WO2009128957A1 - Oligomères d'acrylates durcissables par rayonnement, réductibles par l'eau, et leurs revêtements durcis - Google Patents

Oligomères d'acrylates durcissables par rayonnement, réductibles par l'eau, et leurs revêtements durcis Download PDF

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Publication number
WO2009128957A1
WO2009128957A1 PCT/US2009/002469 US2009002469W WO2009128957A1 WO 2009128957 A1 WO2009128957 A1 WO 2009128957A1 US 2009002469 W US2009002469 W US 2009002469W WO 2009128957 A1 WO2009128957 A1 WO 2009128957A1
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Prior art keywords
ethoxylated
multifunctional acrylate
acrylate oligomer
water
acceptor
Prior art date
Application number
PCT/US2009/002469
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English (en)
Inventor
Michael L. Gould
Sheldon X. Zhang
Hilbert Esselbrugge
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Ashland Licensing And Intellectual Property Llc
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Application filed by Ashland Licensing And Intellectual Property Llc filed Critical Ashland Licensing And Intellectual Property Llc
Publication of WO2009128957A1 publication Critical patent/WO2009128957A1/fr

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    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

  • the invention concerns water-reducible multifunctional acrylate oligomers formed by the reaction of acrylate monomers and oligomers with ⁇ - keto esters (e.g., acetoacetates), ⁇ -diketones (e.g., 2,4-pentanedione), ⁇ -keto amides (e.g., acetoacetanilide, acetoacetamide), and/or other ⁇ -dicarbonyl compounds that can participate in the Michael addition reaction as Michael donors.
  • the constituents of the Michael addition reaction impart hydrophilicity to the resulting oligomer.
  • the invention further pertains to coatings comprising multifunctional acrylate oligomers. Background of the Invention
  • Multifunctional acrylates and methacrylates are commonly utilized in the preparation of crosslinked films, adhesives, foundry sand binders, composite materials, and the like.
  • Uncrosslinked resins prepared via the Michael addition reaction of ⁇ -dicarbonyl compounds with multifunctional acrylates have been disclosed in the art.
  • trimethylol propane triacrylate (TMPTA) can be 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) to make the photoactive oligomer shown in Fig. 1.
  • An advantage of energy-cured acrylic systems is that such systems can be applied and cured with little or no solvent, thus reducing the total amount of HAPS/VOCs released to the environment.
  • a limitation in solvent-free coating systems is achieving sufficient wetting and laydown of liquid films at viscosities suitable for spray application and other typical applications.
  • Medium molecular weight oligomers typically provide robust physical properties to their cured formulated coatings. But, with higher molecular weight comes higher viscosity, in most cases. The viscosity may be reduced with diluent monomers (e.g., HDDA, NPGDA, DPGDA, TRPGDA, etc.) although this often gives rise to worker exposure issues.
  • solvent other than organic solvent such as water, must be chosen to moderate viscosity and improve coating performance.
  • the water-reducible multifunctional acrylate oligomers are formed through the Michael addition reaction between Michael "acceptors”, such as acrylate monomers and oligomers, and Michael “donors", such as ⁇ -keto esters (e.g., acetoacetates), ⁇ -diketones (e.g., 2,4-pentanedione), ⁇ -keto amides (e.g., acetoacetanilide, acetoacetamide), and/or other ⁇ -dicarbonyl compounds that can participate in the Michael addition reaction as Michael donors.
  • Michael "acceptors" such as acrylate monomers and oligomers
  • Michael “donors” such as ⁇ -keto esters (e.g., acetoacetates), ⁇ -diketones (e.g., 2,4-pentanedione), ⁇ -keto amides (e.g., acetoacetanilide, acetoacetamide),
  • the acceptor compounds and/or Michael donor compounds in the Michael addition reaction comprise non-charged moieties, typically ethoxylated species, which results in an oligomer that is hydrophilic.
  • the ethoxylated chain segments impart water affinity to each molecule and levels of ethylene oxide concentrations will impart sufficient water affinity to develop hydrophilicity.
  • the reaction product may be in the form of a stable emulsion, such as a water-in-oil emulsion or an oil-in- water emulsion, depending on the level of water dilution.
  • the oligomers resulting from the Michael addition reaction between ethoxylated Michael donors and/or acceptors can by cured by chemical means, thermally, or by the application of energy, such as exposure to UV or electron beam radiation.
  • energy such as exposure to UV or electron beam radiation.
  • resins comprising the oligomer compounds can be used as coatings for a variety of substrates including metal, plastic, wood, paper, glass and the like, in addition to other substrates as would be appreciated by one skilled in the art.
  • Final film properties e.g., water sensitivity, solvent resistance, hardness, scratch resistance and the like, to name a few) will dictate whether or not water removal prior to cure is necessary.
  • Formulations comprising the resins and oligomers may further comprise other functional materials, additives and fillers.
  • such formulations may comprise both reactive materials (like conventional polyacrylates) and non-reactive materials (like solvents) to enhance the coating properties.
  • additives include a variety of acrylic 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 invention encompasses coating formulations comprising at least ' the oligomers disclosed herein as well as formulations comprising the oligomers, the functional additives and fillers as discussed herein, and, optionally, other materials which would be recognized by one skilled in the art as beneficial in coating formulations.
  • viscosity thinning of the oligomer resulting from the Michael addition reaction between ethoxylated Michael donor and/or acceptor and/or resins comprising these oligomers require thinning, i.e. reduction in viscosity.
  • the oligomer and/or resin may be thinned with solvent, in particular water. In certain embodiments, relatively little amounts of water can provide a significant reduction in oligomer viscosity, thereby making application by spray, flood coat or gravure techniques practical.
  • UV lithographic inks from self-photoinitiating resins in particular, for food applications, such as incorporation of the oligomers into lithographic ink formulated, either alone or with other monomers, such as, propoxylated glycerol triacrylate, for food packaging applications.
  • DETAILED DESCRIPTION OF THE DRAWINGS [0012] Fig.
  • TMPTA trimethylol propane triacrylate
  • EAA ethyl acetoacetate
  • DBU 1 ,8-diazabicyclo[5.4.0]undec-7-ene
  • TMPTA ethoxylated trimethylol propane triacrylate
  • EAA ethyl acetoacetate
  • DBU 1,8- diazabicyclo [5.4.0]undec-7-ene
  • FIG. 3 shows a reaction sequence comprising trimethylol propane triacrylate (TMPTA) reacted in a 2:1 molar ratio with an ethoxylated methoxy polyethylene glycol (MPEG) having an ethoxylation number of 5.2 in the presence of 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) to make a photoactive oligomer in accordance with the invention which is then combined with monomer and solvent and subjected to UV radiation to form a cured network.
