WO2000024786A1 - Procede de stabilisation dans un milieu aqueux, d'un monomere/prepolymere insoluble dans l'eau, durcissable par radiation - Google Patents

Procede de stabilisation dans un milieu aqueux, d'un monomere/prepolymere insoluble dans l'eau, durcissable par radiation Download PDF

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Publication number
WO2000024786A1
WO2000024786A1 PCT/US1998/022634 US9822634W WO0024786A1 WO 2000024786 A1 WO2000024786 A1 WO 2000024786A1 US 9822634 W US9822634 W US 9822634W WO 0024786 A1 WO0024786 A1 WO 0024786A1
Authority
WO
WIPO (PCT)
Prior art keywords
prepolymer
water insoluble
radiation curable
monomer
mixture
Prior art date
Application number
PCT/US1998/022634
Other languages
English (en)
Inventor
Andrew J. Naisby
Original Assignee
Rexam Graphics Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rexam Graphics Inc. filed Critical Rexam Graphics Inc.
Priority to AU12774/99A priority Critical patent/AU1277499A/en
Priority to PCT/US1998/022634 priority patent/WO2000024786A1/fr
Publication of WO2000024786A1 publication Critical patent/WO2000024786A1/fr

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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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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

Definitions

  • the invention pertains to a method of stabilizing a radiation curable water insoluble monomer /prepolymer in an aqueous medium.
  • the stable colloidal emulsion composition once processed, offers all the advantages associated with UV/EB curable systems containing a hydrophobic monomer /prepolymer, but from an environmentally friendly medium.
  • waterborne UN cure formulations offer many advantages; such as the coating is easily sprayed; low shrinkage; reduced or zero monomer content or waterborne UV coatings; water will not penetrate wood pores and remain uncured; better mattability; and improved adhesion.
  • the alternative of using water soluble radiation curable chemicals has limitations, e.g., in the availability of such chemicals, water resistance of the cured material, and controlling the viscosity of the solution. Generally, the more water soluble the material and higher the molecular weight, the higher the viscosity.
  • Still another object of the present invention is to provide one with the opportunity to employ a stable aqueous emulsion composition to form coatings, inks, finishes and the like, from an environmentally friendly medium, while also realizing the advantages and the properties associated with highly crosslinked hydrophobic radiation curable materials.
  • the present invention provides a method of stabilizing a radiation curable, water insoluble monomer/prepolymer in an aqueous medium.
  • the method comprises mixing a radiation curable, water insoluble monomer and/or prepolymer, or mixture of same, with an aqueous mixture containing a colloidal suspension of water insoluble particles.
  • the resultant mixture is stable and can be used to form coatings, inks, finishes and the like, with the desirable properties associated with highly crosslinked hydrophobic radiation curable materials, e.g., solvent and abrasion resistance, while employing an environmentally friendly medium.
  • the stable colloidal solution formed includes two phases, an aqueous phase and a non-aqueous phase.
  • the non-aqueous phase includes a non- water soluble monomer/prepolymer together with a colloidal suspension of water insoluble particles, within the aqueous phase. The mixture remains stable over time.
  • the invention provided herein is a method of stabilizing a radiation curable water insoluble monomer/prepolymer in an aqueous mixture.
  • the method comprises mixing a radiation curable, water insoluble monomer and/or prepolymer with an aqueous mixture conta-iiing a colloidal suspension of water insoluble particles.
  • the result is a stable mixture, which remains stable over time.
  • the water insoluble monomer and/or prepolymer is generally unstable in an aqueous medium, but is believed to become adsorbed onto the water insoluble particles in colloidal suspension within the aqueous mixture.
  • the result is an aqueous emulsion composition or mixture which allows one to employ the benefits of a radiation curable, water insoluble monomer/prepolymer material, yet from an aqueous medium.
  • the radiation curable, water insoluble monomer/prepolymer contain ethylenic unsaturated groups that can be polymerized and/or crosslinked by irradiation with electron bombardment or ultraviolet radiation, generally in the presence of a photoinitiator system.
  • the preferred monomers/pre-polymers are urethane acrylates, carboxy ethyl acrylates, trimethylol propane triacrylate and ethoxylated derivatives thereof, and acrylated amines, although other like materials will be obvious to those skilled in the art.
  • the monomer/prepolymer is preferably mixed with an aqueous mixture containing a colloidal suspension of water insoluble particles of ethylene vinyl acetate, polyvinyl acetate, poly urethane, ethylene vinyl chloride, silicone emulsions and the like.
  • a colloidal suspension of water insoluble particles of ethylene vinyl acetate, polyvinyl acetate, poly urethane, ethylene vinyl chloride, silicone emulsions and the like.
  • suitable particles will be known to those of skill in the art. It is believed that the normally aqueous unstable monomer/prepolymer is stabilized by adsorption onto the colloidally suspended particles, thus allowing the radiation curable monomer/prepolymer to remain itself in colloidal suspension in the aqueous medium.
