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WO1998023683A1 - Compositions durcissables sous l'effet d'un rayonnement a base de composes de polyester insature, d'ether vinylique et d'urethane ether vinylique - Google Patents

Compositions durcissables sous l'effet d'un rayonnement a base de composes de polyester insature, d'ether vinylique et d'urethane ether vinylique Download PDF

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Publication number
WO1998023683A1
WO1998023683A1 PCT/US1997/021542 US9721542W WO9823683A1 WO 1998023683 A1 WO1998023683 A1 WO 1998023683A1 US 9721542 W US9721542 W US 9721542W WO 9823683 A1 WO9823683 A1 WO 9823683A1
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WIPO (PCT)
Prior art keywords
vinyl ether
compound
unsaturated polyester
composition
urethane
Prior art date
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Ceased
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PCT/US1997/021542
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English (en)
Inventor
Charles B. Friedlander
Ronald R. Ambrose
David A. Diehl
Alan B. Weissberg
Carolyn A. Novak
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PPG Industries Inc
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PPG Industries Inc
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Priority to AU74104/98A priority Critical patent/AU7410498A/en
Publication of WO1998023683A1 publication Critical patent/WO1998023683A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters

Definitions

  • the technical field of the present invention relates to radiation curable compositions. Particularly, it relates to radiation curable coating compositions containing unsaturated polyester compounds in combination with vinyl ether compounds.
  • radiation curable coating compositions can be used to meet these objectives.
  • Coatings produced in accordance with U.S. Patent No. 5,536,760 have a relatively fast cure response when exposed to radiation. If a large number of ethylenically unsaturated groups are present in the unsaturated ester compounds, the coatings disclosed therein have the potential of being hard and brittle. Although there are many applications where properties such as hardness and brittleness are highly desirable, it is sometimes equally desirable for radiation-cured coating composition to be hard and flexible. Moreover, notwithstanding their relatively fast cure response, it is also often desirable to even further accelerate the cure rates of such coating compositions.
  • R is a residue of an organic alcohol or polyol, substantially free of maleate or fumarate groups, with a molecular weight from 56 to 2,000;
  • R 4 is hydrogen or methyl.
  • the vinyl e er-containing first component can be produced by conventionally reacting a vinyl ether having either a hydroxyl group or amine group with a saturated backbone containing component.
  • This saturated backbone containing component may be the reaction product of saturated hydroxy functional polyesters, polycarbonates, polycaprolactones, polyethers, bisphenol A alkoxylates or siloxanes with organic polyisocyanates.
  • the group linking the vinyl ether group to the saturated backbone in these patents can be a urethane, urea, ester, ether or thio group.
  • the vinyl ether-containing first component can be poly vinyl ether polyure thanes and saturated polyesters.
  • the second component of U.S. Patent No. 5,334,455 is a compound having epoxy-containing backbones and maleate and/or fumarate end groups.
  • the second component of U.S. Patent No. 5,334,456 is a compound having saturated polyester backbones and maleate and/or fumarate end groups.
  • the second component of U.S. Patent No. 5,340,653 is a compound having urethane backbones and maleate and/or fumarate end groups.
  • the second component each of these patents must be capped with maleate and/or fumarate groups. According to each of these patents, the resulting cured coatings exhibit good flexibility, tensile strength, percent elongation and good adhesion to substrates.
  • U.S. Patent No. 5,200,490 discloses radiation curable coating compositions which contain polyurethane vinyl ethers.
  • polyurethane vinyl ethers are obtained by reacting: (a) 1 NCO equivalent of 1 or more isocyanurate-containing polyisocyanates with (b) 0.01 to 1.0 equivalent of one or more monohydroxy vinyl ethers, and (c) 0 to 0.99 equivalent of functional groups of further compounds which react with NCO groups to saturate isocyanate groups which have not reacted with monohydroxy vinyl ethers so that no free isocyanate is present in the resulting polyurethane vinyl ethers.
  • the isocyanurate-containing compounds disclosed therein are cationically cured, as opposed to free radically cured. Cationic cure systems are sometimes less desirable than free radical cure systems due to the former's moisture sensitivity of the resulting cured coating.
  • One object of the present invention is to provide hard and flexible radiation curable coating compositions which do not require the use of (meth)acrylates as one of their major components.
  • Another object of the present invention is to provide radiation curable coating compositions having an improved cure response.
  • Still another object of the present invention is to provide radiation curable coating compositions with improved oxygen tolerance during the curing process.
  • Yet another object of the present invention is to provide substrates having cured thereon at least one film comprising the radiation curable coating compositions of the present invention.
  • novel, radiation curable coating compositions which include: (a) an unsaturated polyester compound; (b) a polymerizable vinyl ether compound ; and (c) a polymerizable urethane vinyl ether compound having a saturated, urethane-containing backbone with vinyl ether groups.
  • the present invention also provides substrates having cured thereon a film of radiation curable coating compositions described above.
  • unsaturated polyester compound refers to a polyunsaturated polymer (s) and/or an oligomer(s) having more than 2.0 unsaturated ester groups per molecule and being prepared by the reaction of unsaturated carboxylic acids and/or blends of unsaturated and saturated carboxylic acids with polyhydric alcohols and/or blends of polyhydric and monohydric alcohols.
