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WO1990003988A1 - Melanges par exposition de polyurethanes d'ether vinylique et d'elastomeres non satures polymerisables aux ultra-violets, et revetements les contenant - Google Patents

Melanges par exposition de polyurethanes d'ether vinylique et d'elastomeres non satures polymerisables aux ultra-violets, et revetements les contenant Download PDF

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Publication number
WO1990003988A1
WO1990003988A1 PCT/US1989/004240 US8904240W WO9003988A1 WO 1990003988 A1 WO1990003988 A1 WO 1990003988A1 US 8904240 W US8904240 W US 8904240W WO 9003988 A1 WO9003988 A1 WO 9003988A1
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Prior art keywords
mixture
recited
vinyl ether
elastomer
polyurethane
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PCT/US1989/004240
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English (en)
Inventor
Sami A. Shama
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DeSoto Inc
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DeSoto Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/6715—Unsaturated monofunctional alcohols or amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • This invention relates to ultraviolet-curable blends of vinyl ether-terminated polyurethanes and ethylenically unsaturated elastomers, and includes coatings containing these blends. These blends include a catalyst which initiates a cationic cure when exposed to actinic radiation, the unsaturated elastomer participating in the cure and functioning to soften the cured coatings.
  • a catalyst which initiates a cationic cure when exposed to actinic radiation
  • the unsaturated elastomer participating in the cure and functioning to soften the cured coatings.
  • Background Art Ultraviolet-curable coatings based on acrylate- ter inated polyurethanes are well known. Many of the rapidly curing polyurethanes carrying terminal acrylate groups are too hard for some purposes, such as primer coatings for optical glass fiber, so these are combined with liquid materials which function to soften the films which are produced on cure.
  • the present invention provides liquid mixtures (blends) of vinyl ether-terminated polyurethanes and ethylenically unsaturated liquid polymeric elastomers • which are substantially free of hydroxy functionality and which are curable with actinic light in or near the ultraviolet range in the presence of a cationic photoinitiator.
  • the invention includes coating compositions containing these blends in admixture with an amount of a cationic photoinitiator which is effective to initiate a cationic cure when exposed to actinic light. It is surprising to find that the unsaturated elastomer participates in the cationic cure even though it does not participate in a conventional free-radical polymerization. In the coatings of this invention, the unsaturated elastomer functions to soften the cured coatings.
  • polyvinyl ethers of polyols are useful diluents for vinyl ether-terminated polyurethanes, and can be regarded as polyfunctional reactive diluents. But these polyfunctional reactive diluents generally function to harden the cured composition. Monovinyl ethers are usually somewhat volatile, and hence it is preferred not to employ them in ultraviolet-curable coatings which are desirably free of volatile components. This leaves little opportunity to enhance the softness of the cured coatings, so it is desired to minimize the proportion of such reactive diluents herein, or at least to minimize their hardening action by introducing a softening action to counterbalance it.
  • the vinyl ether-terminated polyurethanes are themselves known, and these tend to be hard and brittle when cured, albeit those of relatively lower molecular weight are harder and more brittle than those of relatively higher molecular weight. Regardless of the hardness of the cured polyurethane, for some purposes it is desired to soften these. Softness is here measured by a reduced tensile strength and a reduced modulus of elasticity. It is found that from about 0.1% to about 40%, preferably from 0.5% to 20%, of the ethylenically unsaturated liquid polymeric elastomer based on the total weight of the elastomer and polyurethane, serves to provide desired softness when the mixture is cured by a cationic cure.
  • saturated elastomers are not useful herein. This is because saturated elastomers retard the cure and render it sluggish. The greater the proportion of saturated elastomer, the more it disturbs the desired cationic cure.
  • the coating compositions of the present invention comprise a blend of a vinyl ether-terminated polyurethane and an ethylenically unsaturated liquid polymeric elastomer.
