WO2007055929A1 - Cyclocarbonate-containing energy-curable compositions - Google Patents

Cyclocarbonate-containing energy-curable compositions Download PDF

Info

Publication number
WO2007055929A1
WO2007055929A1 PCT/US2006/041938 US2006041938W WO2007055929A1 WO 2007055929 A1 WO2007055929 A1 WO 2007055929A1 US 2006041938 W US2006041938 W US 2006041938W WO 2007055929 A1 WO2007055929 A1 WO 2007055929A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition according
carbonate
cyclic carbonate
reactor
product
Prior art date
Application number
PCT/US2006/041938
Other languages
French (fr)
Inventor
Shaun Lawrence Herlihy
Brian Rowatt
Robert Stephen Davidson
Original Assignee
Sun Chemical Corporation
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 Sun Chemical Corporation filed Critical Sun Chemical Corporation
Priority to US12/092,749 priority Critical patent/US20080286486A1/en
Priority to EP06826834A priority patent/EP1948711A1/en
Publication of WO2007055929A1 publication Critical patent/WO2007055929A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D263/00Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/18Oxygen atoms
    • C07D263/20Oxygen atoms attached in position 2
    • C07D263/24Oxygen atoms attached in position 2 with hydrocarbon radicals, substituted by oxygen atoms, attached to other ring carbon atoms
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D263/00Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F18/00Homopolymers and 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F18/24Esters of carbonic or haloformic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00Chemical modification by after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/10Printing inks based on artificial resins
    • C09D11/101Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D131/00Coating 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J131/00Adhesives 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/038Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to new compositions, such as printing inks or varnishes, which are energy-curable, e.g. UV curable, via a cationic mechanism and which have excellent cure, as a result of the incorporation in the composition of a novel class of monomer, namely, one or more of the polyfunctional cyclic carbonates.
  • US5567527 describes copolymers of vinyl ethylene carbonate with acrylic monomers, such as methyl methacrylate and butyl acrylate, to yield carbonate functional polymers which will react as crosslinkers specifically with primary amines to give urethane coatings.
  • US5961802 claims a coating composition containing a compound with a plurality of cyclic carbonate groups. This is for cathodic electrodepositing coating by reaction with amine groups and is not UV curing related.
  • US6001535 describes monomers with cyclic carbonate groups, but which include acrylate or methacrylate functional groups. Although a UV curing mechanism is used in the manufacture of printing plates using these materials, the composition cures via a free radical (acrylate) rather than a cationic mechanism as used in the present invention
  • Propylene carbonate a monofunctional cyclic carbonate
  • the cationic photoinitiator commonly being used as a 50% solution in propylene carbonate
  • propylene carbonate is deemed by most formulators and end users to be an unreactive component, and so it would not be expected to have a positive effect on cure.
  • US Patent No. 5,262,449 states specifically that simple alkylene carbonates are merely solvents and play no part in polymerisation, and that they should be used in relatively low amounts to avoid undesired effects.
  • the present invention consists in an energy-curable composition
  • a polyfunctional cyclic carbonate a monomer or oligomer copolymerisable with said polyfunctional cyclic carbonate and a cationic photoinitiator.
  • polyfunctional cyclic carbonate as used herein means a compound having two or more cyclic carbonate groups which are capable of participation in a ring- opening polymerisation process.
  • a preferred class of polyfunctional cyclic carbonate compounds for use in the present invention comprises those compounds of formula (I):
  • Q represents a polyvalent organic residue having a valency x > 1 or a direct bond
  • Y is an aliphatic carbon chain which may be interrupted by one or more oxygen atoms, sulphur atoms, phenylene groups, carbonyl groups, epoxide groups or linear or cyclic carbonate groups;
  • R 1 and R 2 are the same as or different from each other, and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group or a C 2 - C5 carbon chain which is attached to a carbon atom of Y to form a fused ring;
  • R ⁇ represents a hydrogen atom or an alkyl group
  • n and n are the same as or different from each other, and each is zero or a number from 1 to 4, provided that (m+n) is zero or a number from 1 to 4.
  • Q is a polyvalent organic residue having a valency x, which is preferably from 2 to 4.
  • groups which may be represented by Q include bisphenol A and bisphenol F residues, groups of formula -0-CO-CH 2 -, polymethylene groups (e.g. trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene and nonamethylene groups), cycloalkylene groups (e.g. cyclopentylene or cyclohexylene groups), bis(alkylene)oxy (e.g. -CH 2 -O-CH 2 - or -C 2 H 5 -O-C 2 H 5 -), divalent and trivalent groups derived from benzene, and groups derived from polyols and esters thereof,
  • Y is an aliphatic carbon chain which may be interrupted by one or more oxygen atoms, sulphur atoms, phenylene groups, carbonyl groups, epoxide groups or linear or cyclic carbonate groups. It preferably has from 1 to 20 atoms in its aliphatic chain.
  • a further preferred class of compounds for use in the present invention comprises those compounds of formula (II):
  • R , R , R ⁇ and R ⁇ are the same as or different from each other, and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, or an alkoxycarbonylalkyl group;
  • n and n are the same as or different from each other, and each is zero or a number from 1 to 4, provided that (m+n) is zero or a number from 1 to 4;
  • q and r are the same as or different from each other, and each is zero or a number from 1 to 4, provided that (q+r) is zero or a number from 1 to 4.
  • R 1 , R 2 , R 3 or R 4 represents an alkyl group
  • this may be a straight or branched chain group having from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 6 and most preferably from 1 to 3, carbon atoms, and examples of such groups include the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1- ethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3- dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3- dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, hexy
  • R 1 , R 2 , R 3 or R 4 represents a hydroxyalkyl group
  • this may be a straight or branched chain group having from 1 to 6, preferably from 1 to 4, carbon atoms, and examples include the hydroxymethyl, 1- or 2- hydroxyethyl, 1-, 2- or 3- hydroxypropyl, 1- or 2- hydroxy-2-methylethyl, 1-, 2-, 3- or 4- hydroxybutyl, 1-, 2-, 3-, 4- or 5- hydroxypentyl or 1-, 2-, 3-, 4-, 5- or 6- hydroxyhexyl groups.
  • hydroxyalkyl groups having from 1 to 4 carbon atoms, preferably the hydroxymethyl, 2- hydroxyethyl, 3 -hydroxypropyl and 4-hydroxybutyl groups, and most preferably the hydroxymethyl group.
  • R ⁇ , R 2 , R ⁇ or R 4 represents an alkoxyalkyl group
  • the alkoxy and alkyl parts both preferably have from 1 to 6 carbon atoms, and examples include the methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, 2- methoxyethyl, 3-methoxypropyl, 2-methoxypropyl and 4-ethoxybutyl groups.
  • R ⁇ , R 2 , R ⁇ or R 4 represents an alkoxycarbonylalkyl group
  • the alkoxy and alkyl parts both preferably have from 1 to 6 carbon atoms, and examples include the methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, 2-methoxycarbonylethyl, 3- methoxycarbonylpropyl, 2-methoxycarbonylpropyl and 4-ethoxycarbonylbutyl groups.
  • R ⁇ or R 2 represents a carbon chain forming, with a carbon atom of Y a fused ring, this has from 2 to 5 carbon atoms and may be, for example, a dimethylene, trimethylene, tetramethylene or pentamethylene group.
  • the polyfunctional cyclic carbonate may be a polymeric compound having pendant carbonate groups, for example the compounds of formula (IV):
  • p is a number denoting a degree of polymerisation and R represents a hydrogen atom or an alkyl group, e.g. a methyl or ethyl group.
  • the polyfunctional cyclic carbonate may be a polymeric compound having carbonate groups in the main polymer chain, for example a polyvinylene carbonate.
  • Examples of preferred polyfunctional cyclic carbonates for use in the present invention include compounds of formulae:
  • n is a number denoting a degree of polymerisation, as well as epoxidised soya bean oil carbonate or epoxidised linseed oil carbonate.
  • the polyfunctional cyclic carbonate should comprise from 1 to 50% by weight, more preferably from 10 to 30% by weight, and most preferably from 15 to 25% by weight, of the total polymerisable components of the composition.
  • 5-Membered cyclic carbonates are easily prepared on an industrial scale, for example by carbon dioxide insertion into epoxide groups or other known methods.
  • Preferred copolymerisable monomers or oligomers for use in the compositions of the present invention include epoxides, oxetanes, and sulphur analogues thereof, in particular epoxides and/or oxetanes, of which the cycloaliphatic epoxides are preferred.
  • Typical epoxides which may be used include the cycloaliphatic epoxides (such as those sold under the designations Cyracure UVR6105, UVR6107, UVR6110 and UVR6128, by Dow), which are well known to those skilled in the art.
  • epoxides which may be used include such epoxy- functional oligomers/monomers as the glycidyl ethers of polyols [bisphenol A, alkyl diols or poly(alkylene oxides), which be di-, tri-, terra- or hexa- functional].
  • epoxides derived by the epoxidation of unsaturated materials may also be used (e.g. epoxidised soybean oil, epoxidised polybutadiene or epoxidised alkenes).
  • Naturally occurring epoxides may also be used, including the crop oil collected from Vernonia galamensis.
  • Suitable oxetanes include 3-ethyl-3-hydroxyniethyl-oxetane, 3- ethyl-3-[2-ethylhexyloxy)methyl]oxetane, bis[l-ethyl(3-oxetanyl)]methyl ether, bis[l- ethyl(3-oxetanyl)]methyl ether, oxetane functional novolac polymers and methyl silicon trioxetane.
  • vinyl ethers of polyols such as triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether and the vinyl ethers of poly(alkylene oxides)].
  • vinyl ether functional prepolymers include the urethane-based products supplied by Allied Signal.
  • monomers/oligomers containing propenyl ether groups may be used in place of the corresponding compounds referred to above containing vinyl ether groups.
  • reactive species can include styrene derivatives and cyclic esters (such as lactones and their derivatives).
  • the composition of the present invention also contains a cationic photoinitiator.
  • a cationic photoinitiator there is no particular restriction, on the particular cationic photoinitiator used, and any cationic photoinitiator known in the art may be employed.
  • cationic photoinitiators include sulphonium salts (such as the mixture of compounds available under the trade name UVI6992 from Dow Chemical), thianthrenium salts (such as Esacure 1187 available from Lamberti), iodonium salts (such as IGM 440 from IGM) and phenacyl sulphonium salts.
  • particularly preferred cationic photoinitiators are the thioxanthonium salts, such as those described in WO 03/072567 Al, WO 03/072568 Al, and WO 2004/055000 Al, the disclosures of which are incorporated herein by reference.
  • Particularly preferred thioxanthonium salts are those of formulae (I), (II) and (III):
  • each R represents a group of formula (IV):
  • n is a number and X " is an anion, especially the hexafluorophosphates.
  • the hexafluorophosphates of the compounds of formulae (I) and (II) are available from IGM under the trade marks IGM 550 and IGM 650 respectively.
  • composition of the present invention may be formulated as a printing ink, varnish, adhesive, paint or any other coating composition which is intended to be cured by energy, which may be supplied by irradiation, whether by ultraviolet or electron beam.
  • Such compositions will normally contain at least a polymerisable monomer, prepolymer or oligomer, and a cationic photoinitiator, as well as the cyclic carbonate, but may also include other components well known to those skilled in the art, for example, reactive diluents and, in the case of printing inks and paints, a pigment or dye.
  • polyols in ultraviolet cationic curable formulations, which promote the cross-linking by a chain-transfer process.
  • examples of polyols include the ethoxylated/propoxylated derivatives of, for example, trimethylolpropane, pentaerytliritol, di-trimethylolpropane, di-pentaerythritol and sorbitan esters, as well as more conventional poly(ethylene oxide)s and polypropylene oxide)s.
  • Other polyols well known to those skilled in the art are the polycaprolactone diols, triols and tetraols, such as those supplied by Dow.
  • Additives which may be used in conjunction with the principal components of the coating formulations of the present invention include stabilisers, plasticisers, pigments, waxes, slip aids, levelling aids, adhesion promoters, surfactants and fillers.
  • the amounts of the various components of the curable composition of the present invention may vary over a wide range and, in general, are not critical to the present invention. However, we prefer that the amount of the polymerisable components (i.e. the epoxide, oxetane, if used, and other monomers, prepolymers and oligomers, if used) should be from 40 to 90% of the total composition.
  • the epoxide(s) preferably comprise from 30 to 80% of the polymerisable components in the composition of the present invention, and the oxetanes, preferably multi-functional oxetane(s), if used, preferably comprise from 5 to 40% of the polymerisable components in the composition of the present invention.
  • the amount of cationic photoinitiator is normally from 1.0 to 10% by weight, more preferably from 2.0 to 8%, by weight of the entire composition.
  • curable composition may be included in amounts well known to those skilled in the art.
  • the curable compositions of this invention maybe suitable for applications that include protective, decorative and insulating coatings; potting compounds; sealants; adhesives; photoresists; textile coatings; and laminates.
  • the compositions may be applied to a variety of substrates, e.g., metal, rubber, plastic, wood, moulded parts, films, paper, glass cloth, concrete, and ceramic.
  • the curable compositions of this invention are particularly useful as inks for use in a variety, of printing processes, including, but not limited to, lithography, flexography, inkjet and gravure. Details of such printing processes and of the properties of inks needed for them are well known and may be found, for example, in The Printing Ink Manual, 5 th Edition, edited by R.H.
  • compositions of the present invention are used for inks, these typically comprise, as additional components to those referred to above, one or more of pigments, waxes, stabilisers, and flow aids, for example as described in "The Printing InIc Manual”.
  • the invention also provides a process for preparing a cured coating composition, which comprises applying a composition according to the present invention to a substrate and exposing the coated substrate to curing radiation sufficient to cure the coating.
  • Ethoxylated pentaerythritol 3/4 (10.125 g, 0.0375 moles), bromoacetic acid (22.9 g, 0.165 moles), 0.375 g p-toluenesulphonic acid, 0.075 g butylated hydroxytoluene and 50 ml toluene were azeotropically refluxed for 5 hours.
  • the solution was washed with 2 x 100 ml 10% aqueous potassium carbonate solution and 3 x 100 ml deionised water.
  • Varnish formulations were prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW Remainder
  • Varnish formulations were prepared based on
  • AU formulations were printed onto Lenetta charts using a No. I K bar and cured under a 300 W/inch medium pressure mercury arc lamp at 50 m/minute and then left to post-cure for 1 hour.
  • the isopropanol (IPA) solvent resistance of the cured films was assessed using the SATRA STM 421 rub tester at carbonate contents of 0-50% for carbonate functionalities of 1, 2, 3 & 4, and the results are shown in Table 2.
  • Varnish formulations were prepared based on
  • AU formulations were printed onto Lenetta charts using a No. 1 K bar and cured under a 300 W/inch medium pressure mercury arc lamp. All samples cured to a tack free state at a speed of at least 100 m/minute, compared to a tack free cure speed of 110 m/minute for a formulation where no cyclic carbonate compound was present.
  • Varnish formulations were prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW Remainder
  • Varnish formulations were prepared based on
  • Varnish formulations were prepared based on
  • UVR6105 cycloalipliatic epoxide ex DOW 87.9%
  • Varnish formulations were prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW Remainder
  • a varnish formulation was prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW 87.9%
  • Varnish formulations were prepared based on
  • Varnish formulations were prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW 77.9%
  • Example 24 has a low carbonate functionality per gram and extremely soft flexible propylene oxide units in the molecule causing a reduction in tack- free cure speed but the attainment of an extremely flexible coating.
  • Varnish formulations were prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW 87.9%
  • Example 20 which has a low carbonate functionality per gram as it is derived from a difunctional bisphenol A epoxy with an epoxy equivalent weight of 900.
  • a white flexo ink was prepared based on
  • Titanium dioxide (FINNITITAN RDI/S ex Kemira) 40.0%
  • Ebecryl 1360 (Silicone ex Cytec) 2.0%
  • Varnish formulations were prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW 87.9%
  • Varnish formulations were prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW 87.9%
  • a varnish formulation was prepared based on Omnicat BL-550 photoinitiator solution ex IGM 10.0%
  • This formulation was found to have a viscosity of 122 Poise at 25 0 C using an ICI cone and plate viscometer and is therefore capable of being printed by an offset or dry offset process.
  • the formulation was printed onto a Lenetta charts using an IGT CI proofer and cured at 100 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at half power.
  • the varnish was found to be tack free and well cured as defined by the "thumb twist test" in only 1 pass; faster than most commercial varnishes and demonstrates the reactivity of the multifunctional carbonate Example 40.
  • a black ink formulation was prepared based on
  • UVR6105 cycloaliphatic epoxide ex DOW 23.75%
  • This formulation was found to have a viscosity of 67 Poise at 25 °C using an ICI cone and plate viscometer and is therefore capable of being printed by an offset or dry offset process.
  • the formulation was printed at a density of 2.0 onto "polyboard" substrate using an IGT CI proofer and cured at 100 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at full power.
  • the ink was found to be tack free and well cured as defined by the "thumb twist test" in only 1 pass; faster than most commercial free radical curing inks and demonstrates the reactivity of the multifunctional carbonate Example 40.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
  • Epoxy Compounds (AREA)