  • polymerizable vinyl ether compound and “polymerizable urethane vinyl ether compound” as used herein refer to compounds having vinyl ether groups which can react, upon exposure to radiation, with the ethylenic unsaturation of the unsaturated polyester compound.
  • the unsaturated polyester compound which can be used when practicing this invention includes hydroxy functional unsaturated polycarboxylates, polycaprolactones, and the like.
  • the unsaturated polyester compound is a hydroxy functional unsaturated polycarboxylate which is the esterification product of an ethylenically unsaturated carboxylic acid and a polyhydric alcohol.
  • Unsaturated carboxylic acids which can be used in preparing such a preferred unsaturated polyester compound include unsaturated carboxylic acids having an acid functionality of at least two and/or their corresponding anhydrides.
  • unsaturated carboxylic acids and/or their anhydrides which can be used for this purpose include: maleic acid, maleic anhydride, fumaric acid and itaconic acid.
  • maleic anhydride Since it is readily available and relatively inexpensive, maleic anhydride is economically desirable. However, since maleate esters do not copolymerize with vinyl ethers as readily as fumarate esters (e.g. , esters derived from fumaric acid), fumarate esters are preferred for making the unsaturated ester compound of the present invention when increased cure response is an objective.
  • fumarate esters are preferred for making the unsaturated ester compound of the present invention when increased cure response is an objective.
  • the unsaturated carboxylic acids used in preparing the aforementioned preferred unsaturated polyester compound can also be blended with a saturated carboxylic acid.
  • saturated carboxylic acids which can be used for this purpose include: phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, malonic acid, pimelic acid, suberic acid, 2,2-dimethylsuccinic acid, 3,3-dimethylglutaric acid, 2,2-dimethylglutaric acid and mixtures thereof.
  • anhydrides of the saturated carboxylic acids, where they exist can also be used for this purpose.
  • Polyhydric alcohols which can be used in preparing the aforementioned preferred unsaturated polyester compound include: diethylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexane- dimethanol, l,2-bis(hydroxyethyl)cyclohexane, and 2,2-dimethyl-3-hydroxypropyl-2,2- dimethyl-3-hydroxypropionate, neopentyl glycol, 2-methyl-l,3-propane diol and the like and/or mixtures thereof.
  • the polyhydric alcohols which are used in preparing the aforementioned preferred unsaturated polyester compound are diols.
  • polyols having a hydroxyl functionality greater than two may be used for this purpose, it is preferred that the major portion, if not all, of the unsaturated polyester compounds used in this invention be comprised of linear, unsaturated polyester molecules. Since it is readily available and relatively inexpensive, diethylene glycol is a particularly preferred diol which can be used for this purpose.
  • the polyhydric alcohols used in preparing the aforementioned preferred unsaturated polyester compound can also be blended with monohydric alcohols. Examples of monohydric alcohols that can be used for this purpose include C, to C 15 alcohols.
  • the molecular weight of the unsaturated polyester compound employed when practicing this invention can vary widely. However, as measured by gel permeation chromatography (hereinafter "GPC") using a polystyrene standard, the unsaturated polyester compound typically has a peak molecular weight ranging from about 500 to about 50,000; preferably from about 600 to about 25,000; more preferable from about 700 to about 10,000; and even more preferably from about 800 to about 5,000.
  • GPC gel permeation chromatography
  • the unsaturated polyester compound can be prepared by a number of different procedures known to those skilled in the art.
  • the unsaturated polyester compound is prepared by heating a mixture of an unsaturated carboxylic acid or a blend of unsaturated and saturated carboxylic acids with a polyhydric alcohol or a blend of monohydric and polyhydric alcohols for about 1 to about 10 hours at temperatures ranging from about 150° C. to about 250° C, with water formed during the esterification being distilled off using a sparge of an inert gas such as nitrogen. Esterification catalysts, which increase the rate of such a reaction, can also be used in this process.
  • esterification catalysts include: para-toluenesulfonic acid, butylstannoic acid, dibutyltin oxide, stannous fluoride and stannous octoate.
  • the coating compositions prepared in accordance with this invention also include a polymerizable vinyl ether compound.
  • the polymerizable vinyl ether compounds of this invention can react with the unsaturated polyester compounds and include: (a) compounds which have an average of greater than 1.0 reactive vinyl ether groups per molecule and/or (b) a vinyl ether-containing group bonded to an unsaturated polyester compound such that the resulting compound has an average of at least 1.0 reactive vinyl ether group per molecule.
  • the vinyl ether groups of the polymerizable vinyl ether compound are different from, and cocurable with, the ethylenically unsaturated moieties in the backbone of the unsaturated polyester compound(e.g., those provided from the residue of the unsaturated carboxylic acid used in making an unsaturated polyester polymer and/or oligomer).
  • Examples of compounds containing greater than 1.0 reactive vinyl ether groups per molecule include vinyl ethers made in known mariners from di-, tri-, or tetrafunctional polyols, acetylene and a basic catalyst under pressure. It also includes vinyl ether terminated polyesters such as those made in accordance with the processes disclosed in U.S. Patent No. 5,286,835.