  • TMPTA trimethylol propane triacrylate
  • MPEG ethoxylated methoxy polyethylene glycol
  • DBU 1,8-diazabicyclo [5.4.0]undec-7-ene
  • TMPTA ethoxylated trimethylol propane triacrylate
  • MPEG ethoxylated methoxy polyethylene glycol
  • DBU 1 ,8-diazabicyclo [5.4.0]undec- 7-ene
  • One or more of the acceptors and/or Michael donors applied in the Michael addition reaction which results in the oligomer is preferably ethoxylated.
  • the reaction can proceed with a) one or more acceptors that are not ethoxylated and one or more Michael donors wherein at least one Michael donor is ethoxylated, b) one or more acceptors, wherein at least one acceptor is ethoxylated, and one or more Michael donors that are not ethoxylated or c) one or more acceptors and one or more Michael donors wherein at least one acceptor and at least one Michael donor is ethoxylated.
  • the ethoxylated species in the reaction i.e.
  • the ethoxylated acceptor and/or ethoxylated Michael donor has an ethoxylation number (EO) of between about 1 and about 30.
  • EO ethoxylation number
  • the reaction results in an ethoxylated oligomer and/or resin comprising an ethoxylated oligomer which has water affinity and/or is hydrophilic.
  • An embodiment of the invention concerns an oligomer comprising three ethylene oxide side chain units, made by the reaction sequence shown in Fig. 2.
  • the Michael addition reaction oligomer shown in Fig. 2 possesses a greater degree of water affinity than non-ethoxylated compounds, such as the prior art oligomer discussed above and shown in Fig. 1 , but may not possess as much water affinity as other ethoxylated Michael addition reaction oligomers, such as those of Fig. 3 and Fig. 4.
  • the ethoxylated oligomer resulting from the reaction sequence shown in Fig. 2 is capable of aqueous viscosity reduction as a "water-in-oil" emulsion that is stable enough for coating over a period of hours.
  • non-ethoxylated (i.e., hydrophobic) trimethylol propane triacrylate (TMPTA) monomer is reacted with an ethoxylated (i.e., hydrophilic) Michael donor as shown in Fig. 3 to create an ethoxylated oligomer.
  • TMPTA non-ethoxylated trimethylol propane triacrylate
  • the degree of ethoxylation is controlled by selection of the starting methoxy polyethylene glycol (MPEG) alcohol prior to acetoacetylation. In this case, reduction with water is very efficient and the resulting "water-in-oil" mixture is completely clear. Based on the lack of turbidity the inventors theorize without wishing to be bound to any theory that the mixture is very stable, owing in large part to the 'surfactant-like' EO tail on each oligomer. Separation of resin from water occurs, generally over a period of days.
  • TMPEO3TA hydrophilic ethoxylated Michael acceptor
  • the invention demonstrates the advantageous use of these uncrosslinked resins alone or modified by reaction/blending with additional materials in water-reducible coating formulations on a variety of substrates. These additional materials include a variety of acrylic monomers and oligomers, primary and secondary amines, organonitro compounds, acid- functional materials, siloxanes, elastomers, waxes and others to modify and improve coating performance.
  • additional materials include a variety of acrylic monomers and oligomers, primary and secondary amines, organonitro compounds, acid- functional materials, siloxanes, elastomers, waxes and others to modify and improve coating performance.
  • the oligomers of the invention 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, and the like, which decompose to form radicals when heated, or at ambient temperature in the presence of amines or transition metal promoters.
  • Electron beam (EB) radiation is another energy source suitable for initiating reaction of acrylic moieties.
  • the oligomers described herein offer significant advantages over traditional multifunctional acrylic oligomers.
  • viscosity can be reduced by either diluent monomers or water and the oligomers can be cured upon exposure to UV radiation without additional photoinitiator.
  • the amount of water necessary for a desired viscosity reduction will be a function of the specific application, such as a specific coating application technique.
  • the amount of water needed for effective viscosity reduction may be low, in certain embodiments about 5% to about 10% water by weight may be sufficient for effective viscosity reduction.
  • the resins and blends disclosed herein exhibit performance properties that make them 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 while exhibiting wide ranges of hardness, toughness, flexibility, tensile strength, stain resistance, scratch resistance, impact resistance, solvent resistance, and the like. Nearly any desired coating performance parameter can be attained by proper selection of raw material building blocks.
  • Resin performance properties were measured by a variety of different test methods. For purposes of defining properties by means familiar to others skilled in the art, the following test methods were utilized:
  • Example 1 (Comparative) [0028] Trimethylol propane triacrylate (TMPTA), ethyl acetoacetate (EAA) and diazabicycloundecene (DBU) were combined in the reaction sequence shown in Fig. 1 according to the methods described in U.S. Patent Nos. 5,945,489 and 6,025,410, which are incorporated in their entirety herein by reference, to obtain the oligomer shown in Fig. 1 and discussed above. The reactor temperature was set to 80 0 C and held at that temperature for approximately four hours. When the reaction was judged to be complete according to refractometry, the resin was discharged from the reactor and allowed to cool.
  • TMPTA Trimethylol propane triacrylate
  • EAA ethyl acetoacetate
  • DBU diazabicycloundecene
  • Neat resin viscosity at room temperature was measured by a Brookfield viscometer (spindle # 4, 50 rpm). Additional resin samples were diluted with deionized water to 95% and 90% solids and their viscosities were determined and compiled in the data table below. The neat and water-reduced resin products were applied to steel panels and irradiated with UV light from a medium pressure mercury lamp (Fusion "H" bulb) at a total dose of 500 mJ/cm 2 . Table 1 provides the results of the performance testing for the resins and cured films of this example. Water is not effective to reduce viscosity of this oligomer.
  • TMPTA Trimethylol propane triacrylate
  • MPEG350AA methoxy polyethylene glycol 350 acetoacetate
  • DBU diazabicycloundecene
  • the self-initiating photocurable oligomers that range in degree of water affinity (from dispersible with limited emulsion stability to highly water soluble and stable in solution) were made via the Michael addition reaction of ⁇ -ketoesters and polyacrylate monomers. The more highly hydrophilic the Michael donor, the more soluble and stable the final oligomer in aqueous media. Water sensitivity of cured films followed the inverse trend.
  • An additional benefit of cured films made from these oligomers is that they are very tough and flexible, much more than would be expected from standard free radical-cured acrylic systems based on ethoxylated monomers. Degree of cure can be influenced by additional components in order to boost cure response (i.e., cure "speed") on lines with or without infrared, RF or standard "driers".