Abstract

Polyfunctional cyclic carbonates provide a useful additional monomer for energy-initiated cationic copolymerisation with such other monomers and oligomers as epoxides and oxetanes.

Description

CARBONATE CONTAINING ENERGY-CURABLE COMPOSITIONS
The present invention relates to new compositions, such as printing inks or varnishes, which are energy-curable, e.g. UV curable, via a cationic mechanism and which have excellent cure, as a result of the incorporation in the composition of a novel class of monomer, namely, one or more of the polyfunctional cyclic carbonates.
Although many multifunctional cyclic carbonates are known, it has not hitherto been appreciated that they can be useful monomers in energy-curable compositions.
For example, in a review of the applications of alkylene carbonates, primarily the monofunctional ethylene carbonate and propylene carbonate, it is said "five- membered alkylene carbonates undergo ring-opening polymerisation with difficulty", and, while the author discusses in some detail how this polymerisation may, or may not, take place, he does not suggest any uses for the resulting polymers ["Reactive applications of cyclic alkylene carbonates" by John Clements, and available as a download from the Huntsman chemical web site, http://www.huntsman.com/performance products/Media/ZReactive Applications of Cyclic Alkyl ene Carbonates 110903.pdf]
US6143857, US4542069 and various other literature references describe polyvinylene carbonate and copolymers of vinylene carbonate but these are not for energy curing applications.
US5567527 describes copolymers of vinyl ethylene carbonate with acrylic monomers, such as methyl methacrylate and butyl acrylate, to yield carbonate functional polymers which will react as crosslinkers specifically with primary amines to give urethane coatings. US5961802 claims a coating composition containing a compound with a plurality of cyclic carbonate groups. This is for cathodic electrodepositing coating by reaction with amine groups and is not UV curing related.
US6001535 describes monomers with cyclic carbonate groups, but which include acrylate or methacrylate functional groups. Although a UV curing mechanism is used in the manufacture of printing plates using these materials, the composition cures via a free radical (acrylate) rather than a cationic mechanism as used in the present invention
Although the cationic curing of various coating compositions, including printing inks and varnishes, on exposure to ultraviolet radiation (UV) by the ring-opening polymerisation of epoxides has been known for a very long time, it has never achieved much commercial success, as a result, inter alia, of the slow cure speed of such systems. In order to make such systems commercially attractive, it is necessary to improve the cure speed of UV catioiiically curable epoxide-based printing inks and similar coating compositions.
We have surprisingly found that this may be achieved by the incorporation in the coating composition of at least one polyfunctional cyclic carbonate.
Propylene carbonate, a monofunctional cyclic carbonate, is commonly used as a solvent for the cationic photoinitiator in such systems (the cationic photoinitiator commonly being used as a 50% solution in propylene carbonate) and there is pressure from users of these coating compositions to reduce the level of propylene carbonate, on the basis that it may migrate out of the cured composition. Moreover, propylene carbonate is deemed by most formulators and end users to be an unreactive component, and so it would not be expected to have a positive effect on cure. Indeed, US Patent No. 5,262,449 states specifically that simple alkylene carbonates are merely solvents and play no part in polymerisation, and that they should be used in relatively low amounts to avoid undesired effects. Moreover, ink formulators are always trying to improve and extend, the uses of their inks. The discovery of a new class of polymerisable monomer for use in cationic energy curing allows a much wider range of variation in properties of the finished ink to be achieved.
Thus, the present invention consists in an energy-curable composition comprising a polyfunctional cyclic carbonate, a monomer or oligomer copolymerisable with said polyfunctional cyclic carbonate and a cationic photoinitiator.
The term "polyfunctional cyclic carbonate" as used herein means a compound having two or more cyclic carbonate groups which are capable of participation in a ring- opening polymerisation process.
A preferred class of polyfunctional cyclic carbonate compounds for use in the present invention comprises those compounds of formula (I):
Figure imgf000004_0001
in which:
Q represents a polyvalent organic residue having a valency x > 1 or a direct bond;
Y is an aliphatic carbon chain which may be interrupted by one or more oxygen atoms, sulphur atoms, phenylene groups, carbonyl groups, epoxide groups or linear or cyclic carbonate groups;
p is 0 or 1; R1 and R2 are the same as or different from each other, and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group or a C2 - C5 carbon chain which is attached to a carbon atom of Y to form a fused ring;
R^ represents a hydrogen atom or an alkyl group; and
m and n are the same as or different from each other, and each is zero or a number from 1 to 4, provided that (m+n) is zero or a number from 1 to 4.
In these compounds of formula (I), Q is a polyvalent organic residue having a valency x, which is preferably from 2 to 4. Examples of groups which may be represented by Q include bisphenol A and bisphenol F residues, groups of formula -0-CO-CH2-, polymethylene groups (e.g. trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene and nonamethylene groups), cycloalkylene groups (e.g. cyclopentylene or cyclohexylene groups), bis(alkylene)oxy (e.g. -CH2-O-CH2- or -C2H5-O-C2H5-), divalent and trivalent groups derived from benzene, and groups derived from polyols and esters thereof,
Where Y is present, it is an aliphatic carbon chain which may be interrupted by one or more oxygen atoms, sulphur atoms, phenylene groups, carbonyl groups, epoxide groups or linear or cyclic carbonate groups. It preferably has from 1 to 20 atoms in its aliphatic chain.
Of these compounds, we prefer those compounds having the formula (Ia):
Figure imgf000005_0001
(Ia) in which Ra represents a hydrogen atom or a methyl group and n is a degree of polymerisation.
A further preferred class of compounds for use in the present invention comprises those compounds of formula (II):
Figure imgf000006_0001
in which:
R , R , R^ and R^ are the same as or different from each other, and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, or an alkoxycarbonylalkyl group;
m and n are the same as or different from each other, and each is zero or a number from 1 to 4, provided that (m+n) is zero or a number from 1 to 4; and
q and r are the same as or different from each other, and each is zero or a number from 1 to 4, provided that (q+r) is zero or a number from 1 to 4.
In the compounds of formulae (I) and (II), where R1, R2, R3 or R4 represents an alkyl group, this may be a straight or branched chain group having from 1 to 20, more preferably from 1 to 10, still more preferably from 1 to 6 and most preferably from 1 to 3, carbon atoms, and examples of such groups include the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, 2-methylbutyl, 1- ethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3,3- dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3- dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, hexyl, isohexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, pentadecyl, octadecyl, nonadecyl and icosyl groups, but preferably the methyl, ethyl, propyl and t-butyl groups, and most preferably the methyl or ethyl group.
Where R1, R2, R3 or R4 represents a hydroxyalkyl group, this may be a straight or branched chain group having from 1 to 6, preferably from 1 to 4, carbon atoms, and examples include the hydroxymethyl, 1- or 2- hydroxyethyl, 1-, 2- or 3- hydroxypropyl, 1- or 2- hydroxy-2-methylethyl, 1-, 2-, 3- or 4- hydroxybutyl, 1-, 2-, 3-, 4- or 5- hydroxypentyl or 1-, 2-, 3-, 4-, 5- or 6- hydroxyhexyl groups. Of these, we prefer those hydroxyalkyl groups having from 1 to 4 carbon atoms, preferably the hydroxymethyl, 2- hydroxyethyl, 3 -hydroxypropyl and 4-hydroxybutyl groups, and most preferably the hydroxymethyl group.
Where R^, R2, R^ or R4 represents an alkoxyalkyl group, the alkoxy and alkyl parts both preferably have from 1 to 6 carbon atoms, and examples include the methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxymethyl, butoxymethyl, 2- methoxyethyl, 3-methoxypropyl, 2-methoxypropyl and 4-ethoxybutyl groups.
Where R^, R2, R^ or R4 represents an alkoxycarbonylalkyl group, the alkoxy and alkyl parts both preferably have from 1 to 6 carbon atoms, and examples include the methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, butoxycarbonylmethyl, 2-methoxycarbonylethyl, 3- methoxycarbonylpropyl, 2-methoxycarbonylpropyl and 4-ethoxycarbonylbutyl groups.
hi formula (I), where R ^ or R2 represents a carbon chain forming, with a carbon atom of Y a fused ring, this has from 2 to 5 carbon atoms and may be, for example, a dimethylene, trimethylene, tetramethylene or pentamethylene group.
An example of the compounds of formula (II) is the compound of formula (III):
Figure imgf000007_0001
(III) Alternatively, the polyfunctional cyclic carbonate may be a polymeric compound having pendant carbonate groups, for example the compounds of formula (IV):
Figure imgf000008_0001
in which p is a number denoting a degree of polymerisation and R represents a hydrogen atom or an alkyl group, e.g. a methyl or ethyl group.
As a further alternative, the polyfunctional cyclic carbonate may be a polymeric compound having carbonate groups in the main polymer chain, for example a polyvinylene carbonate.
Examples of preferred polyfunctional cyclic carbonates for use in the present invention include compounds of formulae:
Figure imgf000008_0002
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000011_0001
where n is a number denoting a degree of polymerisation, as well as epoxidised soya bean oil carbonate or epoxidised linseed oil carbonate.
We prefer that the polyfunctional cyclic carbonate should comprise from 1 to 50% by weight, more preferably from 10 to 30% by weight, and most preferably from 15 to 25% by weight, of the total polymerisable components of the composition.