  • Vinyl ether-terminated polyurethanes are well known. These are made in conventional fashion from aliphatic monohydric vinyl ethers, which are known and available compounds. These monohydric vinyl ethers are formed in various ways, for example by reaction of a polyhydric alcohol, usually a diol, with acetylene in the presence of potassium hydroxide as catalyst. Thus, any liquid diol, such as 1,4-butane diol, can be partially reacted to form the monovinyl ether, and this monovinyl ether can be separated and is available as such. Other aliphatic monohydric vinyl ethers can be made in the same or other ways. These monohydric vinyl ethers can be used as an unsaturated capping agent for isocyanate-terminated oligomers in the same way that monohydric acrylates are used as capping agents to provide vinyl ether-terminated polyurethanes.
  • This invention will be illustrated using as the vinyl ether, the monovinyl ether of 1,4-butane diol, but it will be understood that other aliphatic monohydric vinyl ethers can be substituted therefor. These other vinyl ethers will be illustrated by the monovinyl ether of 1,4-cyclohexane dimethanol, 1,6-hexane diol, ethylene glycol, or triethylene glycol. Polyols of higher functionality used to provide a monohydric vinyl ether are illustrated by the divinyl ether of trimethylol propane or glycerin.
  • the vinyl ether-terminated polyurethane is the reaction product of an aliphatic monohydric vinyl ether and an isocyanate-terminated oligomer which is the reaction product of an organic diisocyanate with a stoichiometric deficiency of material having a plurality of isocyanate-reactive hydrogen atoms, usually two.
  • Vinyl ether-terminated polyurethanes are described in Bishop, Pasternack and Cutler U.S. Pat. No. 4,472,019 and also in Lapin and House patent 4,751,273. In each of these prior disclosures the vinyl ether- terminated polyurethane is formed by the reaction of an aliphatic monohydric vinyl ether with a diisocyanate. Many organic diisocyanates are disclosed in the Lapin and House disclosure, including those which are preferred herein.
  • the materials having a plurality of isocyanate- reactive hydrogen atoms are usually polyols or polyamines, and their use in stoichiometric deficiency forms isocyanate-terminated oligomers.
  • the polyols are preferably diols, especially polyether diols, such as polyoxyethylene glycol, polyoxypropylene glycol or polytetrahydrofuran, but polyester diols, such as reaction products of diols with caprolactone, are also useful. These diols can have molecular weights of from about 60 to about 3,000, preferably from 300 to 2,000.
  • the corresponding dia ines are also useful, forming isocyanate-terminated polyureas instead of polyurethanes.
  • isocyanate-terminated oligomers are capped in this invention by reaction with an aliphatic monohydric vinyl ether which can be a monovinyl ether or a polyvinyl ether.
  • an aliphatic monohydric vinyl ether which can be a monovinyl ether or a polyvinyl ether.
  • the above-described isocyanate-terminated polyurethanes or polyureas all become vinyl ether-terminated polyurethanes and are referred to herein as polyurethanes.
  • capped polyurethanes can be made in many ways, as by forming an isocyanate- terminated oligomer followed by capping, by prereacting the capping agent with diisocyanate to form a monoisocyanate which is later reacted with polyol or polyamine, or by reacting all of the reactants together at the same time. All of these variations are acceptable and embraced by reference to the reaction product of an aliphatic monohydric vinyl ether, isocyanate-reactive polyol or polyamine, and sufficient organic polyisocyanate (preferably diisocyanate) to react with substantially all of the isocyanate-reactive functionality.
  • the urethane and urea-forming reactions are well known, being easily carried out by heating to moderate temperature, preferably in the presence of an appropriate catalyst, such as dibutyltin dilaurate.
  • the reaction is usually forced by maintaining a temperature of from 40 C to 80 C to insure its completeness.
  • the examples will adequately illustrate the urethane reaction, and reaction with urea can be carried out in the same way except to note that catalyst is not needed.
  • aromatic diisocyanates namely those which are alkylene bisphenyl diisocyanates. These are themselves well known.
  • the alkylene group can contain from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms. These are illustrated by 1,2-diphenylethane diisocyanate and 1,3- diphenylpropane diisocyanate. It is preferred to employ compounds in which the two phenyl groups are carried by the same carbon atom so that the diisocyanate can be regarded as a derivative of methane.