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention porte sur des oligomères d'acrylates multifonctionnels comprenant le produit de réaction d'un donneur et d'un accepteur de Michael, l'oligomère d'acrylate multifonctionnel étant hydrophile. Le donneur et/ou l'accepteur de Michael peuvent être éthoxylés. Les oligomères d'acrylates multifonctionnels peuvent être incorporés dans des compositions de revêtement et de l'eau peut être utilisée pour une réduction de viscosité. Les compositions de revêtement sont typiquement durcissables, par des moyens chimiques, thermiquement ou par l'application d'énergie, par exemple par exposition à un rayonnement ultraviolet ou un rayonnement de faisceau d'électrons.
PCT/US2009/002469 2008-04-18 2009-04-21 Oligomères d'acrylates durcissables par rayonnement, réductibles par l'eau, et leurs revêtements durcis WO2009128957A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010108985A1 (fr) * 2009-03-25 2010-09-30 Dsm Ip Assets B.V. Revêtement antifouling biologique amélioré
EP2695921A1 (fr) * 2012-08-10 2014-02-12 Ricoh Company, Ltd. Composition durcissable par rayonnement actif, composition d'encre d'impression à jet d'encre vulcanisable par rayon actif et composition adhésive durcissable par rayonnement actif utilisant celle-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7094826B2 (en) * 2000-10-14 2006-08-22 Dsm Ip Assets B.V. Aqueous hyperbranched macromolecule coating compositions
US7214725B2 (en) * 2004-04-30 2007-05-08 Ashland Licensing And Intellectual Property Llc Radiation-curable lithographic inks from multifunctional acrylate oligomers
US7317061B2 (en) * 2004-04-29 2008-01-08 Ashland Licensing And Intellectual Property Llc Self-photoinitiating water-dispersible acrylate ionomers and synthetic methods