  • Such compounds include: tripropylene glycol divinyl ether, diethylene glycol divinyl ether, 1 ,4-butanediol divinyl ether, tetraethylene glycol divinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, polytetrahydrofuran divinyl ether, vinyl ether terminated polyesters and the like, and combinations thereof.
  • Triethylene glycol divinyl ether is the preferred vinyl ether compound for use in this invention.
  • One example of a compound having at least 1.0 reactive vinyl ether- containing group bonded to the unsaturated polyester compound which can be used when practicing this invention can be made by polymerizing a hydroxy-functional vinyl ether (e.g., hydroxybutyl vinyl ether) with a polyisocyanate (e.g. , isophorone diisocyanate) to form a half-capped isocyanate adduct. Thereafter, residual isocyanato functionality of the half-capped adduct is reacted with the hydroxyl functionality of an unsaturated polyol so as to structurally incorporate of at least 1.0 reactive vinyl ether groups in the unsaturated polyester compound.
  • a hydroxy-functional vinyl ether e.g., hydroxybutyl vinyl ether
  • a polyisocyanate e.g. , isophorone diisocyanate
  • Examples of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides and polyols which are suitable for preparing such hydroxyl-functional unsaturated polyester resins include those described herein previously.
  • Examples of polyisocyanates which can be used for this purpose include: toluene-2 , 4-diisocy anate , toluene-2 , 6-diisocy anate ; dipheny lmethane-4 ,4 ' -diisocyanate , diphenylmethane-2,4'-diisocyanate; para-phenylene diisocyanate; biphenyl diisocyanate; 3,3'-dimethyl-4,4'-diphenylene diisocyanate; tetramethylene-1 ,4-diisocyanate; hexamethylene-l,6-diisocyanate; 2,2,4-trimethylhexane-l,6-diisocyanate; lysine
  • the resulting unsaturated polyester compounds contain urethane moieties and are usually free of unreacted isocyanate groups.
  • the vinyl ether compound used when practicing this invention can also include a blend of a compound having an average of greater than 1.0 reactive vinyl ether groups per molecule and a compound having at least 1.0 reactive vinyl ether- containing groups bonded to the unsaturated polyester compound. Examples of both such vinyl ether-containing compounds include those previously described herein.
  • the coating compositions prepared in accordance with this invention also include a polymerizable urethane vinyl ether compound.
  • the polymerizable urethane vinyl ether compound of this invention can also react with the unsaturated polyester compound.
  • This urethane vinyl ether compound has a saturated, urethane- containing backbone with vinyl ether groups linked thereto.
  • the urethane vinyl ether compound used when practicing this invention can be produced conventionally by reacting a vinyl ether compound having hydroxyl group and/or amine group functionality with a compound having a saturated, urethane- containing backbone and isocyanate functionality.
  • the compound having the saturated, urethane- containing backbone is typically made by the polymerizing polyisocyanates with saturated, hydroxy-functional compounds.
  • saturated, hydroxy-functional compounds which can be used for this purpose include: polyesters, polycarbonates, polycaprolactones, polyethers, bisphenol A alkoxylates and siloxanes.
  • the saturated, hydroxy-functional compound comprises a saturated polyester which includes soluble reaction products of saturated polycarboxylic acids (or their anhydrides) with polyols.
  • suitable saturated polycarboxylic acids and anhydrides which can be used for this purpose include: phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrachlorophthalic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, malonic acid, pimelic acid, suberic acid, 2,2-dimethyl succinic acid, 3,3-dimethylglutaric acid, 2,2-dimethyl glutaric acid, anhydrides thereof and/or mixtures thereof.
  • polyols examples include: diethylene glycol, ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, glycerol, trimethylolpropane, pentaerythritol, sorbitol, 1,6-hexanediol, 1,4-cyclohexanediol, 1 ,4-cyclohexane- dimethanol, l,2-bis(hydroxyethyl)cyclohexane, and 2,2-dimethyl-3-hydroxypropyl-2,2- dimethyl-3-hydroxypropionate, neopentyl glycol, 2-methyl-l,3-propane diol and the like and/or mixtures thereof.
  • the vinyl ether compounds which react with the aforementioned compounds having a saturated urethane-containing backbone have hydroxyl group and/or amine group functionality.
  • such vinyl ether compounds Preferably, such vinyl ether compounds have hydroxyl group functionality.
  • hydroxy-functional vinyl ether compounds which can be used for this purpose include: triethylene glycol monovinyl ether; 1,4- cyclohexane dimethylol monovinyl ether, l-methyl-3-hydroxypropyl vinyl ether, 4- hydroxybutyl vinyl ether and mixtures thereof.
  • the preferred hydroxy-functional vinyl ether compound used to produce the urethane vinyl ether compounds of this invention is 4-hydroxybutyl vinyl ether.
  • the groups linking the vinyl ether groups to the saturated, urethane-contaimng backbone component is typically at least one of the following: urethane, urea, ester, ether and thio groups.
  • preferred linking groups include urethane, urea and/or ester groups. More preferably, the linking groups are urethanes.