5-Membered cyclic carbonates are easily prepared on an industrial scale, for example by carbon dioxide insertion into epoxide groups or other known methods.
Preferred copolymerisable monomers or oligomers for use in the compositions of the present invention include epoxides, oxetanes, and sulphur analogues thereof, in particular epoxides and/or oxetanes, of which the cycloaliphatic epoxides are preferred.
Typical epoxides which may be used include the cycloaliphatic epoxides (such as those sold under the designations Cyracure UVR6105, UVR6107, UVR6110 and UVR6128, by Dow), which are well known to those skilled in the art.
Other epoxides which may be used include such epoxy- functional oligomers/monomers as the glycidyl ethers of polyols [bisphenol A, alkyl diols or poly(alkylene oxides), which be di-, tri-, terra- or hexa- functional]. Also, epoxides derived by the epoxidation of unsaturated materials may also be used (e.g. epoxidised soybean oil, epoxidised polybutadiene or epoxidised alkenes). Naturally occurring epoxides may also be used, including the crop oil collected from Vernonia galamensis.
Examples of suitable oxetanes include 3-ethyl-3-hydroxyniethyl-oxetane, 3- ethyl-3-[2-ethylhexyloxy)methyl]oxetane, bis[l-ethyl(3-oxetanyl)]methyl ether, bis[l- ethyl(3-oxetanyl)]methyl ether, oxetane functional novolac polymers and methyl silicon trioxetane.
As well as epoxides and optionally oxetanes, other reactive monomers/oligomers which may be used include the vinyl ethers of polyols [such as triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether and the vinyl ethers of poly(alkylene oxides)]. Examples of vinyl ether functional prepolymers include the urethane-based products supplied by Allied Signal. Similarly, monomers/oligomers containing propenyl ether groups may be used in place of the corresponding compounds referred to above containing vinyl ether groups.
Other reactive species can include styrene derivatives and cyclic esters (such as lactones and their derivatives).
The composition of the present invention also contains a cationic photoinitiator. There is no particular restriction, on the particular cationic photoinitiator used, and any cationic photoinitiator known in the art may be employed. Examples of such cationic photoinitiators include sulphonium salts (such as the mixture of compounds available under the trade name UVI6992 from Dow Chemical), thianthrenium salts (such as Esacure 1187 available from Lamberti), iodonium salts (such as IGM 440 from IGM) and phenacyl sulphonium salts. However, particularly preferred cationic photoinitiators are the thioxanthonium salts, such as those described in WO 03/072567 Al, WO 03/072568 Al, and WO 2004/055000 Al, the disclosures of which are incorporated herein by reference.
Particularly preferred thioxanthonium salts are those of formulae (I), (II) and (III):
Figure imgf000013_0001
R-(OCH2CH2CH2CH2)n-OR (III)
in which each R represents a group of formula (IV):
Figure imgf000014_0001
where n is a number and X" is an anion, especially the hexafluorophosphates. The hexafluorophosphates of the compounds of formulae (I) and (II) are available from IGM under the trade marks IGM 550 and IGM 650 respectively.
The composition of the present invention may be formulated as a printing ink, varnish, adhesive, paint or any other coating composition which is intended to be cured by energy, which may be supplied by irradiation, whether by ultraviolet or electron beam. Such compositions will normally contain at least a polymerisable monomer, prepolymer or oligomer, and a cationic photoinitiator, as well as the cyclic carbonate, but may also include other components well known to those skilled in the art, for example, reactive diluents and, in the case of printing inks and paints, a pigment or dye.
It is also common to include polyols in ultraviolet cationic curable formulations, which promote the cross-linking by a chain-transfer process. Examples of polyols include the ethoxylated/propoxylated derivatives of, for example, trimethylolpropane, pentaerytliritol, di-trimethylolpropane, di-pentaerythritol and sorbitan esters, as well as more conventional poly(ethylene oxide)s and polypropylene oxide)s. Other polyols well known to those skilled in the art are the polycaprolactone diols, triols and tetraols, such as those supplied by Dow.
Additives which may be used in conjunction with the principal components of the coating formulations of the present invention include stabilisers, plasticisers, pigments, waxes, slip aids, levelling aids, adhesion promoters, surfactants and fillers.
The amounts of the various components of the curable composition of the present invention may vary over a wide range and, in general, are not critical to the present invention. However, we prefer that the amount of the polymerisable components (i.e. the epoxide, oxetane, if used, and other monomers, prepolymers and oligomers, if used) should be from 40 to 90% of the total composition. The epoxide(s) preferably comprise from 30 to 80% of the polymerisable components in the composition of the present invention, and the oxetanes, preferably multi-functional oxetane(s), if used, preferably comprise from 5 to 40% of the polymerisable components in the composition of the present invention. The amount of cationic photoinitiator is normally from 1.0 to 10% by weight, more preferably from 2.0 to 8%, by weight of the entire composition.
Other components of the curable composition may be included in amounts well known to those skilled in the art.
The curable compositions of this invention maybe suitable for applications that include protective, decorative and insulating coatings; potting compounds; sealants; adhesives; photoresists; textile coatings; and laminates. The compositions may be applied to a variety of substrates, e.g., metal, rubber, plastic, wood, moulded parts, films, paper, glass cloth, concrete, and ceramic. The curable compositions of this invention are particularly useful as inks for use in a variety, of printing processes, including, but not limited to, lithography, flexography, inkjet and gravure. Details of such printing processes and of the properties of inks needed for them are well known and may be found, for example, in The Printing Ink Manual, 5th Edition, edited by R.H. Leach et al., published in 1993 by Blueprint, the disclosure of which is incorporated herein by reference. In particular, unlike many other ink formulations, it is possible to vary the viscosity of coating compositions of the present invention over a very wide range, from the relatively low viscosities required for flexographic and inkjet processes to the rather higher viscosities required for lithographic inks and varnishes.
Where the compositions of the present invention are used for inks, these typically comprise, as additional components to those referred to above, one or more of pigments, waxes, stabilisers, and flow aids, for example as described in "The Printing InIc Manual".
Thus, the invention also provides a process for preparing a cured coating composition, which comprises applying a composition according to the present invention to a substrate and exposing the coated substrate to curing radiation sufficient to cure the coating.
The invention is further illustrated by the following non-limiting Examples. It should be noted that the compounds prepared as Examples No. 5, 7, 11, and 21, which are all monofunctional cyclic carbonates, are not compounds for use in the invention and are included merely for comparative purposes in the evaluation Examples.
Figure imgf000017_0001
50.Og of 3,4-Epoxycyclohexylniethyl 3,4-epoxycyclohexane- carboxylate (0.198moles) and LOg of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 35Opsi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 1500C and there appeared to be no further change in the pressure, the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 63.77g (94.56%) of a clear yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1800cm"1.
EXAMPLE 2
Figure imgf000017_0002
10.Og of vinyl cyclohexene dioxide (0.0714moles) and O.lg of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 150°C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 15O0C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 14.83g (91.06%) of a clear yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1790cm"1.
EXAMPLE 3
Figure imgf000018_0001
20.Og of bis(3,4-epoxycyclohexylmethyl) adipate (0.0546moles) and 0.2g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 150°C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator. Product yield 22.28g (89.83%) of a clear yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1801cm'1.
EXAMPLE 4
Figure imgf000019_0001
50.Og of octanetetrol (0.2809moles), 130.0g ethyl chlorofoπnate (1.197moles) and 550ml of tetrahydrofuran were mixed in a 1 litre three necked round bottomed flask equipped with a stirrer, temperature probe and a dropping funnel. The mixture was cooled to <10°C using an ice/water bath. 120.0g of triethylamine (1.188moles) in 200ml of tetrahydrofuran were added dropwise ensuring- the temperature did not rise above 200C. The mixture was then allowed to rise to room temperature. The precipitate that had formed was removed by filtration. The solvent was then removed by rotary evaporator to yield the product.
Product yield 5O.O8g (77.51%).
The product was analysed by IR.
IR: very strong carbonate peak at 1794cm"1.
EXAMPLE 5
Figure imgf000019_0002
11. Hg of dodecanediol (0.04942moles), 10.73g ethyl chloroformate (0.09885moles) and 60ml of tetrahydrofuran were mixed in a 500ml three necked round bottomed flask equipped with a stirrer, temperature probe and a dropping funnel. The mixture was cooled to 0°C using an ice/water bath. 9.984g of triethylamine (0.09885moles) in 20ml of tetrahydrofuran were added dropwise ensuring the temperature did not rise above 150C. The mixture was then allowed to rise to room temperature. The precipitate that had formed was removed by filtration. The solvent was then removed by rotary evaporator to yield the product.
Product yield 11.16g (90.04%).
The product was analysed by IR.
IR: very strong carbonate peak at 1801cm"1.
EXAMPLE 6
Figure imgf000020_0001
Ethoxylated pentaerythritol 3/4 (10.125 g, 0.0375 moles), bromoacetic acid (22.9 g, 0.165 moles), 0.375 g p-toluenesulphonic acid, 0.075 g butylated hydroxytoluene and 50 ml toluene were azeotropically refluxed for 5 hours. The solution was washed with 2 x 100 ml 10% aqueous potassium carbonate solution and 3 x 100 ml deionised water. The organics were dried using anhydrous magnesium sulphate and then the solvent was removed on a rotary evaporator to yield the intermediate product - [tetra(bromoacetic ester) of ethoxylated pentaerythritol 3A].
