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
  • 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
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G

Definitions

• the invention is directed to the use of vinyl neoester monomers in radiation curable applications such as coatings and adhesives.
• Formulations using vinyl neoesters provide for low VOC compositions having low odor.
• VOC volatile organic compounds
• a typical radiation curable formulation mainly comprises oligomer resin and monomer. Examples of oligomer resins used are epoxy, epoxy-acrylate, and urethane-acrylate.
• Alkyl acrylate, di- or tri-functional acrylate monomers are also used as reactive diluents to provide the required viscosity and the network structure required for a finished product.
• the radiation curable formulation generally contains an initiator, which is capable of being activated by the radiation source, generating free radicals.
• the formulation when cured will be converted into polymeric composition with no residual solvent or water to vaporize.
• radiation curing is energy efficient, cost-effective, provides faster cure, and thus affords higher productivity.
• Coatings can be formulated to 100% solids where minimum waste is generated, and heat sensitive substrates can be easily coated.
• vinyl neoester monomers in radiation curable coatings technology provides a low VOC medium with low odor.
• Typical vinyl neoester monomers have high boiling points, low viscosities, and low odor.
• This family of monomers when mixed with a suitable initiator, can be cured by either ultraviolet (UV) or electron beam radiation. These monomers can be used as a comonomer or as a reactive diluent in commonly used radiation curable formulations.
• the vinyl neoester monomers according to the present inventon have the following general structure: Rt O
• Ri, R 2 , and R ⁇ are independently selected from hydrocarbyl groups, which may be branched or straight chain, each having preferably from 1 to 10 carbon atoms More preferably Ri + R 2 + R ⁇ range from 3 to 23 carbon atoms, still more preferably from 5 to 23 carbon atoms, and even more preferably from 8 to 14 carbon atoms
• a typical commercial product normally contains the blend of various isomers
• vinyl neodecanoate (EXXAR® Neo-10) consists of isomers with average Ri + R 2 + R 3 equal to eight carbon atoms
• EXXAR® Neo-12 the blend of isomers have an average Ri +
• R + Ri equal to ten carbon atoms
• Preferable vinyl neoesters include vinyl neodecanoate (available from ExxonMobil Chemical Company as EXXAR® Neo- 10) and vinyl neododecanoate available from ExxonMobil Chemical Company as EXXAR® Neo-12), have low viscosities, high boiling points in the range of 193-247 ° C, and very low odor These types of monomers are therefore ideal for radiation curable applications that can replace alkyl acrylates Since these monomers also have low viscosity, they can also function as reactive diluents for the high molecular weight oligomer resins In order to demonstrate that vinyl neoester monomers function as reactive diluents and can be cured by radiation, formulations shown in Table 1 were prepared.
• Cyracure® UVR 6100 is a cycloaliphatic epoxide resin available from Union Carbide.
• UVI 6990 and UVI 6974 are mixed triarylsulfonium hexafluoro phosphate and antimonate salts respectively; these photoinitiators are available from Union Carbide.
• FC430 is a coating additive for effective wetting and leveling, available from 3M. Brookfield Viscosities were determined at 25° C using Spindle #18 at 0.6 RPM using Model DV-II.
• Photomer® 3016 is an epoxyacrylate resin from Henkel.
• Irgacure® 651 ( ⁇ , ⁇ -dimethoxy, ⁇ -phenyl acetophenone) is a photoinitiator from Ciba-Geigy Benzophenone is a photoinitiator and triethanolamine is a photoactivator, both available from numerous sources.
• formulations Ex. 5 to Ex. 9 formed 100% solids coatings formulations with necessary viscosity profiles required for coatings applications, toluene was added to all the formulations for comparative purposes and to make other formulations reach the desired flow. Brookfield Viscosites were determined at 25° C using Spindle #31 at 1.5 RPM using Model DV-II.
• oligomer and monomer choices will depend on the final film properties desired.
• the vinyl neoester monomers suitable for this application cover a wide range of molecular weights with Ri + R 2 + R from 5 to 23 carbon atoms.
• oligomer resins used are epoxy acrylate, urethane acrylate, polyester acrylate, epoxy, silicone epoxy, and epoxy silane.
• UV radiation other radiation sources such as electron beam, microwave, and infrared can also be used for similar curing purposes.
• Radiation curable formulations can be used in a wide range of end use coating operations such as in automotive, electronic, release, overprint, pre- finished wood, wood furniture, plastic substrates, hardwood flooring, fiber optics, nail polish, metal containers, coil metal, and the like.
• vinyl neoesters may be used in radiation curable applications.
• Preferred embodiments include:
• a radiation curable formulation comprising a radiation-curable monomer or oligomer resin and a comonomer or reactive diluent having the vinyl neoester structure shown previously, preferably wherein Ri, R 2 , and R ⁇ are independently selected from Cl to CIO hydrocarbyl groups and other preferred and more preferred limitations to these substituents as described above, particularly wherein
• Ri + R 2 + R 3 ranges from 3 to 23 carbon atoms; and most preferably such formulations wherein the comonomer or reactive diluent is selected from vinyl neodecanoate, vinyl neododecanoate, and mixtures thereof; such formulations wherein the vinyl neoester is a comonomer with one or more radiation curable monomers, most preferably alkyl acrylates; or wherein the vinyl neoester is a reactive diluent with a radiation curable oligomer resin, particularly oligomer resins selected from epoxy acrylate, urethane acrylate, polyester acrylate, epoxy, silicone epoxy, epoxy silane, and mixtures thereof.
• the present invention concerns articles coated with such a radiation cureable coating, e.g., an article inch ding a substrate having a coating on at least one surface, the coating comprising a polymer formed by curing, using a radiation source, a radiation curable monomer, particularly alkyl acrylates, and/or oligomer resin (preferably those specifically mentioned above) in the presence of a vinyl neoester as comonomer or reactive diluent.
• a radiation curable monomer particularly alkyl acrylates, and/or oligomer resin (preferably those specifically mentioned above) in the presence of a vinyl neoester as comonomer or reactive diluent.
• oligomer resin selected from epoxy acrylate, urethane acrylate, polyester acrylate, epoxy, silicon epoxy, epoxy silane, and mixtures thereof.
• Still another preferred embodiment is a method of providing a coating using radiation curable formulation, the improvement comprising using a vinyl neoester as comonomer with a radiation curable monomer such as alkyl acrylates or reactive diluent with radiation curable oligomer resins, such as epoxy acrylate, urethane acrylate, polyester acrylate, epoxy, silicon epoxy, epoxy silane, and mixtures thereof.
• a radiation curable monomer such as alkyl acrylates or reactive diluent with radiation curable oligomer resins, such as epoxy acrylate, urethane acrylate, polyester acrylate, epoxy, silicon epoxy, epoxy silane, and mixtures thereof.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Paints Or Removers (AREA)

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• 1999
  • 1999-12-17 EP EP99966443A patent/EP1242541A1/de not_active Withdrawn
  • 1999-12-17 AU AU21977/00A patent/AU2197700A/en not_active Abandoned
  • 1999-12-17 WO PCT/US1999/030268 patent/WO2001044378A1/en not_active Application Discontinuation

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