  • the preferred diisocyanate is 4,4'-diphenylmethane diisocyanate.
  • This invention is especially concerned with coatings which cure to possess sufficient softness for use in contact with the glass surface of optical glass fibers.
  • vinyl ether-terminated polyurethanes having a number average molecular weight in the range of from about 1,500 to about 6,000.
  • the lower end of this range was too hard for use in contact with the optical glass surface, and the upper end of this range was too hard for use as a primary coating on optical glass fiber.
  • the entire range of molecular weight is rendered softer by this invention, and hence is rendered more useful wherever increased softness is desired.
  • the ethylenically unsaturated liquid polymeric elastomers are themselves well known and are hydrocarbons or halogen-substituted hydrocarbons.
  • Liquid polymers of any diethylenically unsaturated C 4 or C 5 hydrocarbon or halogen-substituted hydrocarbon are appropriate, such as butadiene or chloroprene.
  • These polymers are usually of oily liquid character, and those of low viscosity are preferred herein since these reduce the viscosity of the vinyl ether-terminated polyurethane which may be of excessive viscosity (higher than desired for coating application) or even of solid character.
  • Polyisoprene will further illustrate the useful ethylenically unsaturated elastomers, and a liquid polyisoprene is presently preferred and will be used as illustrative.
  • actinic light contemplated herein is desirably ultraviolet light, typically from 200 to 400 nanometers, but the light wavelengths which can be used are intended to include visible light near the ultraviolet range as well as those within it.
  • actinic light is used herein to include light having sufficient energy to initiate the cationic polymerization.
  • coating compositions are catalyzed with a cationic photoinitiator which initiates a cationic cure when exposed to actinic light, usually a sulfonium compound.
  • a cationic photoinitiator which initiates a cationic cure when exposed to actinic light, usually a sulfonium compound.
  • the proportion of said photoinitiator is an effective amount, preferably less than about 1.5% based on the weight of the unsaturated material present.
  • the preferred proportion of catalyst is from 0.1% to 1.4%, most preferably from 0.2-1.0%, on the same weight basis.
  • the cationic photoinitiators are themselves well known and available in commerce. They are typically illustrated by sulfonium compounds, but iodonium compounds are also known cationic photoinitiators, as are diazo compounds. These compounds are used in the proportions which have already been discussed.
  • a preferred, exemplary, catalyst is the triphenylsulfonium salt of hexafluorophosphate which is available in commerce from General Electric Co. under the trade designation UVE 1016.
  • the commercial photoinitiator is supplied as a 50% solution in propylene carbonate. The tiny amount of this volatile solvent introduced with the catalyst is too small to disturb the essentially solvent-free character of the compositions used herein.
  • the commercial catalyst compositions used in the examples herein are only 50% active (50% of the catalyst composition is constituted by propylene carbonate solvent) , so only half of the commercial catalyst provides actual catalytic material.
  • onium salts which are capable of functioning by themselves.
  • Diaryliodonium salts such as the 3M product sold under the trade name FC 509, are also contemplated, but these are normally used in combination with an aryl ketone photoinitiator, like benzophenone.
  • FC 509 aryl ketone photoinitiator
  • iodonium salts normally require aryl ketones to also be present, it is preferred to employ triaryl sulfonium salts, such as the 3M product sold under the trade name FC 508 and the General Electric Co. products sold under the trade names UVE 1014 and UVE 1016. These sulfonium salts do not require aryl ketones to also be present.
  • the cationic cure is itself well known. Amines and carboxyl-functional compounds are known to be deleterious and hence there is no purpose in including them in the coating formulation. It was not known that small amounts of hydroxy functionality would inhibit the cure of vinyl ether systems. It has now been found that the addition of 0.1% of hydroxy functionality by weight of the composition causes the cationic cure in this invention to be about 3 times slower than if that hydroxy functionality had not been added. This will illustrate the importance of having a composition which is substantially hydroxy-free.