Yield = 21.14 g colourless low viscosity liquid.
The product was analysed by IR.
IR: very strong ester peak at 1738cm" . 5.Og of the intermediate product (0.006635moles), 3.23g of glycerine carbonate (0.0274moles), 0.2g of tetrabutyl ammonium bromide, 10.Og of potassium carbonate powder and 25ml of acetone were mixed in a flask equipped with a condenser, mechanical stirrer and a temperature probe. The mixture was heated to reflux for a total of 6 hours. Additional acetone was added to top-up the solvent volume as some solvent was lost by evaporation through the mechanical stirrer joint. The mixture was then cooled and filtered to remove the inorganics. 250ml of ethyl acetate was added to the organic phase which was then washed with 2x100ml of water. The organic phase was then dried with anhydrous magnesium sulphate and the solvent removed on a rotary evaporator to yield the product.
Yield = 3.48g (58.15%) of a viscous liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1792cm"1, very strong ester peak at 1751cm"1.
EXAMPLE 7
Figure imgf000021_0001
10.0g of epoxy hexane (O.lmoles) and 0.2g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 15O0C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 12.8Og (88.89%) of a clear yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1799cm"1.
EXAMPLE 8
Figure imgf000022_0001
20.Og of trimethylol propane triglycidyl ether (0.0662moles) and 0.2g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 1500C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 26.7Og (92.90%) of a clear yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1792cm' -i EXAMPLE 9
Figure imgf000023_0001
20.Og of Vikoflex 7170 epoxidised soyabean oil and 0.4g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 1500C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 18.65g of a clear yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1806cm' -1 EXAMPLE 10
Figure imgf000024_0001
30.Og of Vikoflex 9010 epoxidised linseed oil and 0.6g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 1500C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 1500C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichlorornethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 31.Og of a yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1804cm'1.
EXAMPLE 11
Figure imgf000024_0002
50.Og of ethylhexyl glycidyl ether (0.269moles) and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 61.6g (99.63%) of a yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1797cm"1.
EXAMPLE 12
Figure imgf000025_0001
50.0g of hexanediol diglycidyl ether (0.217moles) and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.5 litre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 1500C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 1500C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 61.Og (88.24%) of a yellow liquid. The product was analysed by IR.
IR: very strong carbonate peak at 1794cm"
EXAMPLE 13
Figure imgf000026_0001
50.0g of 1, 4-cyclohexanedimethanol diglycidyl ether (0.197moles) and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 150°C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 60.Og (89.12%) of a yellow liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1794cm"1.
EXAMPLE 14
Figure imgf000026_0002
50.Og of pentaerythritol tetraglycidyl ether (Polypox Rl 6) (0.139moles) and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 58.9g (79.12%) of a yellow viscous liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1789cm"1.
EXAMPLE 15
Figure imgf000027_0001
50.0g of Epoxy Novolac DEN 431 and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.5litre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 150°C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 1500C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 61.5g of a yellow solid.
The product was analysed by IR.
IR: very strong carbonate peak at 1794cm"1.
EXAMPLE 16
Figure imgf000028_0001
23.6g of glycerine carbonate (0.2moles), 20.2g of triethylamine (0.2moles) and 300ml of dichloromethane were mixed in a 1 litre reaction vessel. The mixture was cooled to 50C. 18.3g of adipoyl chloride (O.lmoles) in 50ml of dichloromethane were then added slowly over approximately 30minutes keeping the temperature in the range 5-10°C. The mixture was then stirred for 5-10minutes and then 200ml of water was added and the solution separated. The dichloromethane layer was washed with 250ml of 10% sodium carbonate solution and then 2 x 200ml of water. The dichloromethane layer was dried with anhydrous magnesium sulphate and the solvent then removed to yield the product.
Product yield 29.998g (86.7%) of a dark brown oil.
The product was analysed by IR.
IR: very strong carbonate peak at 1796cm"1, strong ester peak at 1739cm"1.
EXAMPLE 17
Figure imgf000029_0001
23.6g of glycerine carbonate (0.2moles), 20.2g of triethylamine (0.2moles) and 250ml of dichloromethane were mixed in a 1 litre reaction vessel. The mixture was cooled to 5°C. 23.1g of diethyleneglycol bischloroformate (O.lmoles) in 50ml of dichloromethane were then added slowly over approximately 30minutes keeping the temperature in the range 5-1O0C. The mixture was then stirred for 2 minutes and then 200ml of water was added and the solution separated. The dichloromethane layer was washed with 200ml of 10% sodium carbonate solution and then 2 x 200ml of water. The dichloromethane layer was dried with anhydrous magnesium sulphate and the solvent then removed to yield the product.
Product yield 18.16g (46.1%) of a straw coloured viscous liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1800cm"1, strong ester peak at 1757cm"1.
EXAMPLE 18
Figure imgf000029_0002
23.6g of glycerine carbonate (0.2moles), 20.2g of triethylamine (0.2moles) and 200ml of dichloromethane were mixed in a 1 litre reaction vessel. The mixture was cooled to 5°C. 17.71g of benzene tricarbonyl trichloride (0.0667moles) in 100ml of dichloromethane were then added slowly over approximately 1 hour keeping the temperature in the range 5-100C. 200ml of water was then added and the solution separated. The dichloromethane layer was washed with 200ml of 10% sodium carbonate solution and then 200ml of water. The dichloromethane layer was dried with anhydrous magnesium sulphate and the solvent then removed to yield the product.
Product yield 10.5g (28.85%) of white crystals.
The product was analysed by IR.
IR: very strong carbonate peak at 1794cm"1, strong ester peak at 1735cm"1.
EXAMPLE 19
Figure imgf000031_0001
10.Og of di(trimethylolpropane) (0.04moles), 17.36g ethyl chloroformate (O.lβmoles) and 150ml of tetrahydrofuran were mixed in a 500ml three necked round bottomed flask equipped with a stirrer, temperature probe and a dropping funnel. The mixture was cooled to 00C using an ice/water bath. 16.16g of triethylamine (O.lβmoles) in 40ml of tetrahydrofuran were added dropwise ensuring the temperature did not rise above 1O0C. The mixture was then allowed to rise to room temperature. The precipitate that had formed was removed by filtration. The solvent was then removed by rotary evaporator to yield the crude product. The product was crystallised by adding anhydrous ether. The product was collected by vacuum filtration.
Product yield lO.Olg (82.86%).
The product was analysed by IR.
IR: very strong carbonate peak at 1743cm -1
EXAMPLE 20
Figure imgf000031_0002
10.0g ofpentaerythritol (0.0735moles), 31.91g ethyl chloroformate (0.294moles) and 150ml of tetrahydrofuran were mixed in a 500ml three necked round bottomed flask equipped with a stirrer, temperature probe and a dropping funnel. The mixture was cooled to O0C using an ice/water bath. 29.7 Ig of triethylamine (0.294moles) in 40ml of tetrahydrofuran were added dropwise ensuring the temperature did not rise above 1O0C. An additional 50ml of tetrahydrofuran was added about half way through the triethylamine addition to reduce the viscosity of the mixture so that efficient stirring was obtained. The mixture was then allowed to rise to room temperature. The precipitate that had formed was removed by filtration. The solvent was then removed by rotary evaporator. The crude product was redissolved in 50ml of methyl ethyl ketone / diethyl ether 1:1 and washed with 2x25ml of water. The organics were then dried with anhydrous magnesium sulphate and then the solvent was removed by rotary evaporator to yield the product.
Product yield 5.19g (37.56%).
The product was analysed by IR.
IR: very strong carbonate peak at 1820 and 1755cm"1.
EXAMPLE 21
Figure imgf000032_0001
13.52g of neopentyl glycol (0.13moles), 28.4Og ethyl chloro formate (0.26moles) and 260ml of tetrahydrofuran were mixed in a 500ml three necked round bottomed flask equipped with a stirrer, temperature probe and a dropping funnel. The mixture was cooled to 00C using an ice/water bath. 26.5g of triethylamine (0.26moles) in 65ml of tetrahydrofuran were added dropwise ensuring the temperature did not rise above 100C. The mixture was then allowed to rise to room temperature. The precipitate that had formed was removed by filtration. The solvent was then removed by rotary evaporator to yield the crude product. The crude product was recrystallised from ether.
Product yield 9.68g (57.3%) of white crystals. The product was analysed by IR.
IR: very strong carbonate peak centred at 1743 cm"
EXAMPLE 22
Figure imgf000033_0001
Di(trimethylolpropane) (10.0Og, 0.03995 moles), bromoacetic acid (24.4 Ig, 0.1757moles), 0.375 g p-toluenesulphonic acid, 0.075 g butylated hydroxytoluene and 60ml toluene were azeotropically refluxed for lOhours. The solution was washed with 2 x 100 ml 10% aqueous potassium carbonate solution and 3 x 100 ml deionised water The organics were dried using anhydrous magnesium sulphate and then the solvent was removed on a rotary evaporator to yield the intermediate product - tetra(bromoacetic ester) of di(trimethylolpropane).
Yield = 21.14 g colourless liquid.
The product was analysed by IR.
IR: very strong ester peak at 1738cm"1.