  • Urethane vinyl ether compounds can also be prepared by polymerizing a hydroxy-functional vinyl ether (e.g., hydroxybutyl vinyl ether) with a polyisocyanate (e.g., isophorone diisocyanate) to form a half-capped diisocyanate adduct. Thereafter, residual isocyanato functionality of the half-capped adduct is reacted with the hydroxyl functionality of a saturated polyol so as to structurally incorporate an average of at least 1.0 reactive vinyl ether groups per molecule.
  • a hydroxy-functional vinyl ether e.g., hydroxybutyl vinyl ether
  • a polyisocyanate e.g., isophorone diisocyanate
  • the molecular weight of the urethane vinyl ether compound used when practicing this invention can vary widely. Typically, it has a peak molecular weight, as measured by GPC using a polystyrene standard, ranging from about 200 to about 50,000; preferably from about 300 to about 25,000; more preferably from about 400 to about 15,000; and even more preferably from about 500 to about 5,000.
  • the ratio of the sum of the carbon-carbon double bond equivalents from the vinyl ether and urethane vinyl ether compound to the carbon-carbon double bond equivalents from the unsaturated polyester compound typically ranges from about 0.1:1 to about 1.5:1; preferably from about 0.2:1 to about 1.4:1; and more preferably from about 0.3:1 to about 1.2: 1.
  • That portion derived solely from the urethane vinyl ether compound typically ranges from about 1 % to about 99 % ; preferably from about 3 % to about 85 % ; more preferably from about 5 % to about 65%; and even more preferably from about 10 % to about 50 %.
  • the vinyl ether, urethane vinyl ether and unsaturated polyester compounds are employed in the radiation curable composition of the present invention in relative amounts to obtain the desired ratio of carbon-carbon double bond equivalents so as to provide crosslinking via reaction of ethylenic unsaturation provided from the unsaturated polyester compound with vinyl unsat ⁇ ration provided by the vinyl ether and urethane vinyl ether compound upon free-radical curing of the composition (e.g. , when exposed to radiation).
  • the radiation curable coating composition of the present invention are essentially free of components that would destabilize the coating composition during processing, handling and/or application procedures by initiating the premature polymerization of the vinyl ether and/or urethane vinyl ether compounds (hereinafter referred to as "destabilizing agents").
  • a components that would destabilize the coating compositions prepared in accordance with this invention is oxidizing agents.
  • the presence of a sufficient amount of destabilizing agents (e.g. , peroxides and hydroperoxides) in the unsaturated polyester, vinyl ether and/or urethane vinyl ether compounds may initiate polymerization prior to their being blended together and exposed to radiation.
  • the presence of destabilizing agents in the unsaturated polyester compound may still cause premature polymerization when all of the components are mixed together.
  • the unsaturated polyester, vinyl ether and urethane vinyl ether compounds in a manner such that they are all essentially free of destabilizing agents. It is also possible to handle these compounds and/or any mixture thereof in a manner such that they remain essentially free of destabilizing agents until polymerization is initiated by exposure to radiation. However, in those instances where the processing and/or handling conditions are such that it is difficult to keep the compounds and/or mixtures thereof essentially free of destabilizing agents prior to their exposure to radiation, it is preferred to blend these compounds with a reducing agent so as to decompose at least some of the destabilizing agents which are, or may be, present therein.
  • Reducing agents which can be used to stabilize the radiation curable coating compositions prepared in accordance with this invention are those which, while being able to decompose destabilizing agents do not adversely affect the properties of the compounds which they are blended and/or the resulting radiation curable coating composition.
  • reducing agents include organic phosphites such as: dimethyl-phosphite, dioctyl-phosphite, diphenyl-phosphite, tri-octyl-phosphite, tri- stearyl-phosphite, trimethyl-phosphite, tri-ethyl-phosphite, tri-isopropyl-phosphite, tris- allyl-phosphite, didecyl-phenyl-phosphite, tri-phenyl-phosphite, tris-4-nonylphenyl- phosphite, tris-4-chlorophenyl-phosphite, tri-laurylthio-phosphite, tetraphenyl- dipropylene-glycol-diphosphite and mixtures thereof.
  • organic phosphites such as: dimethyl-phosphite, dioctyl-
  • the mixture of the unsaturated polyester, vinyl ether and urethane vinyl ether compounds is prepared and handled in a manner so as to keep it essentially free of destadilizing agents prior to being exposed to radiation, then it is only necessary to blend reducing agents with those compounds which are not prepared and/or handled in a manner so as to keep them essentially free of destabilizing agents.
  • the amount of a reducing agent necessary to decompose destabilizing agents that are, or may be, present can be added to any one or more of the compounds. However, if all of the reducing agent is added to only some of the compounds, this may not prevent the premature polymerization since the compound(s) to which reducing agents has/have not been added may contain destabilizing agents.
  • each of the compounds are individually blended with reducing agents.
  • the amount of reducing agent employed is that which is necessary to decompose at least some of the destabilizing agents which are, or may be, present in the individual compounds and/or any mixture thereof.
  • the reducing agent is employed in an amount which is necessary to decompose more than 50% of the destabilizing agents present in the individual compounds and/or any mixture thereof, preferably at least 70%, more preferably at least 90%, and even more preferably, at least 95%.