  • Thickness is important in this invention, the cured coatings desirably having a thickness of from 1 to 10 mils, preferably from 2.5 to 6 mils.
  • the coating applied to the glass has a thickness of about 3.0 mils, and it must be cured rapidly throughout that thickness to provide a clear coating of only pale coloration having good physical properties including the capacity to resist considerable elongation without breaking and to resist water (both absorption and extraction) .
  • the rapid cure of these relatively thick coatings is accomplished herein by the application of ultraviolet light in a dosage of at least about 0.5 J/sq cm., and usually somewhat more than that.
  • the coatings evaluated herein have a thickness of about 3 mils and are cured with an exposure of 0.75 J/sq cm in a first instance and with an exposure of 0.5 J/sq cm in a second instance.
  • acrylate- terminated polyurethane compositions it is found that most of these require far more than 0.5 Joules/sq. cm. using a free radical photoinitiator, so the cures provided herein are at least about as rapid as those obtained with the conventional acrylate-functional compositions.
  • vinyl ether-terminated polyurethanes, the unsaturated elastomers and the photoinitiator can be the only materials present, other ethylenically unsaturated materials can also be present, especially vinyl ethers, like isobutyl vinyl ether, octyl vinyl ether, or polyvinyl ethers illustrated by the divinyl ether of 1,4-butane diol, 1,4-cyclohexane diol, or 1,6- hexane diol. These materials are reactive diluents, and they modify the reactivity and viscosity of the liquid coating compositions as well as the hardness of the cured product. It is stressed that while the polyvinyl ethers may introduce some hardness as they thin the coating composition, the elastomer component reduces this hardness.
  • Reactive diluents are not essential in this invention.
  • the vinyl ether-terminated polyurethanes desirably constitute from about 20% to 99% of the mixture with the reactive diluent, preferably from 30% to 80%.
  • the elastomer component used herein is not regarded to be a reactive diluent herein, though some would place it in that category because it is reactive and liquid.
  • the preferred reactive diluents are polyvinyl ethers of polyhydric compounds. These diluents lower viscosity while imparting only limited additional hardness to the composition. As previously stressed, the urethane-forming reaction is pushed to completion to consume substantially all of the hydroxy functionality which is present.
  • hydroxy functionality is here defined to constitute a hydroxy content of less than 0.1% of the weight of the composition.
  • hydroxy- functional vinyl ethers are substantially absent from the composition when vinyl ethers which are not polyurethanes are used as reactive diluents.
  • hydroxybutyl vinyl ether cannot be used as a diluent in this invention because this would increase the hydroxy content of the composition above the stated limit.
  • Even small amounts of hydroxy functionality in the composition to be cured inhibits the cure, so the fastest curing compositions are those which contain the least hydroxy functionality.
  • the preferred range is less than 30%, and is usually at least about 15% because lower relative humidities are difficult to provide.
  • coatings are especially adapted to provide coatings for optical glass fibers in which a more rapid cure and increased softness in comparison with those obtainable from typical vinyl ether-terminated polyurethanes is needed to enable or enhance such utility.
  • Primary coatings and single coating for optical glass fiber as well as ribbon coatings to assemble coated optical fiber in a ribbon provide preferred aspects of this invention.
  • Actinically-cured coatings of general utility are also contemplated herein, this invention being useful whenever greater softness is desired.
  • Other advantages and features of this invention will become apparent to one skilled in the art from the examples tabulated below in which all parts are by weight. TABLE I
  • a vinyl ether-terminated polyurethane oligomer prepared from 3 moles of triethylene glycol monovinyl ether, 3 moles of 4,4 '-diphenylmethane diisocyanate and 1 mole of trimethylol propane in 50% solution in triethylene glycol divinyl ether.
  • the films were provided by drawdowns on glass to provide a nominal thickness of 3 mils.
  • the wet films were exposed to one D lamp and one H lamp to provide a dosage of 0.75 J/sq cm.
  • the cured films were both light yellow in color, but the 161C film was clear while the 162 film was cloudy.