20.Og of the intermediate product (0.02725moles), 13.27g of glycerine carbonate (0.1125moles), 0.82g of tetrabutylammonium bromide, 40.Og of potassium carbonate powder and 100ml of acetone were mixed in a flask equipped with a condenser, mechanical stirrer and a temperature probe. The mixture was heated to reflux for a total of 6 hours. Additional acetone was added to top-up the solvent volume as some solvent was lost by evaporation through the mechanical stirrer joint. The mixture was then cooled and filtered to remove the inorganics. 200ml of ethyl acetate was added to the organic phase which was then washed with 2xl00ml of water. The organic phase was then dried with anhydrous magnesium sulphate and the solvent removed on a rotary evaporator to yield the product. Yield = 20.45g (85.1%) of a viscous liquid.
The product was analysed by IR.
IR: very strong carbonate peak at 1791cm"1, very strong ester peak at 1751cm"1.
EXAMPLE 23
Figure imgf000034_0001
50.Og of DER 330 Epoxy resin of Bisphenol A (180 epoxy equivalent weight) and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 56.Og of a yellow solid.
The product was analysed by IR.
IR: very strong carbonate peak at 1791cm"1.
EXAMPLE 24
Figure imgf000035_0001
40.Og of Glycerol propoxylate triglycidyl ether (average molecular weight 1950) and 0.4g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 150°C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 41.Og of a yellow solid.
The product was analysed by IR.
IR: very strong carbonate peak at 1800cm"1.
EXAMPLE 25
Figure imgf000035_0002
40.Og of triphenylolmethans triglycidyl ether and 0.4g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 1500C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure the reactor was cooled and the pressure released. The product was isolated by dissolving in dichloromethane, washing with 2 x 100ml of water, drying the organic phase with anhydrous magnesium sulphate and removing the solvent on a rotary evaporator.
Product yield 44.2g of a yellow solid.
The product was analysed by IR.
IR: very strong carbonate peak at 1794cm"1.
EXAMPLE 26
Figure imgf000036_0001
50.0g of DEN 438 Epoxy Novolac and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 150°C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 1500C and there appeared to be no further change in the pressure, the reactor was cooled and the pressure released. The product was removed from the reactor.
Product yield 49.4g of a yellow solid.
The product was analysed by IR.
IR: very strong carbonate peak at 1797cm"1.
EXAMPLE 27
Figure imgf000037_0001
50.Og of DER 661 Epoxy resin (500 epoxy equivalent weight) and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 150°C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure, the reactor was cooled and the pressure released. The product was removed from the reactor.
Product yield 50.2g of a yellow solid.
The product was analysed by IR.
IR: carbonate peak at 1798cm"
EXAMPLE 28
Figure imgf000037_0002
50.Og of DER 664 U Epoxy resin (900 epoxy equivalent weight) and 0.5g of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 35Opsi at room temperature. The reactor was then heated to a temperature of approximately 150°C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure, the reactor was cooled and the pressure released. The product was removed from the reactor.
Product yield 50.0g of a yellow solid.
The product was analysed by IR.
IR: carbonate peak at 1799cm"1.
EXAMPLE 29
Varnish formulations were prepared based on
S-biphenyl thianthrenium hexafiuorophosphate 2%
Tegorad 2100 wetting aid ex TEGO 0.1%
Carbonates shown in Table 1 0-50%
UVR6105 cycloaliphatic epoxide ex DOW Remainder
All formulations were printed onto Lenetta charts using a No. 1 K bar and cured under a 300 W/inch medium pressure mercury arc lamp. The maximum line speed for tack free cure was evaluated at a carbonate content of 0-50% for carbonate functionalities of 1, 2, 3 & 4, and is shown in Table 1. Table 1
Figure imgf000039_0001
These results demonstrate that compounds with cyclic carbonate functionalities of 2 or more tend to increase the tack free cure speed over monofunctional carbonates at equivalent levels and carbonate free formulations. Concentrations of around 20% appear to give highest reactivity.
EXAMPLE 30
Varnish formulations were prepared based on
S-biphenyl thianthrenium hexafluorophosphate 2%
Tegorad 2100 wetting aid ex TEGO 0.1%
Carbonates shown in Table 2 0-50% UVR6105 cycloaliphatic epoxide ex DOW Remainder
AU formulations were printed onto Lenetta charts using a No. I K bar and cured under a 300 W/inch medium pressure mercury arc lamp at 50 m/minute and then left to post-cure for 1 hour. The isopropanol (IPA) solvent resistance of the cured films was assessed using the SATRA STM 421 rub tester at carbonate contents of 0-50% for carbonate functionalities of 1, 2, 3 & 4, and the results are shown in Table 2.
Table 2
Figure imgf000041_0001
These results demonstrate that compounds with cyclic carbonate groups increase the IPA resistance of cured films, and in particular compounds with higher carbonate functionalities, particularly tri and tetra functional, maintain high solvent resistance at higher incorporation levels relative to monofunctional materials.
EXAMPLE 31
Varnish formulations were prepared based on
S-biphenyl thianthrenium hexafluorophosphate 3.5%
Tegorad 2100 wetting aid ex TEGO 0.1%
Carbonate Examples 1, 2, 3, 4, 5, 6, 7 15% UVR6105 cycloaliphatic epoxide ex DOW 81.4%
AU formulations were printed onto Lenetta charts using a No. 1 K bar and cured under a 300 W/inch medium pressure mercury arc lamp. All samples cured to a tack free state at a speed of at least 100 m/minute, compared to a tack free cure speed of 110 m/minute for a formulation where no cyclic carbonate compound was present.
These results demonstrate that compounds with cyclic carbonate functionalities of varying structures can be incorporated into formulations without adversely affecting their cure speed.
EXAMPLE 32
Varnish formulations were prepared based on
S-biphenyl isopropyl thioxanthonium hexafluorophosphate 2.0% (Omnicat 550 ex IGM)
Tegorad 2100 wetting aid ex TEGO 0.1 %
Carbonate Examples 9 & 10 0 - 25%
UVR6105 cycloaliphatic epoxide ex DOW Remainder
All formulations were printed onto Lenetta charts using a No. I K bar and cured under a 300 W/inch medium pressure mercury arc lamp. The maximum line speed for tack free cure was evaluated at a carbonate content of 0-25% for carbonate Examples 9 & 10. The results are shown in Table 3. Table 3
Figure imgf000043_0001
These results demonstrate that cyclic carbonate compounds derived from highly flexibilising fatty acid epoxide compounds can be incorporated into formulations at up to 15-20% without significantly affecting their cure speed.
EXAMPLE 33
Varnish formulations were prepared based on
S-biphenyl isopropyl thioxanthonium hexafluorophosphate 2.0% (Omnicat 550 ex IGM)
Tegorad 2100 wetting aid ex TEGO 0.1%
Carbonate Example 4 0-20% UVR6105 cycloaliphatic epoxide ex DOW Remainder
All formulations were printed onto Lenetta charts using a No. 1 K bar and cured at 100 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at half power. Cure was assessed using the well known MEK solvent rub method immediately after cure, 5 minutes, 15 minutes, 1 hour and 3 hours after cure. The results are shown in Table 4.
Table 4
Figure imgf000044_0001
These results demonstrate that the difunctional cyclic carbonate of Example 4 increases the MEK resistance of cured films during the post cure period relative to formulations containing no cyclic carbonate groups.
EXAMPLE 34
Varnish formulations were prepared based on
S-biphenyl isopropyl thioxanthonium 2.0% hexafluorophosphate (Omnicat 550 ex IGM) Tegorad 2100 wetting aid ex TEGO 0.1%
Carbonate Examples 19, 20 & 21 10%
UVR6105 cycloalipliatic epoxide ex DOW 87.9%
A similar formulation was prepared but with no carbonate and an additional 10% epoxide. All formulations were printed onto Lenetta charts using a No. 1 K bar and cured at 100 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at half power. Cure was assessed using the well known MEK solvent rub method immediately after cure, 5 minutes, 15 minutes, 1 hour and 24 hours after cure. All samples cured tack free immediately except for the one containing Example 20, which remained tacky to touch for a few minutes after cure. The results are shown in Table 5.
Table 5
Figure imgf000045_0001
These results demonstrate that multifunctional 6-membered cyclic carbonate compounds such as Examples 19 and 20 increase the MEK resistance of cured films during the post cure period relative to formulations containing no or only monofunctional cyclic carbonate groups. EXAMPLE 35
Varnish formulations were prepared based on
S-biphenyl isopropyl thioxanthonium 2.0% hexafluorophosphate (Omnicat 550 ex IGM)
Tegorad 2100 wetting aid ex TEGO 0.1%
carbonate Example 6 0-28%
UVR6105 cycloaliphatic epoxide ex DOW Remainder
AU formulations were printed onto Lenetta charts using a No. I K bar and cured at 100 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at half power. Cure was assessed using the well known MEK solvent rub method immediately after cure, 15 minutes, 1 hour, 3 hours, 48 hours and 100 hours after cure. All samples cured tack free immediately. The results are shown in Table 6.
Table 6
Figure imgf000046_0001
Figure imgf000047_0001
These results demonstrate that the tetrafunctional cyclic carbonate, Example 6, increases the MEK resistance of cured films during the post cure period relative to formulations containing no cyclic carbonate groups.
EXAMPLE 36
A varnish formulation was prepared based on
S -biphenyl isopropyl thioxanthonium 2.0% hexafiuorophosphate (Omnicat 550 ex IGM)
Tegorad 2100 wetting aid ex TEGO 0.1%
carbonate Example 17 . 10%
UVR6105 cycloaliphatic epoxide ex DOW 87.9%
A similar formulation was prepared but with no carbonate and an additional 10% epoxide. Both formulations were printed onto Lenetta charts using a No. 1 K bar and cured at 100 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at half power. Cure was assessed using the well known MEK solvent rub method immediately after cure, 15 minutes, 30 minutes, 1 hour, 2 hours and 18 hours after cure. Both formulations cured tack free immediately. The results are shown in Table 7. Table 7
Figure imgf000048_0001
These results demonstrate that the difunctional cyclic carbonate Example 17 increases the MEK resistance of cured films during the post cure period relative to formulations containing no cyclic carbonate groups.
EXAMPLE 37
Varnish formulations were prepared based on
S-biphenyl isopropyl thioxanthonium 2.0% hexafluorophosphate (Omnicat 550 ex IGM)
Tegorad 2100 wetting aid ex TEGO 0.1 %
carbonate Examples 16 or 18 10%