  • the amount of reducing agent typically employed is at least about 0.05 weight percent of the respective compound's total resin solids. If two or more of the compounds are blended together prior to being treated with a reducing agent, the amount of reducing agent employed is typically at least about 0.05 weight percent of the blend's total resin solids. Preferably, the amount of reducing agent employed ranges from about 0.05 to about 10 weight percent, more preferably from about 0.1 to about 6 weight percent, and even more preferably from about 0.5 to 3 weight percent. These weight percentages are based upon the respective compound's total resin solids or the blend's total resin solids.
  • reducing agents are preferably permitted to react separately with the contaminated compound(s) for a time sufficient to decompose the oxidizing agents present therein.
  • Dwell time for such a treatment process is temperature dependent.
  • sufficient treatment dwell times typically range from about 1 hour at 100° C. to about 24 hours at ambient temperature, preferably from about 2 hours at 100° C. to about 36 hours at ambient temperatures, and more preferably from about 3 hours at 100° C. to about 48 hours at ambient temperatures.
  • the coating compositions of the present invention can be cured by various conventional means known to those skilled in the art.
  • the coating compositions can be cured by exposure to ionizing radiation (e.g. , by electron beam), actinic energy (e.g. , by ultraviolet light) and/or thermal energy (e.g., heat).
  • ionizing radiation e.g. , by electron beam
  • actinic energy e.g. , by ultraviolet light
  • thermal energy e.g., heat
  • the preferred method of curing the coating compositions of the present invention is by exposure to radiation (e.g. , ionizing and/or actinic radiation).
  • Ionizing radiation is radiation having energy at least sufficient to produce ions either directly or indirectly in a medium such as air or water.
  • ionizing radiation sources include accelerated electrons as produced by generally known electron beam devices.
  • the energy of the accelerated electrons typically ranges from about 50,000 electron volts to about 300,000 electron volts.
  • the amount of ionizing radiation in rads for curing a composition of the invention will vary depending on factors such as the particular formulation of the radiation curable composition, thickness of the applied layer of coating composition on the substrate, temperature of the composition, and the like.
  • coating compositions prepared in accordance with this invention are their excellent degree of cure at low doses of ionizing radiation.
  • a 1 mil (25 micron) thick wet film of a coating composition of this invention can be cured in the presence of oxygen through its thickness to a tack-free state upon exposure to from about 0.5 to about 5 megarads of ionizing radiation.
  • Actinic radiation is light with wavelengths of electromagnetic radiation ranging from the ultraviolet light range, through the visible light range, and into the infrared range.
  • Actinic radiation which can be used to cure coating compositions of this invention generally has wavelengths of electromagnetic radiation ranging from about 150 to about 2,000 nanometers (nm), preferably from about 180 to about 1,000 nm, and more preferably from about 200 to about 500 nm.
  • ultraviolet light sources generally known in the art can be used to cure the radiation curable coatings of this invention.
  • examples of such include: mercury arcs, carbon arcs, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, swirl-flow plasma arcs and ultraviolet light emitting diodes.
  • ultraviolet light-emitting lamps of the medium pressure mercury vapor type are employed when practicing this invention.
  • Such lamps usually have fused quartz envelopes and are ordinarily in the form of long tubes having an electrode at each end.
  • Preferred medium pressure mercury lamps have outputs ranging from about 200 to about 600 watts per inch (about 79 to about 237 watts per centimeter) across the length of the tube.
  • actinic radiation does not possess sufficient energy to produce ions in a medium such as air or water. Accordingly, it is necessary to use formulation additives (e.g., photoinitiators and/or photosensitizers) therewith to initiate the polymerization process.
  • formulation additives e.g., photoinitiators and/or photosensitizers
  • Photoinitiators and/or photosensitizers are typically present in those coating compositions prepared in accordance with this invention which are designed to be cured by actinic radiation since they provide high energy free radicals following radiation. These free radicals, in turn, initiate the polymerization process.
  • photoinitiators When utilized in the coating compositions of this invention, photoinitiators are typically present an amount ranging from about 0.01 to about 20 weight percent, preferably from about 0.05 to about 15 weight percent, and more preferably from about 0.1 to about 10 weight percent. These weight percentages are based upon the total weight of the coating composition.
  • Photoinitiators which can be used to cure coating composition prepared in accordance with this invention include those having an absorption in the range from about 150 to about 2,000 nm, preferably from about 180 to about 1,000 nm, and more preferably from about 200 to about 500 nm.
  • the photoinitiators typically comprise at least one of the following compounds: hydroxy- or alkoxy-functional acetophenone derivatives, or benzoyl diary 1 phosphine oxides.
  • photoinitiators examples include: benzophenone, anthraquinone and thioxanthone, isobutyl benzoin ether, mixtures of butyl isomers of butyl benzoin ether, alpha, alpha-diethoxy acetophenone, alpha, alpha-dimethoxy-alpha-phenylacetophenone, 2-hydroxy-2-methyl-l-phenyl propane 1-one and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.
  • photoinitiators that can be used in the coating compositions of this invention include those set out in U.S. Patent Nos. 4,017,652 and 5,340,653.
  • coating compositions prepared in accordance with this invention are their excellent degree of cure at relatively low doses of actinic radiation.