  • the H & D lamps are similar in that each is 12 inches long and emits about 300 Watt per inch of length.
  • the D lamp emission contains a greater proportion of longer waves which better penetrate the film and is preferred for the cure of thicker films. More particularly, the D lamp emits 25.6 Watt/inch at 200 to 300 nanometers, 63.8 Watt/inch at 300-400 nanometers and 26.9 Watt/inch at 400-470 nanometers.
  • the H lamp emits 44.8 Watt/inch at 200 to 300 nanometers, 31.0 Watt/inch at 300-400 nanometers and 17.7 Watt/inch at 400-470 nanometers.
  • E', tan delta and DMA curve are the results of dynamic mechanical analysis. This is a known method for measuring mechanical stiffness and energy dissipation by imposing an oscillatory strain on the material and determining the resulting strain. E* is the elastic modulus. Tan delta is a ratio of the viscous modulus to the elastic modulus, and the DMA curves are obtained by plotting the various factors. When the plot shows more than one maximum, this indicates phase separation. The unimodal plot reported here indicates the material under test is a single continuous phase.
  • the data demonstrates that blending polyisoprene with the vinyl ether polyurethane oligomer results in significant reduction of the modulus and tensile strength without affecting the glass transition temperature.
  • the percent elongation test requires many repetitions for accuracy and the results reported here are not regarded as determinative since only a single test result is reported. No significant changes in the dynamic mechanical properties are seen between 0 C and 100 C, and this retention of properties with change in temperature helps the composition to retain strength at elevated temperature.
  • a cured film of 4017-162A was refluxed in methyl ethyl ketone (MEK) for 8 hours followed by soaking in MEK for 72 hours. The film was then dried in a vacuum desiccator for 2 hours and then in air for 24 hours before reweighing. No weight change was observed after the described MEK extraction, and this is concluded to indicate the complete coreaction of the elastomer and the vinyl ether-terminated polyurethane during the cure.
  • the effect of polyisoprene on the thermal stability of the blend was studied by heat aging a film of the blended material and the control at 200 C. The results appear below:
  • # represents weight loss in percent following the noted exposure to temperature.
  • S.D. denotes standard deviation
  • thermoplastic rubber namely: a thermoplastic rubbery copolymer of poly(ethylene-butylene)-styrene, for the unsaturated elastomer used in the Table, inhibited the cure of the blend completely, and the stated radiat-ion dosage produced no detectable cure.
  • SUBSTITUTESHEET Additional tests were carried out to provide coatings having utility as primary coatings and single coatings for optical glass fiber. These tests were carried out by adding 5 and 10 parts of polyisoprene to a control which cured to provide a stronger and harder coating than desired. The addition of the polyisoprene did not noticeably vary the viscosity of the coatings, but it did require a somewhat larger amount of catalyst. The results are tabulated below.
  • the oligomer solution used above was made with apparatus consisting of a 500 ml 4-necked round bottom flask fitted with a stirrer, dry nitrogen sparge, 250 ml addition funnel, reflux condenser, thermometer, and a thermostatically controlled heating mantle. 20.91 parts of 4,4•-diphenylmethane diisocyanate were charged to the flask, and heated to 60 C. 22.74 parts of 1,4-butanediol divinyl ether were then added to the flask as a diluent and 7.45 parts of 4-hydroxybutyl vinyl ether were charged to the addition funnel and added over a 10 minute period. The reaction mixture was held at 60 C for an additional two hours.
  • the NCO content was then analyzed and the appropriate amount (to react with the unreacted isocyanate) of an adduct of caprolactone with diethylene glycol having a number average molecular weight of about 1,000 (Tone 220 supplied by Union Carbide Corporation, Chicago, IL can be used) was charged to the addition funnel. 0.06 part of dibutyltin dilaurate catalyst was then added to the flask and the addition funnel contents were added over a ten minute period while holding at 60 C. Thereafter the flask was heated to 70 C and held at that temperature until the NCO content is less than 0.1%. By calculation, the number average molecular weight was determined to be 2400.