  • the amount of monomer/prepolymer (e.g., aery late) that can be successfully stabilized on the colloidal particle will vary based on the acrylate and the type of colloidal particle used. Values typically vary between 20% and 100% by weight of the acrylate to the weight of colloidal particle. Generally, the mixture can be even further stabilized by adjustments in pH, or preferably, by the presence of a suitable surfactant.
  • the mir-L-mum film forming temperature (M.F.F.T.) and glass transition temperature (Tg) of the emulsion particle used to stabilize the acrylate influences the gloss and physical properties of the fully processed mixture (i.e., once the water has been evaporated and the dried film exposed to radiation).
  • the M.F.F.T. may be from about -20°C to +50°C, preferably between about -5°C to +40°.
  • the Tg is preferably between about -40 °C to +40 °C, and most preferably between 0°C and +40°C.
  • the M.F.F.T. and Tg may in fact be higher or lower than the given ranges in any particular composition.
  • the monomer/prepolymer may be cured by electron bombardment or ultraviolet radiation.
  • Optional photoinitiators for use in an ultraviolet light cured system may include alpha hydroxy ketones and phosphine oxides. Other suitable photoinitiators are -mown to those skilled in the art.
  • the stabilized mixture of the present invention has also found particular application in inks.
  • the stable emulsion, containing the radiation curable monomer/prepolymer, are particularly useful in the manufacture of aqueous UN curable ink jet inks. Presence in the ink would allow for subsequent curing of the ink once applied to an ink jet medium, after the water has been removed by wicking so that only the ink remains on the medium.
  • the present invention provides many advantages. Among those is that the present invention provides a method incorporating water insoluble, radiation curable chemicals into an aqueous medium to facilitate a unification of the advantages of using hydrophobic radiation curable chemicals in an environmentally friendly medium, i.e., specifically an aqueous medium.
  • hydrophobic radiation curable chemicals are solvent and water resistance, as well as abrasion resistance.
  • aqueous based radiation curable ink jet inks and spray coatings are useful in the manufacture of aqueous based radiation curable ink jet inks and spray coatings.
  • hybrid systems are possible where a water soluble polymer can be dissolved into the aqueous phase thereby creating a method for enhancing the properties of aqueous ink jet receptive medium.
  • a coating can be manufactured that has both the properties associated with water soluble polymers and the capturing, drying and smear resistance of the water based ink with additional properties of gloss, abrasion, and water resistance associated with hydrophobic radiation cured chemicals.
  • a mixture was prepared in the following proportions.
  • a mixture of lOg of mixture A was added to 25g of Airflex 110 (an ethylene vinyl acetate aqueous emulsion). This was mixed thoroughly before adding 5.0g of water thereby making mixture B.
  • Airflex 110 an ethylene vinyl acetate aqueous emulsion
  • Airflex 110 Water 5.0 grams Airflex 110 is supplied as a 55% solids emulsion in water by Air Products.
  • Both mixture A and mixture B were coated using a Meyer rod to give the appropriate film thicknesses.
  • the support for each coating was a clear biaxially orientated polyester film supplied by ICI Melineax division.
  • the grade used was Melineax 401.
  • Mixture A was coated to a thickness of 10 microns and then irradiated with UV radiation in the region of 200-350 nm with an energy dose of 1000 mJ/c ⁇ r 2 .
  • Mixture B was coated to a wet thickness of 60 microns, the water content was totally removed in a thermal convection oven at 220 °F. The resultant coating was then irradiated (10 microns in thickness) with UV identically to that used with mixture A (i.e., UV wavelength 200nm-250nm, energy of 1000 mJ/cm" 2 ).
  • Pencil hardness The hardness of pencil required to leave a permanent abrasion on the surface of the cured coating. Adhesion. The percentage removed of the cured coating after the coating has been scored with a knife. Solvent Resistance. Methyl ethyl ketone was applied to the coating. The number of subsequent rubs required to destroy the coating was recorded.
  • Coating B provides distinct advantages in handling and the coating procedure since it is of lower viscosity and is from an aqueous medium as opposed to the organic based solvent of Coating A. As well, surprising adhesion of Coating B to the polyester substrate was observed.
  • This example illustrates the incorporation of the present invention into an aqueous ink jet ink.
  • a non UV curable aqueous ink jet ink was compared against a UV curable ink jet ink.
  • the method of incorporating the UV curable species into an aqueous medium is identical to that used in Example 1.
  • Ink-jet ink 1. (Non UV curable).
  • An ink-jet cartridge was filled with ink-jet ink 1 (RSP101-4) and one was filled with ink-jet ink 2.
  • the ink-jet cartridge used was the Hewlett Packard 51626A.
  • the filled cartridges were installed into an ink jet printer, the Encad Novajet ⁇ .
  • a test plot was made onto plain paper so that a direct comparison could be made of the two ink types.
  • the printed sheet was irradiated with UV light in the region of 200-350nm at an energy dose between 500-1000 mJ/cm "2 .
  • the example illustrates that the physical performance of an ink-jet ink can be improved using UV reactive species and that these can easily be incorporated into an aqueous ink using the stabilization technique of the present invention.