  • a 1 mil (25 micron) thick wet film of a coating composition of this invention which includes a photoinitiator can be cured through its thickness to a tack-free state upon exposure to actinic radiation by passing the film at a rate of about 20 feet per minute (about 6 meters per minute) or more under four or fewer medium pressure mercury vapor lamps operating at about 200 watts per inch (about 79 watts per centimeter) at a distance of about 4 inches (about 10 centimeters) from the surface of the wet film.
  • coating compositions prepared in accordance with this invention additionally contain a light stabilizer.
  • One example of a particularly preferred light stabilizer is bis(l,2,2,6,6-pentamethyl-4-piperidinyl) sebacate.
  • a light stabilizer is commercially available from Ciba-Geigy, Inc. as TINUVIN ® 292 hindered amine light stabilizer.
  • the radiation curable composition of the invention can additionally contain other ethylenically unsaturated monomers or oligomers, examples of which include: vinyl monomers such as vinyl acetate, styrene, vinyl toluene, divinyl benzene, methylvinyl ether, ethylvinyl ether and butylvinyl ether; acrylic and methacrylic esters such as methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, glycerol di(me) vinyl
  • Coating compositions of this present invention can optionally contain a solvent component.
  • solvents which can be used for this purpose include: conventional aliphatic and aromatic solvents or diluents known in the art.
  • Coating compositions of this invention can optionally contain a pigment component.
  • the pigment component typically comprises pigments which do not absorb or block that portion of the light spectrum which is necessary to initiate the photocuring process.
  • pigments which can be used in the coating compositions of this invention talc, calcium carbonate, aluminum silicate, magnesium silicate, barytes, titanium dioxide and silica.
  • compositions of the present invention may be thermally cured in the presence of a thermal free-radical initiator.
  • thermal initiators suitable for this purpose include: benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, cyclohexanone peroxide, 2,4-dichlorobenzoyl peroxide, bis(p-bromobenzoyl) peroxide, acetyl peroxide, N,N-azobis(isobutyrylnitrite), metallic dryer systems, redox systems, and the like.
  • Coating compositions of this invention can be in either a liquid or a solid
  • coating compositions can be applied to a variety of substrates, examples of which include: cellulosic materials (e.g., wood, paper, particleboard, chipboard), metals, metals having primers thereon, glass, plastics, metallized plastics, and the like and/or combinations thereof.
  • cellulosic materials e.g., wood, paper, particleboard, chipboard
  • metals e.g
  • This example illustrates the preparation of an unsaturated polyester compound which can be used in radiation curable coating compositions.
  • the charge was gradually heated to 250° F. (121° C.) at which time a nitrogen sparge was applied. Heating was continued to a temperature of 410° F. (210° C.) while a total of 564 milliliters of distillate containing water was removed at a head temperature which did not exceed 212° F. (100° C).
  • the unsaturated polyester was cooled to 189° F. (87° C.) at which time 11.20 grams dipropylene glycol tetraphenyl diphosphite and 18.7 grams triphenyl phosphite were added thereto. The charge was then held for three hours at about 190° F. (88° C.) The resulting product was an unsaturated polyester resin having an acid value of 4.6 milligrams of KOH/gram of sample, and a Gardner-Holdt bubble tube viscosity of Z4+ at a 100 percent by weight solids.
  • EXAMPLE 2 EXAMPLE 2
  • This example illustrates the preparation of a urethane vinyl ether compound having a saturated urethane-containing polyester backbone and vinyl ether groups.
  • a first reaction vessel equipped with means for steam distillation and an nitrogen sparge was charged with 740 grams phthalic anhydride, 830 grams isophthalic acid, 1040 grams neopentyl glycol, 1060 grams diethylene glycol and 4.0 grams butyl stannoic acid catalyst. The charge was gradually heated to a temperature of 209° C. while a total of 605 milliliters of distillate containing water was removed. The resulting product was a saturated polyester resin having an acid value of 1.1 milligrams of KOH/gram of sample.
  • This saturated polyester resin was then cooled to 36° C. at which time 368 grams of the divinyl ether of triethylene glycol was added thereto.
  • the saturated polyester resin had a Gardner-Holdt bubble tube viscosity of Z3 ⁇ at 25° C; a number- average molecular weight of 452 as determined by GPC using a polystyrene standard; and a measured hydroxyl value of 277.8 milligrams of KOH/gram of sample.
  • a second reaction vessel equipped with means for maintaining a blanket of nitrogen was charged at ambient temperature with 777 grams isophorone diisocyanate, 302.8 grams triethylene glycol divinyl ether, 11.0 grams triphenyl phosphite and 6.6 grams tetraphenyl dipropylene glycol diphosphite.
  • the charge was heated under nitrogen to 105° C. over 30 minutes and held at that temperature for about 3 hours.
  • the charge was then cooled to 60° C. over 1.25 hours. Thereafter, the vessel was allowed to cool to ambient temperature.
  • the charge was then heated under nitrogen to 34° C, and 0.2 grams dibutyl tin dilaurate was added thereto.
  • the saturated urethane vinyl ether compound from Example 2 was treated with a reducing agent.
  • the reducing agent was added at the end of the reaction rather than in the second reaction vessel.