UVR6105 cycloaliphatic epoxide ex DOW 87.9% Both formulations were printed onto Lenetta charts using a No. 1 K bar and cured at 100 m/minute under a 300 W/ϊnch medium pressure mercury arc lamp operating at half power. Both samples cured to give a tack free film immediately on cure. This demonstrates that the multifunctional cyclic carbonate Examples 16 and 18 can be incorporated into formulations without affecting their cure speed.
EXAMPLE 38
Varnish formulations were prepared based on
S-biphenyl thianthrenium 2.0% hexafluorophosphate
Tegorad 2100 wetting aid ex TEGO 0.1%
carbonate Examples 15, 23, 24, or 25 20%
UVR6105 cycloaliphatic epoxide ex DOW 77.9%
A similar formulation was prepared but with no carbonate and an additional 20% epoxide. All formulations were printed onto Lenetta charts using a No. 1 K bar and cured under a 300 W/inch medium pressure mercury arc lamp operating at half power. The maximum line speed for tack free cure was evaluated at carbonate content of 20% for carbonate Examples 15, 23, 24, and 25. The results are shown in Table 8.
Table 8
Figure imgf000050_0001
* turns bright orange on UV irradiation, fading with time
These results demonstrate that cyclic carbonate compounds derived from rigid polymer epoxides can provide substantial improvements in tack free cure speed. Example 24 has a low carbonate functionality per gram and extremely soft flexible propylene oxide units in the molecule causing a reduction in tack- free cure speed but the attainment of an extremely flexible coating.
EXAMPLE 39
Varnish formulations were prepared based on
S-biphenyl thianthrenium hexafluorophosphate 2%
Tegorad 2100 wetting aid ex TEGO 0.1%
Carbonates shown in Table 9 10%
UVR6105 cycloaliphatic epoxide ex DOW 87.9%
A similar formulation was prepared but with no carbonate and an additional 10% epoxide. All formulations were printed onto Lenetta charts using a No. 1 K bar and cured under a 300 W/inch medium pressure mercury arc lamp at 50 m/minute and then left to post-cure for 1 hour. The isopropanol (IPA) solvent resistance of the cured films was assessed using the SATRA STM 421 rub tester and the results are shown in Table 9.
Table 9
Figure imgf000051_0002
These results demonstrate that rigid polymer compounds with cyclic carbonate groups increase the JPA resistance of cured films, The exception is Example 20 which has a low carbonate functionality per gram as it is derived from a difunctional bisphenol A epoxy with an epoxy equivalent weight of 900.
EXAMPLE 40
Figure imgf000051_0001
74.65g of D.E.R. 354 liquid epoxy resin (Dow Chemical Company) and 0.74g of tetrabutyl ammonium bromide were mixed in a 0.51itre Paiτ pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 35Opsi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure, the reactor was cooled and the pressure released. The product was removed from the reactor.
Product yield 75g of a glassy solid.
The product was analysed by IR.
IR: very strong carbonate peak at 1794cm'
EXAMPLE 41
Figure imgf000052_0001
50.64g of resorcinol diglycidyl ether and 0.5Og of tetrabutyl ammonium bromide were mixed in a 0.51itre Parr pressure reactor with a magnetic stirrer The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 1500C and there appeared to be no further change in the pressure, the reactor was cooled and the pressure released. The product was removed from the reactor.
Product yield 65g of a glassy solid.
The product was analysed by IR.
IR: very strong carbonate peak at 1793cm
EXAMPLE 42
Figure imgf000053_0001
1:1 Copolymer
50.Og of vinyl ethylene carbonate and 15Og of o-xylene were mixed in a 500ml round bottomed flask equipped with a stirrer, condenser and nitrogen inlet/outlet. The mixture was heated to 100°C under a nitrogen atmosphere. 50.Og of glycidyl methacrylate and 2.Og of l,l'-azobis(cyclohexane carbonitrile) were added over a period of 140minutes. The temperature was then maintained at 100°C for a further 85minutes. A further 0.2g of 1,1 '-azobis(cyclohexane carbonitrile) in 2Og of o-xylene was added and the mixture stirred for a further 2hours at 1000C. The mixture was then cooled to room temperature. The solvent was removed by rotary evaporator to yield the product.
Product yield 99g of a viscous liquid.
The product was analysed by IR and GPC.
IR: very strong ester peak at 1728cm"1, very strong carbonate peak at 1805cm' -1 GPC: Mn 4636, Mw 12485, D 2.7.
EXAMPLE 43
Figure imgf000055_0001
50.74g of EPICLON HP-4032D from Dainippon Ink and Chemical Company, Japan, and 0.5Og of tetrabutyl ammonium bromide were mixed in a 0.51itre Pan- pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to an initial pressure of approximately 350psi at room temperature. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 15O0C and there appeared to be no further change in the pressure, the reactor was cooled and the pressure released. The product was removed from the reactor.
Product yield 58g of a glassy solid.
The product was analysed by IR. IR: very strong carbonate peak at 1790cm"1.
EXAMPLE 44
A white flexo ink was prepared based on;
Titanium dioxide (FINNITITAN RDI/S ex Kemira) 40.0%
UVR6105 cycloaliphatic epoxide ex DOW 30.3%
OXT-221 (dioxetane monomer ex Toagosei)! 10% Carbonate examples 10%
Omnicat 650 (photoinitiator ex IGM) 5%
Solsperse 32000 pigment dispersant solution 2.5%
Ebecryl 1360 (Silicone ex Cytec) 2.0%
Tego Airex 920 (antifoam ex Goldschmidt) 0.2%
A similar formulation was prepared but with no carbonate and an additional 10% cycloaliphatic epoxide. All formulations were printed onto Lenetta charts using a No. 0 K bar and cured under a 300 W/inch medium pressure mercury arc lamp operating at full power. The maximum line speed for tack free cure was evaluated using the thumb twist test at a carbonate content of 10% for carbonate Examples 1, 4 & 8. The results are shown in Table 10.
Table 10
Figure imgf000056_0001
The results demonstrate that multifunctional cyclic carbonates can be used to increase the cure speed of flexo ink formulations. EXAMPLE 45
Varnish formulations were prepared based on
Omnicat 650 photoinitiator ex IGM 2.0%
Tegorad 2100 wetting aid ex TEGO 0.1%
Carbonate Example 4, 40 or 41 10%
UVR6105 cycloaliphatic epoxide ex DOW 87.9%
A similar formulation was prepared but with no carbonate and an additional 10% cycloaliphatic epoxide. All formulations were printed onto Lenetta charts using a No. 0 K bar and cured at 60 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at half power. Prints were tested for isopropanol (IPA) resistance at various time intervals following cure using a Satra STM421 rub tester with the foam pad soaked in IPA. The results are shown in Table 11.
Table 11
Figure imgf000057_0001
These results demonstrate that multifunctional cyclic carbonates can be used to significantly improve the solvent resistance of a cationic curing coating relative to formulations containing no cyclic carbonate groups.
EXAMPLE 46
Figure imgf000059_0001
2Og of EPICLON HP -4700 from Dainippon Ink and Chemical Company, Japan and 0.2Og of tetrabutyl ammonium bromide were heated to 100°C in a 0.51itre Pan- pressure reactor with a magnetic stirrer. The reactor was sealed and carbon dioxide gas was pressurised into the reactor to approximately 350psi. The reactor was then heated to a temperature of approximately 15O0C. The temperature / pressure profile was monitored throughout. When the temperature had been held constant at 150°C and there appeared to be no further change in the pressure, the reactor was cooled and the pressure released. The product was removed from the reactor.
Product yield ~15g of a very hard glassy solid.
The product was analysed by JR. IR: very strong carbonate peak at 1790cm"1.
EXAMPLE 47
Varnish formulations were prepared based on
Omnicat 650 photoinitiator ex IGM 2.0%
Tegorad 2100 wetting aid ex TEGO 0.1% Carbonate Example 43 10%
UVR6105 cycloaliphatic epoxide ex DOW 87.9%
A similar formulation was prepared but with no carbonate and an additional 10% cycloaliphatic epoxide. AU formulations were printed onto Lenetta charts using a No. 0 K bar and cured at 60 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at half power. Prints were tested for isopropanol (IPA) resistance at various time intervals following cure using a Satra STM421 rub tester with the foam pad soaked in IPA. The results are shown in Table 12.
Table 12
Figure imgf000060_0001
These results demonstrate that multifunctional cyclic carbonates such as Example 43 can be used to significantly improve the solvent resistance of a cationic curing coating relative to formulations containing no cyclic carbonate groups.
EXAMPLE 48
A varnish formulation was prepared based on Omnicat BL-550 photoinitiator solution ex IGM 10.0%
Tegorad 2100 wetting aid ex TEGO 0.2%
Carbonate Example 40 40%
UVR6105 cycloaliphatic epoxide ex DOW 49.8%
This formulation was found to have a viscosity of 122 Poise at 25 0C using an ICI cone and plate viscometer and is therefore capable of being printed by an offset or dry offset process. The formulation was printed onto a Lenetta charts using an IGT CI proofer and cured at 100 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at half power. The varnish was found to be tack free and well cured as defined by the "thumb twist test" in only 1 pass; faster than most commercial varnishes and demonstrates the reactivity of the multifunctional carbonate Example 40.
A similar formulation where the carbonate Example 40 was replaced by the highly viscous novolac oxetane monomer PNOX (ex Toagosei) was found to have a viscosity of 57 Poise at 25 0C and cured at a similarly fast rate.
EXAMPLE 49
A black ink formulation was prepared based on
Omnicat BL-550 photoinitiator solution ex IGM 20.0%
Special black 250 pigment 15.0%
OXT 221 dioxetane monomer 10.0%
Solsperse 32000 pigment dispersant 1.25% Carbonate Example 40 30%
UVR6105 cycloaliphatic epoxide ex DOW 23.75%
This formulation was found to have a viscosity of 67 Poise at 25 °C using an ICI cone and plate viscometer and is therefore capable of being printed by an offset or dry offset process. The formulation was printed at a density of 2.0 onto "polyboard" substrate using an IGT CI proofer and cured at 100 m/minute under a 300 W/inch medium pressure mercury arc lamp operating at full power. The ink was found to be tack free and well cured as defined by the "thumb twist test" in only 1 pass; faster than most commercial free radical curing inks and demonstrates the reactivity of the multifunctional carbonate Example 40.