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

Abstract

L'invention concerne un procédé de stabilisation dans un milieu aqueux d'un monomère et/ou prépolymère insolubles dans l'eau. Ledit procédé consiste à mélanger le monomère et/ou prépolymère insolubles dans l'eau, durcissables par radiation, à un mélange aqueux contenant une suspension colloïdale de particules insolubles dans l'eau. On produit ainsi un mélange stable qui peut être utilisé comme revêtement pour divers substrats, de manière à leur conférer certaines caractéristiques, telles que la résistance à l'abrasion, ainsi que dans des encres comme, par exemple, les encres d'impression à jet d'encre.
PCT/US1998/022634 1998-10-28 1998-10-28 Procede de stabilisation dans un milieu aqueux, d'un monomere/prepolymere insoluble dans l'eau, durcissable par radiation WO2000024786A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU12774/99A AU1277499A (en) 1998-10-28 1998-10-28 Method of stabilizing a radiation curable, water insoluble monomer/prepolymer inan aqueous medium
PCT/US1998/022634 WO2000024786A1 (fr) 1998-10-28 1998-10-28 Procede de stabilisation dans un milieu aqueux, d'un monomere/prepolymere insoluble dans l'eau, durcissable par radiation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/022634 WO2000024786A1 (fr) 1998-10-28 1998-10-28 Procede de stabilisation dans un milieu aqueux, d'un monomere/prepolymere insoluble dans l'eau, durcissable par radiation

Publications (1)

Publication Number Publication Date
WO2000024786A1 true WO2000024786A1 (fr) 2000-05-04

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PCT/US1998/022634 WO2000024786A1 (fr) 1998-10-28 1998-10-28 Procede de stabilisation dans un milieu aqueux, d'un monomere/prepolymere insoluble dans l'eau, durcissable par radiation

Country Status (2)

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AU (1) AU1277499A (fr)
WO (1) WO2000024786A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6534618B1 (en) 2000-11-27 2003-03-18 Corning Incorporated Methods of drying optical fiber coatings
CN103436113A (zh) * 2013-08-23 2013-12-11 南通市康桥油脂有限公司 一种过氯乙烯涂料
JP2016033205A (ja) * 2014-03-31 2016-03-10 株式会社日本触媒 活性エネルギー線硬化型水性樹脂組成物
US9574101B2 (en) 2012-12-21 2017-02-21 Rohm And Haas Company Acrylic dispersions with multi-functional acrylates for UV-cure coatings
CN107674553A (zh) * 2017-11-13 2018-02-09 中国海洋石油集团有限公司 一种航空飞行器外蒙皮用涂料体系及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103614066A (zh) * 2013-11-25 2014-03-05 广东巴德士化工有限公司 一种油性uv底上专用的水性uv哑光清面漆