  • the charged vessel was heated to 70° C, at which time 11.0 grams triphenyl phosphite and 6.6 grams tetraphenyl dipropylene glycol diphosphite were added thereto. The charge was then gradually heated to 100° C. and held at that temperature for about 3 hours.
  • Examples 4 and 5 represent coating compositions prepared in accordance with the present invention.
  • Example 4 represents a coating composition suitable for cure by ionizing radiation
  • Example 5 represents a coating composition suitable for cure by actinic radiation.
  • Example 4 The coating compositions of Examples 4 and 5 were prepared by mixing the ingredients set forth in TABLE 1.
  • TABLE 1 the triethylene glycol divinyl ether was blended with 0.3 weight percent triphenyl phosphite and 0.5 weight percent tetraphenyl dipropylene glycol diphosphite and, thereafter, held at room temperature for at least 16 hours prior to use. These weight percentages were based upon the weight of the triethylene glycol divinyl ether. Values in TABLE 1 represent percent by weight resin solids.
  • Samples 4a, 4b, 4c, and 4d were drawn down on the backside of Penopac Form 1A paper substrate (commercially available from Leneta Co.) using a Pamarco handproofer draw-down bar with a 360 dots per inch (940 dots per centimeter) roller (commercially available from Pamarco Inc.) to provide wet films having a thickness of 0.09 mil (2.3 microns). The films were then cured and subjected to a mar test and a smudge test to determine their degree of cure.
  • the mar tests were performed by rubbing the cured film with a corner of a commercially-available wooden tongue depressor under the pressure generated merely from the weight of the hand holding the tongue depressor. If visible scratches were produced and remained, the film was considered to be marred. The number and severity of scratches determined the degree of mar. The full range of the cure scale with regard to the mar test is as follows:
  • Examples 6 through 9 represent coating compositions prepared in accordance with the present invention. Of these coating compositions, those prepared in Examples 6 and 7 include an optional acrylate component, and those prepared in Examples 8 and 9 did not include an optional acrylate component.
  • Examples.6, 7, 8 and 9 were prepared by mixing together the ingredients set forth in TABLE 3.
  • TABLE 3 the triethylene glycol divinyl ether was blended with 0.3 weight percent triphenyl phosphite and 0.5 weight percent tetraphenyl dipropylene glycol diphosphite and, thereafter, held at room temperature for at least 16 hours prior to use. These weight percentages were based upon the weight of the triethylene glycol divinyl ether. Values in TABLE 3 represent percent by weight resin solids.
  • Epoxy diacrylate 3 16.0 17.0 — —
  • DAROCURE 1173 photoinitator commercially available from Ciba-Geigy Corp.
  • Examples 10 and 11 represent comparative coating compositions which do not contain a urethane vinyl ether compound
  • Examples 12 and 13 represent coating compositions prepared in accordance with the present invention.
  • a comparison of Examples 10 and 12 and a comparison of Examples 11 and 13 demonstrate the improved cure response and oxygen tolerance during the curing process of radiation curable coating compositions prepared in accordance with the present invention.
  • the coating compositions of Examples 10, 11, 12 and 13, were prepared by mixing together the ingredients in TABLE 5.
  • the triethylene glycol divinyl ether was blended with 0.3 weight percent triphenyl phosphite and 0.5 weight percent tetraphenyl dipropylene glycol diphosphite and, thereafter, held at room temperature for at least 16 hours prior to use. These weight percentages were based upon the weight of the triethylene glycol divinyl ether. Values in TABLE 5 represent percent by weight resin solids.
  • Example 10 Samples of each composition of Example 10, 11, 12 and 13 were drawn down on the backside of Penopac Form 1A paper substrate using a Pamarco handproofer draw-down bar with a 360 dots per inch roller to provide wet films having a thickness of about 0.09 mil (2.3 microns). The films were cured as set forth in TABLE 6. TABLE 6 also sets out level of cure observations as set out above. TABLE 6
  • Examples 14 and 16 represent comparative radiation curable coating compositions
  • Examples 15 and 17 represent radiation curable coating compositions prepared in accordance with the present invention.
  • Coating compositions of Examples 14, 15, 16 and 17 were prepared by mixing together the ingredients set forth in TABLE 7.
  • TABLE 7 the triethylene glycol divinyl ether and the polytetrahydrofuran divinyl ether were separately blended with 0.3 weight percent triphenyl phosphite and 0.5 weight percent tetraphenyl dipropylene glycol diphosphite and, thereafter, held at room temperature for at least 16 hours prior to use. These weight percentages were based upon the weight of the divinyl ether to which they were added. Values in TABLE 7 represent percent by weight resin solids.
  • Examples 18 and 19 represent coating compositions prepared in accordance with the present invention.
  • the coating compositions for Examples 18 and 19 were prepared by mixing the ingredients set forth in the following TABLE 9.
  • the coating composition represented in Example 18 contains approximately 10% by weight solids of the urethane vinyl ether compound from Example 3, and the composition represented by Example 19 contains approximately 40% by weight solids of the urethane vinyl ether compound from Example 22.
  • Values in TABLE 9 represent percent by weight by solids.