Claims

CLAIMS:
1. An energy-curable composition comprising a polyfunctional cyclic carbonate, a monomer or oligomer copolymerisable with said polyfunctional cyclic carbonate and a cationic photoinitiator.
2. A composition according to Claim 1, in which said polyfunctional cyclic carbonate is a compound of formula (I):
Figure imgf000063_0001
in which:
Q represents a polyvalent organic residue having a valency x > 1 or a direct bond;
Y is an aliphatic carbon chain which may be interrupted by one or more oxygen atoms, sulphur atoms, phenylene groups, carbonyl groups, epoxide groups or linear or cyclic carbonate groups;
p is 0 or 1;
RI and R^ are the same as or different from each other, and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group or a C2 - C5 carbon chain which is attached to a carbon atom of Y to form a fused ring;
R^ represents a hydrogen atom or an alkyl group; and m and n are the same as or different from each other, and each is a number from 0 to 4, provided that (m+n) is zero or a number from 1 to 4.
3. A composition according to Claim 2, in which said polyfunctional cyclic carbonate is a compound of formula:
Figure imgf000064_0001
in which Ra represents a hydrogen atom or a methyl group and n is a degree of polymerisation.
4. A composition according to Claim 2, in which said polyfunctional cyclic carbonate is a compound of formula:
Figure imgf000064_0002
Figure imgf000065_0001
Figure imgf000066_0001
where n is a number denoting a degree of polymerisation.
5. A composition according to Claim 2, in which said polyfunctional cyclic carbonate is epoxidised soya bean oil carbonate or epoxidised linseed oil carbonate.
6. A composition according to Claim 1, in which said polyfunctional cyclic carbonate is a compound of formula (II):
Figure imgf000067_0001
in which:
R% R , R^ and R^ are the same as or different from each other, and each represents a hydrogen atom, an alkyl group, a hydroxyalkyl group, an alkoxyalkyl group, or an alkoxycarbonylalkyl group;
m and n are the same as or different from each other, and each is zero or a number from 1 to 4, provided that (m+n) is zero or a number from 1 to 4; and
q and r are the same as or different from each other, and each is a number from 0 to 4, provided that (q+r) is a number from 1 to 4.
7. A composition according to Claim 6, in which said polyfunctional cyclic carbonate is a compound of formula:
Figure imgf000067_0002
8. A composition according to Claim 1, in which said polyfunctional cyclic carbonate is a polymeric compound having pendant carbonate groups.
9. A composition according to Claim 8, in which said polyfunctional cyclic carbonate is a compound of formula:
Figure imgf000068_0001
in which p is a number denoting a degree of polymerisation and R represents a hydrogen atom or an alkyl group.
10. A composition according to Claim 1, in which said polyfunctional cyclic carbonate is a polymeric compound having carbonate groups in the main polymer chain.
11. A composition according to Claim 10, in which said polyfunctional cyclic carbonate is a polyvinylidene carbonate.
12. A composition according to any one of the preceding Claims, in which said copolymerisable monomer or oligomer is an epoxide, an oxetane, or a sulphur analogue thereof.
13. A composition according to Claim 12, in which said copolymerisable monomer or oligomer is an epoxide or an oxetane.
14. A composition according to Claim 13, in which said copolymerisable monomer or oligomer is an epoxide and an oxetane.
15. A composition according to Claim 13, in which said copolymerisable monomer or oligomer is a cycloaliphatic epoxide.
16. A composition according to any one of the preceding Claims, in which the polyfunctional cyclic carbonate comprises from 1 to 50% by weight of the total polymerisable components of the composition.
17. A composition according to Claim 16, in which the polyfunctional cyclic carbonate comprises from 10 to 30% by weight of the total polymerisable components of the composition.
18. A composition according to Claim 17, in which the polyfunctional cyclic carbonate comprises from 15 to 25% by weight of the total polymerisable components of the composition.
19. A composition according to any one of the preceding Claims, formulated as a printing ink, varnish or adhesive.
20. A composition according to Claim 19, additionally comprising a colorant.
21. A composition according to Claim 19, formulated as an inkjet ink.
22. A composition according to Claim 19, formulated as a flexographic ink.
23. A composition according to Claim 19, formulated for gravure printing.
24. A composition according to Claim 19, formulated for lithographic printing.
25. A composition according to Claim 24 which is a varnish.
26. A composition according to Claim 24 which is a printing ink.
27. A method of producing a cured coating, which comprises applying a composition according to any one of the preceding Claims to a substrate and exposing the composition to curing energy.
28. A method according to Claim 27, in which said curing energy is ultraviolet.
PCT/US2006/041938 2005-11-14 2006-10-27 Cyclocarbonate-containing energy-curable compositions WO2007055929A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/092,749 US20080286486A1 (en) 2005-11-14 2006-10-27 Carbonate Containing Energy-Curable Compositions
EP06826834A EP1948711A1 (en) 2005-11-14 2006-10-27 Cyclocarbonate-containing energy-curable compositions

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0523200.4 2005-11-14
GB0523200A GB2432160A (en) 2005-11-14 2005-11-14 Energy curable cyclic carbonate compositions

Publications (1)

Publication Number Publication Date
WO2007055929A1 true WO2007055929A1 (en) 2007-05-18

Family

ID=35516908

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/041938 WO2007055929A1 (en) 2005-11-14 2006-10-27 Cyclocarbonate-containing energy-curable compositions

Country Status (4)

