel panel and irradiated with UV light from a 600 W/in medium pressure mercury lamp (Fusion "H" bulb). The following properties were tabulated for the resin prepared above:
Figure imgf000025_0001
The novel resins and blends disclosed here exhibit performance properties that make them very effective coating materials and these properties can be modified greatly depending upon composition. Resins can be produced that show excellent adhesion to metals, plastics, wood, paper and glass. They exhibit wide ranges of hardness, toughness, flexibility, tensile strength, stain resistance, scratch resistance, impact resistance, solvent resistance, etc. Almost any desired coating performance parameter can be attained by proper selection of raw material building blocks.

Claims

Having thus described the invention, we claim,
1. A liquid, uncrosslinked, UV-curable Michael addition resin, comprising the reaction product of; A. a Type I and/or Type II photoinitiator-modified Michael donor and a Michael acceptor, B. a Type I and/or Type II photoinitiator-modified Michael acceptor and a Michael donor, or C. a Michael donor, a Michael acceptor and a Type I and/or Type II photoinitiator.
2. The Michael addition resin of claim 1 , wherein the Type I photoinitiator is a substituted benzoin, a benzyl ketal, an acetophenone, an acyl phosphine oxide or mixtures thereof.
3. The Michael addition resin of claim 1 , wherein the Type II photoinitiator is a substituted benzophenone, a thioxanthone, a camphorquinone a bisimidazole or mixtures thereof.
4. The Michael addition resin of claim , wherein the Michael donor is a β- ketoester, a β-ketoamide, a β-ketoanilide or mixtures thereof.
5. The Michael addition resin of claim 1 , wherein the Michael acceptor is a multifunctional acrylate.
6. The Michael addition resin of claim 1 , wherein the Michael acceptor is a mixture of a multifunctional acrylate and a monofunctional acrylate.
7. The Michael addition resin of claim 5, wherein the Michael acceptor is a monoacrylate, a diacrylate, a triacrylate, a tetraacrylate.
8. The Michael addition resin of claim 4, wherein the Michael donor has a functionality of 2, 4, 6 or mixtures thereof.
9. the MicKaei addition resin of claim 1 , further comprising an amine synergist.
10. The Michael addition resin of claim 1 , further comprising a catalyst.
11. The Michael addition resin of claim 1 , further comprising a reactive diluent.
12. A modified Michael donor or acceptor containing a Type I and/or Type II photoactive moiety.
13. The modified Michael donor or acceptor of claim 12, wherein the Type I photoactive moiety is a substituted benzoin, a benzyl ketal, an acetophenone, an acyl phosphine oxide or mixtures thereof.
14. The modified Michael donor or acceptor of claim 12, wherein the Type II photoactive moiety is a substituted benzophenone, a thioxanthone, a camphorquinone a bisimidazole or mixtures thereof.
15. The modified Michael donor or acceptor of claim 12, wherein the Michael donor contains a Type I photoactive moiety having the mixed structures
Figure imgf000027_0001
16. The modified Michael donor or acceptor of claim 12, wherein the Michael donor contains a Type II photoactive moiety having the structure, including isomers
Figure imgf000027_0002
wnere w, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group.
17. The modified Michael donor or acceptor of claim 12, wherein the Michael donor contains a Type II photoactive moiety having the structure, including isomers
Figure imgf000028_0001
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group.
18. The modified Michael donor or acceptor of claim 12, wherein the Michael donor contains a Type II photoactive moiety having the structure, including isomers
Figure imgf000028_0002
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group, and R is a simple alkyl or aryl group.
19. The modified Michael donor or acceptor of claim 12, wherein the Michael donor contains a Type II photoactive moiety having the structure, including isomers
Figure imgf000029_0001
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group.
20. The modified Michael donor or acceptor of claim 12, wherein the Michael donor contains a Type II photoactive moiety having the structure, including formula isomers
Figure imgf000029_0002
where W, X, Y and/or Z are, independent of each other, a halogen, hydrogen, alkyl, alkoxy, aryl, amino, alkylamino, nitrile, nitro, sulpho-, or phospho- group.
21. A coating comprising the cured, crosslinked residue of the Michael addition product of claim 1.
22. The coating of claim 21 , wherein the Michael addition product is cured by exposure to actinic radiation.
23. An article, comprising; A. a substrate, and B. a cured, crosslinked residue of the Michael addition product of claim 1.
24. The article of claim 23, wherein the substrate is metal, plastic, wood, paper or glass.
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