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287039A (en) * 1978-12-14 1981-09-01 Basf Aktiengesellschaft Radiation-curable aqueous binder dispersions, their preparation and their use
US4451509A (en) * 1982-01-14 1984-05-29 Bayer Aktiengesellschaft Radiation-hardenable aqueous binder emulsions of acrylate prepolymer with unsaturated polyester emulsifier having benzyloxy and alkylene-oxy groups
US4861916A (en) * 1985-04-03 1989-08-29 Merck Patent Gesellschaft Mit Beschrankter Haftung Photoinitiators for photopolymerization of unsaturated systems
US5075348A (en) * 1990-11-01 1991-12-24 Dow Corning Corporation Multifunctional acrylate based abrasion resistant coating composition
US5318850A (en) * 1991-11-27 1994-06-07 General Electric Company UV curable abrasion-resistant coatings with improved weatherability
US5565501A (en) * 1994-04-18 1996-10-15 Mitsubishi Chemical Corporation Active-energy-ray-curable coating composition
US5565302A (en) * 1995-04-21 1996-10-15 W. R. Grace & Co.-Conn. Process for preparing photosensitive resin composition
US5708048A (en) * 1992-06-25 1998-01-13 General Electric Company Radiation curable hardcoat compositions
US5830927A (en) * 1994-04-19 1998-11-03 Lehigh University Printing ink compositions, methods for making same and uses thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4287039A (en) * 1978-12-14 1981-09-01 Basf Aktiengesellschaft Radiation-curable aqueous binder dispersions, their preparation and their use
US4451509A (en) * 1982-01-14 1984-05-29 Bayer Aktiengesellschaft Radiation-hardenable aqueous binder emulsions of acrylate prepolymer with unsaturated polyester emulsifier having benzyloxy and alkylene-oxy groups
US4861916A (en) * 1985-04-03 1989-08-29 Merck Patent Gesellschaft Mit Beschrankter Haftung Photoinitiators for photopolymerization of unsaturated systems
US5045573A (en) * 1985-04-03 1991-09-03 Merck Patent Gesellschaft Mit Beschrankter Haftung Photoinitiators for photopolymerization of unsaturated systems
US5075348A (en) * 1990-11-01 1991-12-24 Dow Corning Corporation Multifunctional acrylate based abrasion resistant coating composition
US5318850A (en) * 1991-11-27 1994-06-07 General Electric Company UV curable abrasion-resistant coatings with improved weatherability
US5708048A (en) * 1992-06-25 1998-01-13 General Electric Company Radiation curable hardcoat compositions
US5565501A (en) * 1994-04-18 1996-10-15 Mitsubishi Chemical Corporation Active-energy-ray-curable coating composition
US5830927A (en) * 1994-04-19 1998-11-03 Lehigh University Printing ink compositions, methods for making same and uses thereof
US5565302A (en) * 1995-04-21 1996-10-15 W. R. Grace & Co.-Conn. Process for preparing photosensitive resin composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6534618B1 (en) 2000-11-27 2003-03-18 Corning Incorporated Methods of drying optical fiber coatings
US9574101B2 (en) 2012-12-21 2017-02-21 Rohm And Haas Company Acrylic dispersions with multi-functional acrylates for UV-cure coatings
CN103436113A (zh) * 2013-08-23 2013-12-11 南通市康桥油脂有限公司 一种过氯乙烯涂料
JP2016033205A (ja) * 2014-03-31 2016-03-10 株式会社日本触媒 活性エネルギー線硬化型水性樹脂組成物
CN107674553A (zh) * 2017-11-13 2018-02-09 中国海洋石油集团有限公司 一种航空飞行器外蒙皮用涂料体系及其制备方法
CN107674553B (zh) * 2017-11-13 2020-01-21 中国海洋石油集团有限公司 一种航空飞行器外蒙皮用涂料体系及其制备方法

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