  • TEGDVE is triethylene glycol divinyl ether.
  • the tensile strength and modulus are greatly reduced, the addition of 10% of polyisoprene not causing much more of a reduction than the addition of 5%, leading to the conclusion that a lesser modification can be obtained using a relatively small addition.
  • Either of the two additions makes the tested composition useful for either primary coating or single coating utility in the coating of optical glass fiber by applying a coating having a thickness of 3 mils to the freshly drawn fiber and then curing it with ultraviolet light as described previously.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Des mélanges liquides polymérisables par exposition au rayonnement actinique lorsqu'ils sont catalysés à l'aide d'une photoamorce cationique, comprennent du polyuréthane à terminaison d'éther vinylique ainsi qu'un élastomère polymère liquide non saturé d'éthylène. L'élastomère non saturé participe à la polymérisation cationique et adoucit les revêtements polymérisés. Dans ce but l'élastomère est présent dans une quantité comprise entre 0,1 % et 40 % sur la base du poids total du mélange de celui-ci avec le polyuréthane.
PCT/US1989/004240 1988-10-03 1989-09-28 Melanges par exposition de polyurethanes d'ether vinylique et d'elastomeres non satures polymerisables aux ultra-violets, et revetements les contenant Ceased WO1990003988A1 (fr)

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US251,788 1988-10-03

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US5181269A (en) * 1991-09-17 1993-01-19 At&T Bell Laboratories Optical fiber including acidic coating system
WO1998006783A1 (fr) * 1996-08-12 1998-02-19 Ucb, S.A. Compositions de resines durcissant sous l'effet de rayonnements
US5902837A (en) * 1995-08-09 1999-05-11 Sanyo Chemical Industries, Ltd. Photo-curing resin composition comprising a propenyl ether group-containing compound
WO2003060029A3 (fr) * 2002-01-15 2004-03-25 Basf Ag Revetements durcissables par radiation a adherence amelioree
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US8231970B2 (en) 2005-08-26 2012-07-31 Ppg Industries Ohio, Inc Coating compositions exhibiting corrosion resistance properties and related coated substrates
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Cited By (11)

* Cited by examiner, † Cited by third party
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US5181269A (en) * 1991-09-17 1993-01-19 At&T Bell Laboratories Optical fiber including acidic coating system
EP0533397A1 (fr) * 1991-09-17 1993-03-24 AT&T Corp. Fibre optique avec revêtement acide
US5902837A (en) * 1995-08-09 1999-05-11 Sanyo Chemical Industries, Ltd. Photo-curing resin composition comprising a propenyl ether group-containing compound
WO1998006783A1 (fr) * 1996-08-12 1998-02-19 Ucb, S.A. Compositions de resines durcissant sous l'effet de rayonnements
WO2003060029A3 (fr) * 2002-01-15 2004-03-25 Basf Ag Revetements durcissables par radiation a adherence amelioree
US8231970B2 (en) 2005-08-26 2012-07-31 Ppg Industries Ohio, Inc Coating compositions exhibiting corrosion resistance properties and related coated substrates
US8283042B2 (en) 2005-08-26 2012-10-09 Ppg Industries Ohio, Inc. Coating compositions exhibiting corrosion resistance properties, related coated substrates, and methods
WO2008027679A1 (fr) * 2006-08-31 2008-03-06 Ppg Industries Ohio, Inc. Primaire universel
US7816418B2 (en) 2006-08-31 2010-10-19 Ppg Industries Ohio, Inc. Universal primer
US10072179B2 (en) 2013-04-26 2018-09-11 Dsm Ip Assets B.V. Vinyl functionalized urethane resins for powder coating compositions
US10196539B2 (en) 2013-11-21 2019-02-05 Dsm Ip Assets B.V. Thermosetting powder coating compositions comprising methyl-substituted benzoyl peroxide

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Publication number Publication date
EP0437531A1 (fr) 1991-07-24
JPH04502777A (ja) 1992-05-21
EP0437531A4 (en) 1991-08-07

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