  • Sample 18a and 19a One sample of each of the coating compositions of Examples 18 and 19 (hereinafter designated as Sample 18a and 19a, respectively) was drawn down on aluminum substrate using a 0.018 inch (0.46 millimeters) wirewound draw bar.
  • Samples 18b and 19b One sample of each of the coating compositions of Examples 18 and 19 (hereinafter designated as Samples 18b and 19b, respectively) was drawn down using a 0.032 inch (0.81 millimeters)wire wound draw bar.
  • Each of the applied Samples 18a, 19a, 18b and 19b was cured by electron beam (EB curing conditions: 3 MR; 7.9 mpm; 5 mA; 35 ppm Oxygen).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention se rapporte à une composition durcissable sous l'effet d'un rayonnement comprenant: (a) un composé polyester insaturé, (b) un composé éther vinylique polymérisable, et (c) un composé uréthane éther vinylique polymérisable. Le composé polyester insaturé est caractérisé en ce qu'il comprend plus de 2,0 groupes esters insaturés par molécule et en ce qu'il constitue le produit de la réaction d'acides carboxyliques insaturés et/ou de mélanges d'acides carboxyliques insaturés et saturés avec des polyalcools et/ou des mélanges de polyalcools et de monoalcools. Le composé éther vinylique polymérisable est caractérisé en ce qu'il comprend au moins l'un des composants suivants: (a) un composé comprenant en moyenne plus de 1,0 groupe réactionnel éther vinylique par molécule, et (b) un groupe contenant de l'éther vinylique lié au composé polyester insaturé de manière qu'il y a en moyenne au moins 1,0 groupe réactionnel éther vinylique par molécule. Le composé éther uréthane vinylique polymérisable est caractérisé en ce qu'il présente un squelette contenant de l'uréthane saturé et des groupes éther vinylique. Les composés éther vinylique polymérisable et uréthane éther vinylique peuvent réagir, lorsqu'ils sont exposés à un rayonnement, avec la liaison éthylénique du composé polyester insaturé.
PCT/US1997/021542 1996-11-27 1997-11-21 Compositions durcissables sous l'effet d'un rayonnement a base de composes de polyester insature, d'ether vinylique et d'urethane ether vinylique Ceased WO1998023683A1 (fr)

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US08/758,616 1996-11-27

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000008109A1 (fr) * 1998-08-07 2000-02-17 Basf Aktiengesellschaft Liant durcissable par un rayonnement haute energie et/ou par la chaleur
EP1085529A3 (fr) * 1999-09-15 2001-04-04 Shipley Company LLC Composition diélectrique
US6617417B1 (en) 1999-02-02 2003-09-09 Ashland, Inc. Unsaturated polyester resin compositions
CN114269814A (zh) * 2019-05-31 2022-04-01 俄勒冈州立大学 由植物油基聚酯的uv固化制成的压敏粘合剂

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EP0322808A2 (fr) * 1987-12-28 1989-07-05 Ppg Industries, Inc. Compositions radiodurcissables à base de polyesters insaturés et de composés comprenant au moins deux groupes vinyl-éther
WO1990010660A1 (fr) * 1989-03-07 1990-09-20 Desoto, Inc. Compositions durcissables a radicaux libres
EP0636669A2 (fr) * 1993-07-30 1995-02-01 Dsm N.V. Composition de liant pour peintures en poudre, durcissable par irradiation
WO1996001283A1 (fr) * 1994-07-05 1996-01-18 Ppg Industries, Inc. Compositions de polyester et d'ether vinylique durcissables par radiations et comportant un diluant reactif

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0322808A2 (fr) * 1987-12-28 1989-07-05 Ppg Industries, Inc. Compositions radiodurcissables à base de polyesters insaturés et de composés comprenant au moins deux groupes vinyl-éther
WO1990010660A1 (fr) * 1989-03-07 1990-09-20 Desoto, Inc. Compositions durcissables a radicaux libres
EP0636669A2 (fr) * 1993-07-30 1995-02-01 Dsm N.V. Composition de liant pour peintures en poudre, durcissable par irradiation
WO1996001283A1 (fr) * 1994-07-05 1996-01-18 Ppg Industries, Inc. Compositions de polyester et d'ether vinylique durcissables par radiations et comportant un diluant reactif

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000008109A1 (fr) * 1998-08-07 2000-02-17 Basf Aktiengesellschaft Liant durcissable par un rayonnement haute energie et/ou par la chaleur
US6617417B1 (en) 1999-02-02 2003-09-09 Ashland, Inc. Unsaturated polyester resin compositions
EP1085529A3 (fr) * 1999-09-15 2001-04-04 Shipley Company LLC Composition diélectrique
US6440642B1 (en) 1999-09-15 2002-08-27 Shipley Company, L.L.C. Dielectric composition
SG93890A1 (en) * 1999-09-15 2003-01-21 Shipley Co Llc Dielectric composition
CN114269814A (zh) * 2019-05-31 2022-04-01 俄勒冈州立大学 由植物油基聚酯的uv固化制成的压敏粘合剂
US12291598B2 (en) 2019-05-31 2025-05-06 Oregon State University Pressure sensitive adhesives made from UV curing of plant oil-based polyesters

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