Country Link
US (1) US20080286486A1 (en)
EP (1) EP1948711A1 (en)
GB (1) GB2432160A (en)
WO (1) WO2007055929A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010287564A (en) * 2009-06-15 2010-12-24 Taiwan Hopax Chemicals Manufacturing Co Ltd Electrolyte for electrochemical elements, and its electrochemical element
FR2952933A1 (en) * 2009-11-20 2011-05-27 Centre Nat Rech Scient BISCARBONATE PRECURSORS, PROCESS FOR PREPARING THEM AND USES THEREOF
JP5581435B1 (en) * 2013-11-13 2014-08-27 大都産業株式会社 Curable resin composition
WO2015164692A1 (en) 2014-04-25 2015-10-29 Valspar Sourcing, Inc. Polycyclocarbonate compounds and polymers formed therefrom
JP2015227373A (en) * 2010-06-10 2015-12-17 日産化学工業株式会社 Cyclocarbonate group-containing compound
US10717897B2 (en) 2014-04-25 2020-07-21 The Sherwin-Williams Company Polycyclocarbonate compounds and polymers and compositions formed therefrom
WO2022174360A1 (en) 2021-02-22 2022-08-25 Thierry Schwitzguebel Anisotropic polycyclic carbonates

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010089264A1 (en) * 2009-02-05 2010-08-12 Basf Se Method for producing bicarbonates
JP5741340B2 (en) * 2010-09-29 2015-07-01 Jsr株式会社 Resist underlayer film forming composition, polymer, resist underlayer film, pattern forming method, and semiconductor device manufacturing method
FR2997700B1 (en) * 2012-11-05 2015-01-16 Bostik Sa POLYETHER POLYOL POLYETHER [4- (METHYLETHER) -1,3-DIOXOLANE-2-ONE POLYMERS]
JP6635668B2 (en) * 2015-03-24 2020-01-29 日鉄ケミカル&マテリアル株式会社 Carbonate resin, production method thereof, carbonate resin composition and cured product thereof
FR3097752B1 (en) * 2019-06-27 2023-10-13 Oreal Process for coloring keratin fibers using a particular cyclic polycarbonate, a compound comprising at least one amine group and a coloring agent, composition and device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05331366A (en) * 1992-03-31 1993-12-14 Res Dev Corp Of Japan Curable composition and method for curing the same
DE4324614A1 (en) * 1993-07-22 1995-01-26 Agfa Gevaert Ag Monomers with cyclic carbonate groups
US5961802A (en) * 1997-09-30 1999-10-05 Basf Corporation Cathodic electrocoat composition having latent functionality
JP2004010625A (en) * 2002-06-03 2004-01-15 Konica Minolta Holdings Inc Active energy ray curing ink for ink jet and method for ink-jet recording
JP2005314687A (en) * 2004-03-31 2005-11-10 Sekisui Chem Co Ltd Photo-curable resin composition, cationic photopolymerization initiator, adhesive for display element and display element
GB2423520A (en) * 2005-02-25 2006-08-30 Sun Chemical Ltd Energy-curable coating composition

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4273668A (en) * 1977-09-14 1981-06-16 General Electric Company Arylsulfonium salt-solvent mixtures
DE3243591A1 (en) * 1982-11-25 1984-05-30 Hoechst Ag, 6230 Frankfurt VINYLENE CARBONATE POLYMERYSATE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE
US5262449A (en) * 1990-09-10 1993-11-16 Isp Investments Inc. Radiation curable coating compositions
EP0548087B1 (en) * 1990-09-10 1996-10-23 Isp Investments Inc. Radiation curable coating compositions
US5567527A (en) * 1995-02-21 1996-10-22 Eastman Chemical Company Copolymers containing 1,3-dioxolane-2-one-4-yl groups and coatings made therefrom
JP3866037B2 (en) * 1998-04-17 2007-01-10 三洋化成工業株式会社 Curable composition and cured product thereof
US6232361B1 (en) * 1998-12-11 2001-05-15 Sun Chemical Corporation Radiation curable water based cationic inks and coatings
US6143857A (en) * 1999-03-23 2000-11-07 Cryovac, Inc. Linear vinylene carbonate/1-olefin copolymer and articles formed therefrom
US6635689B1 (en) * 2000-06-26 2003-10-21 3M Innovative Properties Company Accelerators for cationic polymerization catalyzed by iron-based catalysts
US6783228B2 (en) * 2002-12-31 2004-08-31 Eastman Kodak Company Digital offset lithographic printing
JP2004323642A (en) * 2003-04-23 2004-11-18 Riso Kagaku Corp Cationically polymerizable composition and ink

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05331366A (en) * 1992-03-31 1993-12-14 Res Dev Corp Of Japan Curable composition and method for curing the same
DE4324614A1 (en) * 1993-07-22 1995-01-26 Agfa Gevaert Ag Monomers with cyclic carbonate groups
US5961802A (en) * 1997-09-30 1999-10-05 Basf Corporation Cathodic electrocoat composition having latent functionality
JP2004010625A (en) * 2002-06-03 2004-01-15 Konica Minolta Holdings Inc Active energy ray curing ink for ink jet and method for ink-jet recording
JP2005314687A (en) * 2004-03-31 2005-11-10 Sekisui Chem Co Ltd Photo-curable resin composition, cationic photopolymerization initiator, adhesive for display element and display element
GB2423520A (en) * 2005-02-25 2006-08-30 Sun Chemical Ltd Energy-curable coating composition

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 29 June 1998 (1998-06-29), WEBSTER, DEAN C. WEBSTER, DEAN C.: "Cyclic carbonate functional polymers. Synthesis and applications Cyclic carbonate functional polymers. Synthesis and applications", XP009078653, retrieved from STN Database accession no. 1998:398760 *
DATABASE WPI Week 199403, Derwent World Patents Index; AN 1994-023040, XP002419010 *
DATABASE WPI Week 200428, Derwent World Patents Index; AN 2004-297877, XP002419012 *
DATABASE WPI Week 200582, Derwent World Patents Index; AN 2005-801553, XP002419011 *
DECKER, CHRISTIAN ET AL DECKER, CHRISTIAN ET AL: "Recent advances in UV-curing chemistry Recent advances in UV-curing chemistry", RADTECH '92 NORTH AM. UV/EB CONF. EXPO., CONF. PROC. , VOLUME 1, 260-74 PUBLISHER: RADTECH INT. NORTH AM., NORTHBROOK, ILL. CODEN: 58SXA8 RADTECH '92 NORTH AM. UV/EB CONF. EXPO., CONF. PROC. , VOLUME 1, 260-74 PUBLISHER: RADTECH INT. NORTH AM., NORTH, 1992, XP009078637 *
POLYMER NEWS , 23(6), 187-192 CODEN: PLYNBU; ISSN: 0032-3918 POLYMER NEWS , 23(6), 187-192 CODEN: PLYNBU; ISSN: 0032-3918, 1998 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010287564A (en) * 2009-06-15 2010-12-24 Taiwan Hopax Chemicals Manufacturing Co Ltd Electrolyte for electrochemical elements, and its electrochemical element
JP2016128416A (en) * 2009-11-20 2016-07-14 サントル ナシオナル ドゥ ラ ルシェルシェサイアンティフィク(セエヌエールエス) Dicarbonate precursor, and production method and use of the same
FR2952933A1 (en) * 2009-11-20 2011-05-27 Centre Nat Rech Scient BISCARBONATE PRECURSORS, PROCESS FOR PREPARING THEM AND USES THEREOF
WO2011061452A3 (en) * 2009-11-20 2011-07-21 Centre National De La Recherche Scientifique (C.N.R.S) Bicarbonate precursors, method for preparing same and uses thereof
JP2013511500A (en) * 2009-11-20 2013-04-04 サントル ナシオナル ドゥ ラ ルシェルシェサイアンティフィク(セエヌエールエス) Dicarbonate precursor, process for its production and use thereof
US9115111B2 (en) 2009-11-20 2015-08-25 Centre National De La Recherche Scientifique (C.N.R.S.) Bicarbonate precursors, method for preparing same and uses thereof
JP2015227373A (en) * 2010-06-10 2015-12-17 日産化学工業株式会社 Cyclocarbonate group-containing compound
JP5581435B1 (en) * 2013-11-13 2014-08-27 大都産業株式会社 Curable resin composition
WO2015164692A1 (en) 2014-04-25 2015-10-29 Valspar Sourcing, Inc. Polycyclocarbonate compounds and polymers formed therefrom
EP3134484A4 (en) * 2014-04-25 2018-04-11 Valspar Sourcing, Inc. Polycyclocarbonate compounds and polymers formed therefrom
US10000461B2 (en) 2014-04-25 2018-06-19 Swimc Llc Polycyclocarbonate compounds and polymers formed therefrom
US10717897B2 (en) 2014-04-25 2020-07-21 The Sherwin-Williams Company Polycyclocarbonate compounds and polymers and compositions formed therefrom
US10759773B2 (en) 2014-04-25 2020-09-01 Swimc Llc Polycyclocarbonate compounds and polymers formed therefrom
US12077676B2 (en) 2014-04-25 2024-09-03 Swimc Llc Polycyclocarbonate compounds and polymers and compositions formed therefrom
WO2022174360A1 (en) 2021-02-22 2022-08-25 Thierry Schwitzguebel Anisotropic polycyclic carbonates

Also Published As

Publication number Publication date
GB2432160A (en) 2007-05-16
US20080286486A1 (en) 2008-11-20
GB0523200D0 (en) 2005-12-21
EP1948711A1 (en) 2008-07-30

Similar Documents

Publication Publication Date Title
EP1948711A1 (en) Cyclocarbonate-containing energy-curable compositions
US8785515B2 (en) Sensitizer for cationic photoinitiators
CA2589123A1 (en) Cationically curable coating compositions
AU2006218944B2 (en) Sprayable coating composition
KR101495125B1 (en) Active energy ray-curable composition and method for producing the same
ES2349430T3 (en) COMPOSITION OF HARMFUL COATINGS BY ENERGY.
AU2006218942B2 (en) Coating compositions
JP2012211327A (en) Inkjet ink
JP2006083389A (en) Photocationic-curable composition
JP4352862B2 (en) Cycloaliphatic compounds having an oxetane ring
JP4760827B2 (en) 1,3-propanediol derivative having oxetane ring
JP2005060423A (en) Curable composition comprising norbornane ring-containing epoxy compound
JP2005132886A (en) Oxetane resin comprising polyaddition reaction product of dicyclopentadiene with phenol
JP2006206762A (en) Oxetane-ring-containing dihydroxybenzene derivative mixture

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 12092749

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

REEP Request for entry into the european phase

Ref document number: 2006826834

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2006826834

Country of ref document: EP