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7094826B2 (en) * 2000-10-14 2006-08-22 Dsm Ip Assets B.V. Aqueous hyperbranched macromolecule coating compositions
US7317061B2 (en) * 2004-04-29 2008-01-08 Ashland Licensing And Intellectual Property Llc Self-photoinitiating water-dispersible acrylate ionomers and synthetic methods
US7214725B2 (en) * 2004-04-30 2007-05-08 Ashland Licensing And Intellectual Property Llc Radiation-curable lithographic inks from multifunctional acrylate oligomers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010108985A1 (fr) * 2009-03-25 2010-09-30 Dsm Ip Assets B.V. Revêtement antifouling biologique amélioré
CN102361941A (zh) * 2009-03-25 2012-02-22 帝斯曼知识产权资产管理有限公司 改进的防生物结垢涂层
EP2695921A1 (fr) * 2012-08-10 2014-02-12 Ricoh Company, Ltd. Composition durcissable par rayonnement actif, composition d'encre d'impression à jet d'encre vulcanisable par rayon actif et composition adhésive durcissable par rayonnement actif utilisant celle-ci
CN103576456A (zh) * 2012-08-10 2014-02-12 株式会社理光 活性射线能固化的组合物以及油墨组合物和粘合剂组合物
US10005922B2 (en) 2012-08-10 2018-06-26 Ricoh Company, Ltd. Active ray-curable composition, and active ray-curable inkjet printing ink composition and active ray-curable adhesive composition using the same

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